CN114606579A - Ammonification method and device for polyacrylonitrile spinning solution - Google Patents
Ammonification method and device for polyacrylonitrile spinning solution Download PDFInfo
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- CN114606579A CN114606579A CN202011412180.6A CN202011412180A CN114606579A CN 114606579 A CN114606579 A CN 114606579A CN 202011412180 A CN202011412180 A CN 202011412180A CN 114606579 A CN114606579 A CN 114606579A
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- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 177
- 238000009987 spinning Methods 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 67
- 238000004176 ammonification Methods 0.000 title claims description 19
- 239000000243 solution Substances 0.000 claims abstract description 117
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 106
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 51
- 239000011259 mixed solution Substances 0.000 claims abstract description 42
- 239000002002 slurry Substances 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 21
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 8
- 238000003860 storage Methods 0.000 claims description 31
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000005484 gravity Effects 0.000 claims description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims description 2
- 239000000835 fiber Substances 0.000 abstract description 10
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000005587 bubbling Effects 0.000 abstract description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 18
- 239000004917 carbon fiber Substances 0.000 description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- 238000003763 carbonization Methods 0.000 description 13
- 230000003647 oxidation Effects 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 13
- 238000002166 wet spinning Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 239000002243 precursor Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 239000012456 homogeneous solution Substances 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 230000007847 structural defect Effects 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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Classifications
-
- 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
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- 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
- D01D1/00—Treatment of filament-forming or like material
- D01D1/10—Filtering or de-aerating the spinning solution or melt
- D01D1/103—De-aerating
-
- 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
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
-
- 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
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses an ammoniation method and a device of polyacrylonitrile spinning solution, wherein the ammoniation method comprises the following steps: (1) quantitatively mixing an ammoniation reagent and a solvent to obtain a mixed solution with controllable ammonia content; (2) dispersing polyacrylonitrile powder into the mixed solution with controllable ammonia content prepared in the step (1), and uniformly stirring to obtain polyacrylonitrile slurry; (3) heating and dissolving the polyacrylonitrile slurry liquid prepared in the step (2) to obtain a transparent and uniform polyacrylonitrile solution; (4) and (4) performing defoaming treatment on the polyacrylonitrile fiber obtained in the step (3) to obtain the polyacrylonitrile spinning solution. Compared with an ammonia bubbling method and a solution polymerization method which are commonly adopted in the prior art, the ammoniation method for mixing and heating the ammoniated solution and the polyacrylonitrile powder can flexibly adjust the polyacrylonitrile content in the spinning solution, meet the requirement of the spinning process on the pressure before spinning, and reduce the pressure of the spinning caused by the viscosity increase caused by ammoniation; ammoniation treatment is carried out by adopting ammonia water, so that ammoniation degree can be controlled while sufficient ammoniation reaction is ensured, and the method is suitable for popularization and use.
Description
Technical Field
The invention belongs to the field of polyacrylonitrile spinning, and particularly relates to an ammoniation method and an ammoniation device for polyacrylonitrile spinning solution.
Background
Nowadays, carbon fiber materials have been widely used in military fields such as aerospace, national defense and military, and civil fields such as sports goods and medical equipment. The Polyacrylonitrile (PAN) based carbon fiber has a wide application prospect in the fields by virtue of the characteristics of high strength, high modulus, low density, high temperature resistance, friction resistance, good electrical conductivity, good thermal conductivity, special chemical corrosion resistance and the like.
At present, the preparation process of PAN protofilament can be divided into a one-step method and a two-step method according to the preparation process, wherein the one-step method adopts homogeneous solution polymerization to prepare spinning solution for spinning, and the two-step method adopts heterogeneous precipitation polymerization to prepare PAN polymer powder, and then adopts a proper solvent to dissolve the powder to prepare the spinning solution. Wherein the spinning flexibility of the two-step process is greater.
Since the PAN filaments have a partial structure which is retained to some extent during the subsequent pre-oxidation and carbonization processes, the structure of the filaments largely determines the properties of the final carbon fiber. In order to improve the performance of the carbon fiber, the stable and continuous preparation of high-quality PAN precursor is the key. In the production process of the PAN precursor, the coagulation forming process of the spinning solution in the coagulation bath has great influence on the structure and the performance of the PAN precursor. The spinning solution coagulation forming is completed by carrying out double diffusion on the solvent and the precipitating agent and precipitating PAN molecules. Because the solidification double diffusion rate in the wet spinning process is high, the PAN fiber is easy to form structural defects such as macropores, a skin-core structure, an irregular fiber structure and the like, and the structural defects are transmitted to the PAN fiber and the carbon fiber, so that the performance and the application field of the carbon fiber are seriously weakened. The process of solidification double diffusion has great relation with the hydrophilic property of the spinning solution, and the improvement of the hydrophilic property of the spinning solution can slow down the solidification forming speed of the spinning solution and the structural defects of macropores, skin-core structures, irregular fiber structures and the like. Therefore, improving the hydrophilicity of the dope is one of the key technologies for producing high-quality PAN precursor.
At present, there are two main methods for improving the hydrophilicity of PAN dope in patent reports: firstly, a comonomer containing hydrophilic groups and acrylonitrile are subjected to homogeneous solution polymerization reaction to prepare a high-hydrophilicity PAN spinning solution, and Chinese patents CN201310514441.9, CN201210239630.5 and the like are related and reported; secondly, the PAN spinning solution is prepared by homogeneous solution polymerization and then ammoniated by ammonia gas, and Chinese patents CN201310132151.8, CN201110180192.5 and the like are reported. The above methods can improve the hydrophilicity of the spinning solution, but have some disadvantages, mainly as follows: firstly, the solid content of the spinning solution prepared by homogeneous solution polymerization is poor in adjustability, and the viscosity of the spinning solution after ammoniation is not easy to adjust and control; secondly, the ammoniation degree of the spinning solution is difficult to control, the difference between batches is large, and the quality stability of the product is influenced; thirdly, ammonia gas is not easy to be uniformly mixed and reacted with the high-viscosity spinning solution; fourthly, ammoniation can generate a barrier effect on solution polymerization reaction and simultaneously generate adverse effects on mass transfer and heat transfer in the polymerization process.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a polyacrylonitrile spinning solution ammonification technology adopting two-step spinning, which mixes prepared ammonia-containing mixed solution with polyacrylonitrile powder, completes the ammonification process in the process of forming slurry, and prepares the spinning solution by heating, thereby improving the hydrophilicity of the PAN spinning solution and realizing the stable production of compact PAN precursor with a circular section.
In order to solve the technical problems, the invention adopts the technical scheme that:
the invention provides an ammoniation method of polyacrylonitrile spinning solution, which comprises the following steps:
(1) quantitatively mixing an ammoniation reagent and a solvent to obtain a mixed solution with controllable ammonia content;
(2) dispersing polyacrylonitrile powder into the mixed solution with controllable ammonia content prepared in the step (1), and uniformly stirring to obtain polyacrylonitrile slurry;
(3) heating and dissolving the polyacrylonitrile slurry liquid prepared in the step (2) to obtain a transparent and uniform polyacrylonitrile solution;
(4) and (4) defoaming the polyacrylonitrile solution prepared in the step (3) to prepare the polyacrylonitrile spinning solution.
In the scheme, the ammoniation method for the two-step spinning provided by the invention can flexibly select the solvent type and the preparation concentration of the spinning solution according to the requirements of the spinning process, and avoids the defects of unstable ammoniation process and poor process adjustability in the one-step solution polymerization spinning. Specifically, the polymerized polyacrylonitrile powder is dispersed in the mixed liquid with controllable ammonia content to form slurry, so that on one hand, the stable content of the ammoniation reagent can be ensured, the condition that the ammonia content is lost in the one-step polymerization process is avoided, and on the other hand, the mixed liquid with controllable ammonia content is adopted instead of directly adding ammonia water, so that a viscous system formed by the ammonia water and the polyacrylonitrile powder can be prevented from influencing the mixing effect of the ammonia water and the polyacrylonitrile powder, and a better ammoniation effect is obtained.
According to the ammonification method, the ammonification reagent in the step (1) is selected from ammonia water with the mass concentration of 25-28%.
According to the ammoniation method, the mass concentration of ammonia in the mixed liquid with the controllable ammonia content in the step (1) is 0.01-1%, and preferably 0.02-0.4%.
In the scheme, the ammoniation process provided by the invention is stable, so that a solution with a mass concentration lower than that of ammonia in an ammoniation reagent used in one-step spinning can be generally adopted, and a good ammoniation effect can be realized. In addition, the finally formed polyacrylonitrile spinning solution can not generate the phenomena of gel, dark color and the like in a short time, and the service life of the polyacrylonitrile spinning solution is prolonged.
According to the ammonification method, the polyacrylonitrile slurry in the step (2) contains 18-22% by mass of polyacrylonitrile.
According to the ammonification method, the heating temperature in the step (3) is 90-130 ℃, and the heating time is 0.3-5 min; preferably, the heating temperature is 100-120 ℃, and the heating time is 1-3 min; more preferably, the heating process is carried out in a tubular heat exchanger, and the heating time is the residence time of the polyacrylonitrile slurry liquid in the tubular heat exchanger.
According to the ammonification method, the temperature of the defoaming treatment in the step (4) is 65-80 ℃, and the preferable temperature is 70-75 ℃.
According to the ammonification method, the pH value of the polyacrylonitrile spinning solution subjected to the defoaming treatment in the step (4) is 7-10, and preferably 8-9.
According to the ammoniation method, the solvent in the step (1) is one or more selected from N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and sodium thiocyanate aqueous solution; n, N-dimethylacetamide is preferred.
Specifically, the ammoniation method of the polyacrylonitrile spinning solution provided by the invention comprises the following steps:
(1) quantitatively mixing 25-28% ammonia water and a solvent to obtain a mixed solution with controllable ammonia content, wherein the mass concentration of the ammonia in the mixed solution is 0.01-1%, and the storage temperature of the mixed solution is-15-5 ℃;
(2) dispersing polyacrylonitrile powder into the mixed solution with controllable ammonia content prepared in the step (1), and uniformly stirring to obtain polyacrylonitrile slurry, wherein the mass fraction of polyacrylonitrile in the slurry is 18-22%;
(3) heating the polyacrylonitrile slurry liquid prepared in the step (2) in a tubular heat exchanger at the temperature of 90-130 ℃ for 0.3-5 min, and dissolving to prepare a transparent and uniform polyacrylonitrile solution;
(4) and (4) defoaming the polyacrylonitrile solution prepared in the step (3) at the temperature of 65-80 ℃ to prepare a polyacrylonitrile spinning solution, wherein the pH of the polyacrylonitrile spinning solution is 7-10.
The invention also provides a device for realizing the ammonification method of the polyacrylonitrile spinning solution, which comprises a plurality of material storage tanks which are arranged layer by layer from top to bottom along the gravity direction, wherein an ammonia water storage tank and a solvent storage tank are arranged on the top layer and are connected with a mixed liquid storage tank arranged on the middle layer through a weightlessness weighing system, the mixed liquid storage tank and a polyacrylonitrile powder material storage tank arranged on the middle layer are connected with a slurry kettle arranged on the bottom layer through the weightlessness weighing system, and the slurry kettle is sequentially connected with a tubular heat exchanger and a defoaming kettle which are arranged on the bottom layer.
The device further comprises the following steps of; the mixed liquid storage tank is internally provided with a stirring device and a refrigerating device, and the storage temperature of the mixed liquid with controllable ammonia content in the mixed liquid storage tank is-15-5 ℃, preferably-10-5 ℃.
In the scheme, the weightless weighing system controls the discharge screw machine or the electric vibrator according to the reduction rate of the weight of the materials in the weighing hopper so as to achieve the purpose of quantitative feeding. The operation flow of the device is as follows by combining an ammoniation method: accurately feeding the solvent from the volume storage tank and the ammonia water from the ammonia water storage tank into a mixed liquid storage tank through a weightlessness weighing system, fully mixing the solvent and the ammonia water under the stirring condition, and storing at the temperature of-15-5 ℃; then accurately feeding the ammonia-containing solution from the mixed solution storage tank and PAN powder from the polyacrylonitrile storage tank into a slurry kettle through a weightlessness weighing system, and fully stirring to prepare uniformly dispersed slurry liquid; then, the slurry liquid is stably fed into a tube type heat exchanger through a gear metering pump 1, so that the slurry is fully dissolved at the temperature of 90-130 ℃ to obtain a polyacrylonitrile solution; and finally, inputting the polyacrylonitrile solution into a defoaming kettle for defoaming through a gear metering pump 2, thereby realizing the preparation of the uniform ammoniated PAN spinning solution.
After adopting the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts a two-step method to prepare the PAN spinning solution, wherein the PAN content is flexible and adjustable, the requirement of the spinning process on the pressure before spinning is met, and particularly the pressure of the spinning caused by viscosity increase due to ammoniation is reduced;
2. the invention adopts the prepared ammonia-containing mixed liquid to disperse the polyacrylonitrile powder, realizes the ammonification of PAN, overcomes the defects of difficult ammonia metering, difficult mixing and the like when an ammonia bubbling method is used in the prior art, and further reduces the defoaming difficulty;
3. according to the invention, ammonia water is adopted to carry out ammoniation treatment on the PAN spinning solution, so that the contact of ammonia and acidic groups in PAN can be effectively ensured, the ammoniation reaction is facilitated, the ammoniation quality is ensured, and the ammoniation degree is controllable;
4. the ammoniation spinning solution provided by the invention has certain storage performance due to the adoption of relatively stable ammoniation treatment.
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention, are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention without limiting the invention to the right. It is obvious that the drawings in the following description are only some embodiments, and that for a person skilled in the art, other drawings can be derived from them without inventive effort. In the drawings:
FIG. 1 is a device for implementing an ammonification method of polyacrylonitrile spinning solution provided by the invention;
FIG. 2 is a SEM image of a cross-section of a PAN precursor obtained in example 1 of the present invention;
FIG. 3 is a SEM image of a cross-section of a PAN precursor obtained in example 2 of the present invention;
FIG. 4 is a SEM image of a cross-section of a PAN filament obtained in example 3 of the present invention;
FIG. 5 is a SEM image of a cross-section of a PAN precursor obtained in example 4 of the present invention;
FIG. 6 is a SEM image of a cross-section of a PAN filament obtained in comparative example 1 of the present invention.
It should be noted that the drawings and the description are not intended to limit the scope of the inventive concept in any way, but to illustrate it by a person skilled in the art with reference to specific embodiments.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and the following embodiments are used for illustrating the present invention and are not intended to limit the scope of the present invention.
In the description of the present invention, it should be noted that the terms "upper", "lower", "front", "rear", "left", "right", "vertical", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; may be directly connected or indirectly connected through an intermediate. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Example 1
In this example, polyacrylonitrile spinning solution was aminated by the following method:
(1) quantitatively mixing 25% ammonia water and a solvent DMAc to obtain a mixed solution with controllable ammonia content, wherein the mass concentration of the ammonia in the mixed solution is 0.02%, and the storage temperature of the mixed solution is-10 ℃;
(2) dispersing polyacrylonitrile powder into the mixed solution with controllable ammonia content prepared in the step (1), and uniformly stirring to obtain polyacrylonitrile slurry, wherein the mass fraction of polyacrylonitrile in the slurry is 20%;
(3) heating the polyacrylonitrile slurry liquid prepared in the step (2) in a tubular heat exchanger by low-pressure steam at the temperature of 130 ℃ for 0.3min, and dissolving to prepare a transparent and uniform polyacrylonitrile solution;
(4) and (4) defoaming the polyacrylonitrile solution prepared in the step (3) at 75 ℃ to prepare a polyacrylonitrile spinning solution, wherein the pH of the polyacrylonitrile spinning solution is 7.
The uniformly aminated PAN spinning solution prepared in the example was made into 25K protofilaments with a fineness of 1.15dtex by a wet spinning technique. The filament cross-section is shown in figure 2. And performing pre-oxidation and carbonization treatment to obtain the high-performance carbon fiber with the tensile strength of 5.4GPa and the tensile modulus of 240 GPa.
Example 2
In this example, polyacrylonitrile spinning solution was aminated by the following method:
(1) quantitatively mixing ammonia water with the mass concentration of 28% and a solvent DMAc to obtain a mixed solution with the controllable ammonia content, wherein the mass concentration of the ammonia in the mixed solution is 0.03%, and the storage temperature of the mixed solution is-10 ℃;
(2) dispersing polyacrylonitrile powder into the mixed solution with controllable ammonia content prepared in the step (1), and uniformly stirring to obtain polyacrylonitrile slurry, wherein the mass fraction of polyacrylonitrile in the slurry is 20%;
(3) heating the polyacrylonitrile slurry liquid prepared in the step (2) in a tubular heat exchanger by low-pressure steam at the temperature of 130 ℃ for 5min, and dissolving to prepare a transparent and uniform polyacrylonitrile solution;
(4) and (4) defoaming the polyacrylonitrile solution prepared in the step (3) at 75 ℃ to prepare polyacrylonitrile spinning solution, wherein the pH of the polyacrylonitrile spinning solution is 8.
The uniformly aminated PAN spinning solution prepared in the example was made into 25K protofilaments with a fineness of 1.15dtex by a wet spinning technique. The filament cross-section is shown in figure 3. The high-performance carbon fiber with the tensile strength of 5.5GPa and the tensile modulus of 240GPa is prepared through pre-oxidation and carbonization treatment.
Example 3
In this example, polyacrylonitrile spinning solution was aminated by the following method:
(1) quantitatively mixing ammonia water with the mass concentration of 26% and a solvent DMAc to obtain a mixed solution with controllable ammonia content, wherein the mass concentration of the ammonia in the mixed solution is 0.05%, and the storage temperature of the mixed solution is-10 ℃;
(2) dispersing polyacrylonitrile powder into the mixed solution with controllable ammonia content prepared in the step (1), and uniformly stirring to obtain polyacrylonitrile slurry, wherein the mass fraction of polyacrylonitrile in the slurry is 20%;
(3) heating the polyacrylonitrile slurry liquid prepared in the step (2) in a tubular heat exchanger by low-pressure steam at the temperature of 130 ℃ for 0.3min, and dissolving to prepare a transparent and uniform polyacrylonitrile solution;
(4) and (4) defoaming the polyacrylonitrile solution prepared in the step (3) at 75 ℃ to prepare polyacrylonitrile spinning solution, wherein the pH of the polyacrylonitrile spinning solution is 8.
The uniformly aminated PAN spinning solution prepared in the example was made into 25K protofilaments with a fineness of 1.15dtex by a wet spinning technique. The filament cross-section is shown in figure 4. The high-performance carbon fiber with the tensile strength of 5.4GPa and the tensile modulus of 240GPa is prepared through pre-oxidation and carbonization treatment.
Example 4
In this example, polyacrylonitrile spinning solution was aminated by the following method:
(1) quantitatively mixing ammonia water with the mass concentration of 27% and a solvent DMAc to obtain a mixed solution with the controllable ammonia content, wherein the mass concentration of the ammonia in the mixed solution is 0.075%, and the storage temperature of the mixed solution is-10 ℃;
(2) dispersing polyacrylonitrile powder into the mixed solution with controllable ammonia content prepared in the step (1), and uniformly stirring to obtain polyacrylonitrile slurry, wherein the mass fraction of polyacrylonitrile in the slurry is 20%;
(3) heating the polyacrylonitrile slurry liquid prepared in the step (2) in a tubular heat exchanger by low-pressure steam at the temperature of 130 ℃ for 0.3min, and dissolving to prepare a transparent and uniform polyacrylonitrile solution;
(4) and (4) defoaming the polyacrylonitrile solution prepared in the step (3) at 75 ℃ to prepare polyacrylonitrile spinning solution, wherein the pH of the polyacrylonitrile spinning solution is 8.5.
The uniformly aminated PAN spinning solution prepared in the embodiment is prepared into 25K protofilament with the fineness of 1.15dtex by adopting a wet spinning technology. The filament cross-section is shown in figure 5. The high-performance carbon fiber with the tensile strength of 5.4GPa and the tensile modulus of 240GPa is prepared through pre-oxidation and carbonization treatment.
Example 5
In this example, polyacrylonitrile spinning solution was aminated by the following method:
(1) quantitatively mixing 25% ammonia water and a solvent DMAc to obtain a mixed solution with controllable ammonia content, wherein the mass concentration of the ammonia in the mixed solution is 1%, and the storage temperature of the mixed solution is 5 ℃;
(2) dispersing polyacrylonitrile powder into the mixed solution with controllable ammonia content prepared in the step (1), and uniformly stirring to obtain polyacrylonitrile slurry, wherein the mass fraction of polyacrylonitrile in the slurry is 18%;
(3) heating the polyacrylonitrile slurry liquid prepared in the step (2) in a tubular heat exchanger by low-pressure steam at 90 ℃ for 2.2min, and dissolving to prepare a transparent and uniform polyacrylonitrile solution;
(4) and (4) defoaming the polyacrylonitrile solution prepared in the step (3) at the temperature of 65 ℃ to prepare a polyacrylonitrile spinning solution, wherein the pH of the polyacrylonitrile spinning solution is 10.
The uniformly aminated PAN spinning solution prepared in the example was made into 25K protofilaments with a fineness of 1.15dtex by a wet spinning technique. And carrying out pre-oxidation and carbonization treatment to obtain the high-performance carbon fiber with the tensile strength of 5.0GPa and the tensile modulus of 240 GPa.
Example 6
In this example, the mass concentration of ammonia in the mixed solution in the step (1) was adjusted to 0.5% based on example 5, and the pH of the polyacrylonitrile spinning solution finally obtained was 9.5. In another embodiment of this example, the uniformly aminated PAN dope obtained in this example was converted into 25K filaments having a fineness of 1.15dtex by wet spinning technique as in example 5. And performing pre-oxidation and carbonization treatment to obtain the high-performance carbon fiber with the tensile strength of 5.1GPa and the tensile modulus of 240 GPa.
Example 7
In this example, polyacrylonitrile spinning solution was aminated by the following method:
(1) quantitatively mixing ammonia water with the mass concentration of 26% and a solvent DMAc to obtain a mixed solution with controllable ammonia content, wherein the mass concentration of the ammonia in the mixed solution is 0.4%, and the storage temperature of the mixed solution is-15 ℃;
(2) dispersing polyacrylonitrile powder into the mixed solution with controllable ammonia content prepared in the step (1), and uniformly stirring to obtain polyacrylonitrile slurry, wherein the mass fraction of polyacrylonitrile in the slurry is 22%;
(3) heating the polyacrylonitrile slurry liquid prepared in the step (2) in a tubular heat exchanger by low-pressure steam at 110 ℃ for 1.5min, and dissolving to prepare a transparent and uniform polyacrylonitrile solution;
(4) and (4) defoaming the polyacrylonitrile solution prepared in the step (3) at the temperature of 80 ℃ to prepare a polyacrylonitrile spinning solution, wherein the pH of the polyacrylonitrile spinning solution is 9.5.
The uniformly aminated PAN spinning solution prepared in the example was made into 25K protofilaments with a fineness of 1.15dtex by a wet spinning technique. And performing pre-oxidation and carbonization treatment to obtain the high-performance carbon fiber with the tensile strength of 5.3GPa and the tensile modulus of 240 GPa.
Example 8
In this example, the mass concentration of ammonia in the mixed solution in the step (1) was adjusted to 0.2% based on example 7, and the final polyacrylonitrile spinning solution was adjusted to pH 9. In another embodiment of this example, the uniformly aminated PAN dope obtained in this example was converted into 25K filaments having a fineness of 1.15dtex by wet spinning technique as in example 7. And performing pre-oxidation and carbonization treatment to obtain the high-performance carbon fiber with the tensile strength of 5.4GPa and the tensile modulus of 240 GPa.
Example 9
In this example, the mass concentration of ammonia in the mixed solution in the step (1) was adjusted to 0.1% based on example 7, and the final polyacrylonitrile spinning solution was adjusted to pH 9. In another embodiment of this example, the uniformly aminated PAN dope obtained in this example was converted into 25K filaments having a fineness of 1.15dtex by wet spinning technique as in example 7. And carrying out pre-oxidation and carbonization treatment to obtain the high-performance carbon fiber with the tensile strength of 5.5GPa and the tensile modulus of 240 GPa.
Comparative example 1
In the comparative example, on the basis of example 1, polyacrylonitrile powder in the same amount as that in example 1 was dissolved in a solvent DMAc to prepare a spinning solution with PAN mass fraction of 20%, and the spinning solution was not aminated, and the pH of the spinning solution was measured to be 4.0.
The uniformly aminated PAN spinning solution prepared in the comparative example is prepared into 25K protofilament with the titer of 1.15dtex by adopting a wet spinning technology. The filament cross-section is shown in figure 6. The high-performance carbon fiber with the tensile strength of 4.7GPa and the tensile modulus of 230GPa is prepared through pre-oxidation and carbonization treatment.
Comparative example 2
In the comparative example, on the basis of example 1, polyacrylonitrile powder in the same amount as that in example 1 was dissolved in a solvent DMAc to prepare a spinning solution with 20 mass percent PAN, and then ammonia gas having the same ammonia content as that in the mixed solution in example 1 was introduced to obtain an ammoniated spinning solution with a measured pH of 7.0.
The uniformly aminated PAN spinning solution prepared in the comparative example is prepared into 25K protofilament with the titer of 1.15dtex by adopting a wet spinning technology. The high-performance carbon fiber with the tensile strength of 4.8GPa and the tensile modulus of 230GPa is prepared through pre-oxidation and carbonization treatment.
Comparative example 3
The comparative example adopts a two-step method in the prior art, polyacrylonitrile solution is obtained through the reaction of acrylonitrile, comonomer and initiator, polyacrylonitrile spinning solution (wherein the polyacrylonitrile content is the same as that in the example 5 of the invention) is prepared after demonomerization and deaeration, an ammonia reagent with the ammonia content the same as that in the mixed solution in the example 5 is added, and the pH value of the obtained ammoniated spinning solution is 7.0 through determination. The high-performance carbon fiber with the tensile strength of 4.9GPa and the tensile modulus of 240GPa is prepared through pre-oxidation and carbonization treatment.
Experimental example 1
The polyacrylonitrile fibers prepared in the embodiments 1 to 9 and the comparative examples 1 to 3 are subjected to hydrophilic performance and spinning solution stability tests, and the hydrophilic performance is represented by calculating the saturated moisture absorption rate (%), wherein the specific test method comprises the following steps: the sample was dried at 105 ℃ for 16 hours and the weight m1 was determined; then placing the dried sample in a constant temperature and humidity machine with the temperature of 20 ℃ and the relative humidity of 65% for 24 hours, measuring the weight m2 of the sample, and then calculating the saturated moisture absorption rate (%) (m2-m1)/m1 x 100%, wherein the stability of the spinning solution is characterized by the change of the characteristics of the spinning solution after being placed for a period of time at normal temperature and pressure, and the results are shown in the following table:
as can be seen from the above table, the polyacrylonitrile fibers prepared in embodiments 1 to 9 provided by the present invention have the advantages of good hydrophilic property and capability of being stored for a certain period of time at normal temperature and pressure. Comparative example 1 no ammoniation treatment was performed on polyacrylonitrile, and although the obtained fiber was round in cross section, the hydrophilic property was poor and the application range was small. While the comparative example 2 is polyacrylonitrile fiber prepared by ammoniation with ammonia gas, which is commonly used in the prior art, the comparative document 3 is prepared by a two-step method, and the spinning solution formed by polymerization is ammoniated by a solution with a certain ammonia content, both of which have the defect of unstable ammoniation process, although the prepared polyacrylonitrile fiber is improved in hydrophilicity compared with the comparative example 1 which is not ammoniated, the method is not as the embodiment of the present application. In addition, the polyacrylonitrile prepared by the comparative examples 2 and 3 has an unsatisfactory ammoniation effect, so that the spinning solution is continuously darkened and increased in viscosity after being placed for about 6 hours, and is further darkened and increased in viscosity in the subsequent 18-48 hours.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. An ammoniation method of polyacrylonitrile spinning solution is characterized by comprising the following steps:
(1) quantitatively mixing an ammoniation reagent and a solvent to obtain a mixed solution with controllable ammonia content;
(2) dispersing polyacrylonitrile powder into the mixed solution with controllable ammonia content prepared in the step (1), and uniformly stirring to obtain polyacrylonitrile slurry;
(3) heating and dissolving the polyacrylonitrile slurry liquid prepared in the step (2) to obtain a transparent and uniform polyacrylonitrile solution;
(4) and (4) defoaming the polyacrylonitrile solution prepared in the step (3) to prepare the polyacrylonitrile spinning solution.
2. The method for ammoniating polyacrylonitrile spinning solution according to claim 1, wherein the ammoniating reagent in the step (1) is ammonia water with mass concentration of 25-28%.
3. The ammonification method of polyacrylonitrile spinning solution according to claim 1, wherein the mass concentration of ammonia in the mixed solution with controllable ammonia content in the step (1) is 0.01-1%, preferably 0.02-0.4%.
4. The ammonification method of polyacrylonitrile spinning solution according to claim 1, wherein the polyacrylonitrile slurry liquid in the step (2) contains 18-22% by mass of polyacrylonitrile.
5. The ammonification method of polyacrylonitrile spinning solution according to claim 1, wherein the heating temperature in the step (3) is 90-130 ℃, and the heating time is 0.3-5 min; preferably, the heating temperature is 100-120 ℃, and the heating time is 1-3 min; more preferably, the heating process is carried out in a tubular heat exchanger, and the heating time is the residence time of the polyacrylonitrile slurry liquid in the tubular heat exchanger.
6. The ammonification method of polyacrylonitrile spinning solution according to claim 1, wherein the temperature of the defoaming treatment in the step (4) is 65-80 ℃, preferably 70-75 ℃.
7. The ammonification method of polyacrylonitrile spinning solution according to claim 6, wherein the pH of the polyacrylonitrile spinning solution after the defoaming treatment in the step (4) is 7-10, preferably 8-9.
8. The method for ammonifying polyacrylonitrile spinning solution according to claim 1, wherein the solvent in the step (1) is one or more selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and sodium thiocyanate aqueous solution; n, N-dimethylacetamide is preferred.
9. The device for realizing the ammonification method of the polyacrylonitrile spinning solution according to any one of claims 1 to 8, which is characterized by comprising a plurality of material storage tanks which are arranged in layers from top to bottom according to the gravity direction, wherein an ammonia water storage tank and a solvent storage tank are arranged on the top layer and are connected with a mixed liquid storage tank arranged on the middle layer through a weightlessness weighing system, the mixed liquid storage tank and a polyacrylonitrile powder material storage tank arranged on the middle layer are connected with a slurry kettle arranged on the bottom layer through the weightlessness weighing system, and the slurry kettle is sequentially connected with a tubular heat exchanger and a defoaming kettle which are arranged on the bottom layer.
10. The device according to claim 9, wherein the mixed liquid storage tank is provided with a stirring device and a refrigerating device, and the storage temperature of the mixed liquid with controllable ammonia content in the mixed liquid storage tank is-15-5 ℃, preferably-10-5 ℃.
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