CN113617064A - Continuous defoaming device for high-viscosity fluid, application of continuous defoaming device and defoaming method for polyamide acid spinning solution - Google Patents
Continuous defoaming device for high-viscosity fluid, application of continuous defoaming device and defoaming method for polyamide acid spinning solution Download PDFInfo
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/0036—Flash degasification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/0073—Degasification of liquids by a method not covered by groups B01D19/0005 - B01D19/0042
- B01D19/0078—Degasification of liquids by a method not covered by groups B01D19/0005 - B01D19/0042 by vibration
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
Abstract
The invention belongs to the technical field of preparation of high-performance fibers, and discloses a continuous defoaming device for high-viscosity fluid, application and a polyamic acid spinning solution defoaming method. The defoaming inner member disperses the high-viscosity fluid injected into the defoaming device body to form a film-shaped liquid film, so that the defoaming time is shortened, the defoaming efficiency is improved, efficient continuous production is realized, and the stability of fiber performance is ensured. The device has the advantages of large flux, simple operation and large operation elasticity, and can be widely applied to various fiber preparation processes and other chemical deaeration units.
Description
Technical Field
The invention belongs to the technical field of preparation of high-performance fibers, and particularly relates to a continuous defoaming device for a high-viscosity fluid, application of the continuous defoaming device and a defoaming method for a polyamic acid spinning solution in a polyimide fiber preparation process.
Background
The high-performance fiber refers to a chemical fiber with special physical and chemical structure, performance and application, or special functions, and can be classified into corrosion-resistant fiber, high-temperature-resistant fiber, high-strength and high-modulus fiber, flame-resistant fiber and the like according to different performances. The polyimide fiber is one of important varieties of high-performance fibers and has the characteristics of high strength, high modulus and high temperature resistance. According to theory, the fiber modulus synthesized by pyromellitic dianhydride (PMDA) and p-phenylenediamine (PPD) can reach 410GPa, is second only to carbon fiber, and has high thermal stability. Wherein, the initial decomposition temperature of the wholly aromatic polyimide fiber is generally above 500 ℃, the maximum thermal weight loss rate is generally 550-650 ℃, and the thermal decomposition temperature of the biphenyl polyimide fiber is more as high as 600 ℃. The polyimide fiber has a large amount of imine rings, aromatic rings, other heterocyclic rings and the like in a molecular main chain, the molecular chain has higher rigidity, carbon, oxygen and double bonds in the imine rings are connected, and the conjugated effect generated by the aromatic heterocyclic rings is added, so that the main chain bond energy and intermolecular hydrogen bond acting force are higher, so that the fiber has the characteristics of high strength and modulus, radiation resistance, high temperature resistance, excellent thermal stability, dielectric property and the like, and is widely applied to the fields of nuclear energy industry, space station construction, medical equipment, military national defense, sea-crossing bridges, novel buildings, ocean development, sports equipment, protective equipment, environmental protection industry and the like.
The preparation method of the polyimide fiber comprises wet spinning, dry spinning or dry-wet spinning, and can adopt one-step spinning or two-step spinning. Since most of polyimide is insoluble or poorly soluble, it is difficult to spin directly using a polyimide solution, and thus, the preparation of polyimide fibers is mostly performed using a two-step process. Firstly, carrying out solution polycondensation on aromatic diamine and dianhydride monomers in an aprotic polar solvent to obtain a precursor, namely a polyamic acid (PAA) solution, spinning to obtain polyamic acid nascent fiber, and then carrying out thermal imidization or chemical imidization treatment on the polyamic acid nascent fiber to obtain the polyimide fiber. In the process of producing the polyimide fiber, the quality of the defoaming effect of the spinning solution directly influences the quality of the polyamic acid nascent fiber, and further influences the quality of a polyimide fiber end product. The quality of the defoaming effect also directly determines whether the later spinning, drying, drafting and other processes can be smoothly carried out. The polyamic acid spinning solution generates bubbles in the polymerization or conveying process, and the larger bubbles can cause the interruption of spinning through a spinneret orifice to generate broken filaments or broken filaments. Smaller bubbles will remain in the fiber through the spinneret holes, causing bubble filaments which are easily broken to form broken filaments and filaments during drawing. In addition, when the deaeration is insufficient, the draft multiple of the precursor cannot be increased, and the required fineness, strength and elongation at break cannot be achieved, and the strength of the polyamic acid nascent fiber and the polyimide fiber is finally affected. Therefore, the bubbles in the polyamic acid dope must be completely removed before spinning. However, the spinning solution has a large viscosity, and the bubbles are difficult to remove.
CN104492126A discloses a defoaming device, a defoaming method and application of a polyimide spinning solution, the method synthesizes polyimide solution by dianhydride and diamine monomers, then the obtained intermediate polyimide solution is heated to about 300 ℃, and the polyimide spinning solution is obtained by intramolecular dehydration and ring closure; or dehydrating and cyclizing the intermediate polyimide solution under the action of a dehydrating agent to obtain the polyimide spinning solution. And injecting the obtained polyimide spinning solution into a defoaming device, dispersing and defoaming the injected polyimide spinning solution by arranging a shunting module in the defoaming device, and starting a vacuum module to strengthen the defoaming effect. In addition, the device also comprises a bubble grinding module which is used for extruding and grinding bubbles in the polyimide spinning solution. The device also comprises an external circulation module which is used for refluxing the spinning solution to an injection port of the defoaming device and carrying out the defoaming treatment again when the polyimide spinning solution still has bubbles after the vacuum defoaming and bubble rolling defoaming treatment of the film.
At present, the conventional defoaming methods in the spinning production comprise standing normal-pressure defoaming, chemical defoaming and standing vacuum defoaming. The spinning solution of the polyamic acid mostly adopts an intermittent standing defoaming method: the polyamic acid spinning solution is defoamed by intermittent standing under normal pressure or intermittent standing under vacuum to reach the spinning condition. The intermittent static defoaming method is to transfer the polyamic acid solution obtained by polymerization reaction into one or more defoaming kettles for vacuum static or normal pressure static, so as to defoam the spinning solution naturally. In this method, the viscosity of the polyamic acid solution obtained by the polymerization reaction is large, the standing and defoaming time is difficult to control, and the standing time is too long, so that the risk of degradation of the polyamic acid solution itself is increased. In addition, a plurality of deaeration kettles need to be put into the equipment, the requirements on the tightness and the material of the deaeration kettles are high, the occupied area is large, the production cost is high, continuous production cannot be realized in the polymerization reaction and spinning stages, and the stability of the fiber performance cannot be guaranteed.
Disclosure of Invention
From the prior published technology, most attention is paid to the preparation of polyimide fibers and a preparation method thereof, and less attention is paid to a defoaming device and a defoaming method of a spinning solution in the preparation process of the polyimide fibers.
The invention aims to solve the problems of long defoaming time and low defoaming efficiency caused by high viscosity of polyamide acid spinning solution in the preparation process of polyimide fibers in the prior art, and provides a continuous defoaming device for high-viscosity fluid and a defoaming method of polyamide acid spinning solution. The defoaming device has the advantages of large flux, simple operation, high defoaming efficiency and large operation flexibility, and can be widely applied to various fiber preparation processes and other chemical defoaming units.
In order to achieve the above object, a first aspect of the present invention provides a continuous defoaming device for high viscosity fluid, including a defoaming device body, a fluid inlet disposed at the top of the defoaming device body, and a fluid outlet disposed at the bottom of the defoaming device body, wherein a plurality of stages of defoaming internal members are installed in the defoaming device body, and a collecting-redistributor is installed between two adjacent stages of defoaming internal members.
The upper part of the defoaming inner member is a conical defoaming inner member tower body, a plurality of defoaming inner member supporting pieces are mounted at the lower part of the defoaming inner member tower body, the defoaming inner member supporting pieces are arranged in an annular structure along the circumferential direction of the defoaming inner member tower body at vertical intervals, and the top point of the defoaming inner member tower body is closed.
Preferably, a distributor is installed at the bottom of the injection port, and the bottom of the distributor is connected to the top of the defoaming inner member at the highest stage close to the fluid injection port.
Preferably, the collection-redistribution device is a hollow truncated cone-shaped collection-redistribution device tower body with a funnel structure.
Preferably, a ring grid plate is arranged in the circumferential direction of the lower part of the collection-redistribution tower body, and the height of the ring grid plate relative to the edge of the bottom of the collection-redistribution tower body is 0.1-50 mm, preferably 0.5-30 mm, and more preferably 1-10 mm.
Preferably, a plurality of collecting-redistributor supporting pieces are vertically arranged at intervals along the circumferential direction at the bottom of the ring grid plate, and the height of each collecting-redistributor supporting piece relative to the bottom of the collecting-redistributor tower body is 50-100 mm, preferably 5-80 mm, and more preferably 10-50 mm.
Preferably, the distance between the maximum outer peripheral outline of the defoaming inner member and the inner side wall of the defoaming device body is 1-300mm, and preferably 2-100 mm.
Preferably, the cone angle of the tower body of the defoaming inner member is 15-165 degrees, preferably 60-150 degrees, and more preferably 120-150 degrees;
the diameter of each component support in the defoaming is 0.1-15mm, the length of each component support is 50-1500 mm, and/or the arrangement distance of each component support is 1-80 mm.
Preferably, a plurality of ultrasonic generators are uniformly distributed at the bottom of the defoaming device body.
Preferably, the top of the defoaming device body is provided with a vacuumizing module.
The invention provides an application of the defoaming device in defoaming of high-viscosity fluid.
Preferably, the high viscosity fluid comprises one or more of polyimide fibers, carbon fibers, aramid fibers, and high viscosity fluids produced during the production of high performance fibers; preferably, the viscosity of the high-viscosity fluid is 0.1 pas to 2000 pas.
In a third aspect of the present invention, there is provided a defoaming method of a polyamic acid spinning solution, comprising the steps of:
s1) in an aprotic polar solvent, dianhydride and diamine monomers are polymerized to obtain polyamic acid spinning solution;
s2), leading the polyamic acid spinning solution into a defoaming device body through a fluid injection port, dispersing and flowing through a defoaming inner member with a defoaming inner member support and the collecting-redistributor, forming a film-shaped spinning solution film on the defoaming inner member, and defoaming to obtain the spinnable polyamic acid spinning solution.
Preferably, the film-like spinning solution has a thickness of 0.1 to 25mm, preferably 0.5 to 15mm, and more preferably 1 to 10 mm.
Preferably, the retention time of the polyamic acid spinning solution in the defoaming device body is 5-90 min.
According to the technical scheme, the continuous defoaming device for the high-viscosity fluid and the defoaming method for the polyamic acid spinning solution provided by the invention have the advantages that the defoaming inner member with the defoaming inner member supporting piece is arranged in the defoaming device body, and the defoaming inner member disperses the high-viscosity fluid injected into the defoaming device body to form a film-shaped liquid film; the arrangement of the support of the defoaming inner component can prevent the shrinkage of a liquid film, has good film forming property and strengthens the redistribution of fluid; the high-viscosity fluid is in unconstrained free falling film movement under the action of gravity on a defoaming inner member, the flux is large, the amplification effect is good, the surface updating frequency is high, the bubble removing path can be shortened, the bubbles of the high-viscosity fluid can be easily raised, the defoaming effect is enhanced in the vacuumizing module, the defoaming time is shortened, the defoaming efficiency is improved, and therefore continuous production can be realized in the polymerization reaction before defoaming and the spinning stage after defoaming, and the stability of the performance of nascent fibers is ensured; by the design of the collecting-redistributor and the coupling of adjustable interlayer spacing and wire spacing, the uniform and controllable residence time of the high-viscosity fluid in the defoaming device can be realized; the defoaming device is simple to operate, low in cost, large in flux, large in defoaming area and wide in applicability.
Drawings
Fig. 1 is a schematic structural diagram of a defoaming apparatus according to an embodiment of the present invention;
FIG. 2 is a schematic structural view of a defoaming inner member according to an embodiment of the present invention;
FIG. 3 is a schematic view of a collection-redistribution structure without collection-redistribution supports according to an embodiment of the present invention;
FIG. 4 is a schematic structural view of a collection-redistribution with collection-redistribution support according to an embodiment of the present invention;
FIG. 5 is an enlarged partial view of a collection-redistribution with collection-redistribution support according to one embodiment of the present invention;
FIG. 6 is a schematic view showing the constitution of a defoaming apparatus for a polyimide dope used in a comparative example.
Description of the reference numerals
1 fluid injection port
2 defoaming inner member
21 debubbling inner member tower body 22 debubbling inner member support
3 defoaming device body
4 fluid discharge port
5 distributor
6 Collection-redistributor
61 collector-redistributor support 62 collector-redistributor tower
63 Ring grid plate
7 vacuumizing module 8 ultrasonic generator
9 injection port 10 shunting module
External circulation control valve of 11 bubble grinding module 12
13 discharge port 14 external circulation module
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In the present invention, the use of the terms of orientation such as "upper (high), lower (low), left, right" generally means upper (high), lower (low), left, right; "inner and outer" refer to the inner and outer relative to the profile of the components themselves. The present invention will be described in detail below with reference to the accompanying drawings in conjunction with embodiments.
The invention provides a continuous defoaming device for high-viscosity fluid, which has the advantages of improved defoaming efficiency, simple structure and easy operation, and referring to fig. 1, the continuous defoaming device comprises a defoaming device body 3, a fluid injection port 1 arranged at the top of the defoaming device body 3 and a fluid discharge port 4 arranged at the bottom of the defoaming device body 3, a multistage defoaming inner member 2 is arranged in the defoaming device body 3, a collecting-redistributor 6 is arranged between two adjacent stages of defoaming inner members 2, and the defoaming inner members 2 are used for dispersing and defoaming the high-viscosity fluid injected into the defoaming device body 3.
Specifically, the defoaming device may be a continuous defoaming device. The fluid injection port 1 is located at the top of the defoaming apparatus body 3, and the fluid injection port 1 is preferably located at the center of the top of the defoaming apparatus body 3, and is connected to, for example, an injection pump for receiving a high-viscosity fluid.
Further, the defoaming device also comprises an injection pump and an injection amount adjusting device. The injection pump is preferably a gear pump, connected to the fluid injection port 1, for pumping a highly viscous fluid; the injection amount adjusting device adjusts the pumping amount of the high-viscosity fluid according to the difference of the viscosity of the high-viscosity fluid, and avoids the influence on the production efficiency due to too little high-viscosity fluid pumped or the influence on the defoaming effect due to too much high-viscosity fluid pumped.
A distributor 5 is installed at the bottom of the injection port 1, and the bottom of the distributor 5 is connected to the top of the defoaming inner member 2 at the highest stage close to the fluid injection port 1.
Specifically, the defoaming inner member 2 is provided at an upper portion in the defoaming apparatus main body 3, and the upper portion of the defoaming inner member 2 is a defoaming inner member tower 21 having a conical structure.
According to a preferred embodiment of the present invention, referring to fig. 2, the bottom surface of the tower 21 of the defoaming inner member is smaller than the cross-sectional area of the defoaming apparatus main body 3, and the bottom surface of the defoaming inner member 2 is preferably spaced from the inner side wall of the defoaming apparatus main body 3 by 1-300mm, preferably 2-100 mm; the cone angle of the tower body 21 of the defoaming inner member is 15-165 degrees, preferably 60-150 degrees, and more preferably 120-150 degrees.
According to a preferred embodiment of the invention, the lower part of the defoaming inner member tower body 21 is connected with a plurality of defoaming inner member supporting pieces 22, the plurality of defoaming inner member supporting pieces 22 are vertically arranged in a ring-shaped structure along the circumferential direction of the defoaming inner member tower body 21 at intervals, and the diameter of each defoaming inner member supporting piece 22 is 0.1-15mm, preferably 1-8 mm; the length is 50-1500 mm, preferably 200-750 mm; the arrangement pitch is 1-80mm, preferably 5-30 mm.
In the preferred embodiment of the present invention, the top end of the defoaming inner member 2 is close to the distributor 5 located at the center of the top of the defoaming apparatus main body 3, and the bottom surface of the defoaming inner member support 22 is close to the collecting-redistributor 6. When the high viscosity fluid is received by the circular distributor 5 connected with the fluid injection port 1 and enters the defoaming device body 3, the high viscosity fluid flows downwards along the outer wall of the side surface of the defoaming inner member 2 under the action of gravity and forms a film-shaped liquid film under the shunting action of the tower body 21 of the defoaming inner member, and the film-shaped liquid film continues to flow downwards along the support 22 of the defoaming inner member under the action of gravity and moves in an unconstrained free falling film when flowing to the bottom surface of the conical inner member.
In the present invention, the provision of the de-foaming internals supporter 22 prevents the shrinkage of highly viscous fluids such as spinning liquid films, provides good film formation and enhances fluid redistribution. Part of bubbles of the film-shaped liquid film are quickly broken in a vacuum environment; the defoaming inner member 2 has a large film formation area and a high liquid film renewal rate, and bubbles in the liquid film easily rise to the surface of the liquid film and are rapidly broken. The liquid film after passing through the defoaming inner member support 22 falls into the collecting-redistributor 6 and then enters the lower-level defoaming inner member 2 to continue to form and defoam, so that the retention time of the high-viscosity fluid in the defoaming device body 3 is uniform and controllable, and the defoaming efficiency is improved.
Specifically, a collecting-redistributor 6 is arranged between two adjacent stages of defoaming inner members 2 in the defoaming device body 3, the collecting-redistributor 6 includes a collecting-redistributor tower 62 with a hollow truncated cone-shaped funnel structure, and a ring grid plate 63 arranged along the circumferential direction of the lower part of the collecting-redistributor tower 62, the height of the ring grid plate 63 relative to the bottom edge of the collecting-redistributor tower 62 is 0.1-50 mm, preferably 0.5-30 mm, more preferably 1-10 mm, as shown in fig. 3 and 4, and/or a ring of collecting-redistributor supporting members 61 is arranged at the bottom of the collecting-redistributor 6, the ring grid plate 63 and the collecting-redistributor supporting members 61 can form a gap at the bottom of the collecting-redistributor 6, and the gap is used for passing through high-viscosity fluid in the collecting-redistributor 6, as shown in fig. 4.
The collecting-redistributor tower body 62 of the collecting-redistributor 6 is used for collecting the high-viscosity fluid which slides on the upper stage defoaming inner member 2, and the high-viscosity fluid collected by the collecting-redistributor tower body 62 passes through the gap between the ring grid plate 63 and the collecting-redistributor support member 61 and then is redistributed to the lower stage defoaming inner member 2 to continue to form the film and defoam.
Furthermore, a plurality of ultrasonic generators 8 are uniformly distributed at the bottom of the defoaming device body 3, the liquid film of the high-viscosity fluid falls into the bottom of the defoaming device body 3 and is accumulated, and the residual bubbles are removed by the ultrasonic generators 8 and then are discharged from the fluid outlet 4.
According to a preferred embodiment of the present invention, the vacuum module 7 is disposed on the top of the defoaming apparatus body 3, and the vacuum module 7 can reduce the gas phase partial pressure of the defoaming apparatus body 3, so that the desorbed bubble gas is exhausted from the vacuum module 7, thereby improving the defoaming efficiency.
Compared with the traditional intermittent normal-pressure static defoaming device or vacuum static defoaming device or chemical defoaming device, the vertical multistage falling-film continuous defoaming device can perform quick and efficient continuous defoaming under the auxiliary vacuum and/or ultrasonic conditions of the vacuumizing module 7 and the ultrasonic generator 8, improve the production efficiency, realize efficient continuous production, and has the advantages of good film forming property, high surface updating frequency and high defoaming efficiency.
Specifically, the vacuum unit is a water ring vacuum pump or an oil pump, preferably an oil pump.
According to the continuous defoaming device for the high-viscosity fluid provided by the embodiment of the invention, the defoaming inner member 2 is arranged in the defoaming device body 3, and the defoaming inner member 2 disperses the high-viscosity fluid injected into the defoaming device body 3 to form a film-shaped liquid film, so that bubbles in stock solution of the high-viscosity fluid are easy to rise to the surface of the solution, and the defoaming effect is enhanced in a vacuum environment; the defoaming inner member support 22 of the defoaming inner member 2 can ensure the film-forming property of a liquid film, shorten the defoaming time and improve the defoaming efficiency, and the defoaming device of the invention can be used for defoaming the polyamic acid spinning solution, so that the polymerization reaction before defoaming and the spinning stage after defoaming can realize continuous production, and the stability of fiber performance is ensured; the defoaming device is simple to operate, high in flux and low in cost.
The invention preferably provides a defoaming method of the polyamic acid spinning solution, which comprises the following steps:
s1) in an aprotic polar solvent, dianhydride and diamine monomers are polymerized at low temperature to obtain polyamic acid spinning solution;
s2), the polyamic acid spinning solution is introduced into the defoaming apparatus main body 3, and dispersed and flowed through the defoaming inner member 2 provided with the defoaming inner member support 22 to form a film-like spinning solution film on the defoaming inner member 2, and defoaming is completed to obtain a spinnable polyamic acid spinning solution.
Wherein the film-shaped spinning solution has a thickness of 0.1 to 25mm, preferably 0.5 to 15mm, and more preferably 1 to 10mm, and in a preferred embodiment of the present invention, the residence time of the polyamic acid spinning solution in the defoaming device body 3 is 5 to 90 min.
Specifically, the viscosity of the obtained polyamic acid spinning solution is 5 to 300 Pa.s, preferably 100-200 Pa.s.
Injecting the polyimide spinning solution into the defoaming device body 3 through the fluid injection port 1 and the distributor 5; vacuumizing, and setting the vacuum degree to be 10-100 kPa.
The polyamic acid spinning solution is dispersed and flowed through the defoaming member 2 to form a film-like spinning solution film, and vacuum defoaming is completed.
A spinnable polyamic acid dope was obtained.
Specifically, the method for obtaining the polyamic acid spinning dope is as follows:
drying dianhydride and diamine monomers in aprotic polar solvent such as Dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), etc., and polymerizing at low temperature to synthesize polyamide acid (PAA) solution;
specifically, the injection rate of the polyamic acid spinning solution is adjusted to 50-500cm by the injection amount adjusting device3S, preferably 100-300cm3S; the preferable injection rate is matched with the polyamic acid spinning solution with the preferable viscosity, so that the influence on the production efficiency caused by pumping too little polyamic acid spinning solution or the influence on the defoaming effect caused by pumping too much polyamic acid spinning solution is avoided.
Further, in the above step, the degree of vacuum is preferably set to 50kPa, the polyamic acid spinning solution flows downward along the outer wall of the side surface of the defoaming inner member 2 under the action of gravity by the drainage of the conical defoaming inner member 2 to form a film-like spinning solution film, the portion of the bubble in the film-like spinning solution film in the preferred vacuum environment is rapidly broken, the bubble in the liquid film and not coming out is continuously flowed downward along the defoaming inner member support 22 to move in an unconstrained free falling film manner, the surface of the liquid film is continuously updated, the bubble is easily raised to the liquid surface and rapidly broken, and the defoaming inner member support 22 is arranged to prevent the shrinkage of the spinning solution film, ensure good film-forming property and enhance the redistribution of the fluid.
According to the defoaming method of the polyamic acid fiber spinning solution provided by the embodiment of the invention, the film-shaped spinning solution film with high surface renewal frequency is formed, so that bubbles in the polyamic acid fiber spinning solution are easy to rise to the surface of the solution, and the defoaming effect is enhanced in a vacuum environment; the defoaming inner member supporting piece 22 and the collecting-redistributor 6 are coupled with adjustable interlamellar spacing and filament spacing, so that the retention time of the spinning dope in the defoaming device body 3 is uniform and controllable, good film-forming property of the spinning dope is ensured, the quality of the polyamic acid fiber spinning dope is ensured, the defoaming time is shortened, and the defoaming efficiency is improved.
The embodiment of the invention provides an application method of the polyamic acid spinning solution obtained by the device and the method, the obtained polyamic acid spinning solution is filtered by a filter material and is sprayed out through a spinneret orifice to form filaments, and wet spinning or dry-jet wet spinning is carried out to obtain the polyamic acid nascent fiber.
Further, the polyamic acid nascent fiber obtained in the above is washed with water, dried, oiled, dried and densified, and subjected to thermal imidization treatment to obtain the polyimide fiber.
The defoaming method is also suitable for defoaming carbon fibers, aramid fibers and high-performance fibers; and/or can be used for defoaming materials with the viscosity of 0.1 Pa.s-2000 Pa.s.
According to a preferred embodiment of the present invention, the present invention provides a continuous defoaming device for high viscosity fluid, comprising a defoaming device body 3, a fluid inlet 1 is arranged on the top of the defoaming device body 3, a fluid outlet 4 is arranged on the bottom of the defoaming device body 3, a plurality of stages of defoaming inner members 2 are arranged in the defoaming device body 3, a collecting-redistributor 6 is arranged between two adjacent stages of the defoaming inner members 2, furthermore, a distributor 5 connected to the fluid inlet 1 is arranged on the top of the highest stage of the defoaming inner member 2, the defoaming inner member 2 is provided with a defoaming inner member tower body 21 and a defoaming inner member support 22, the maximum outer peripheral outline of the defoaming inner member 2 is 1-300mm away from the inner side wall of the defoaming device body 3, the conical angle of the defoaming inner member tower body 21 is 15-165 degrees, the diameter of each defoaming inner member supporting piece 22 is 0.1-15mm, the length is 50-1500 mm, and the arrangement distance is 1-80 mm; the collecting-redistributor 6 is provided with a collecting-redistributor tower body 61, a collecting-redistributor support member 62 and a ring grid plate 63, the height of the ring grid plate 63 relative to the bottom edge of the collecting-redistributor tower body 62 is 20mm, the height of the collecting-redistributor support member 61 relative to the bottom of the collecting-redistributor tower body 62 is 80mm, furthermore, a vacuumizing module 7 and a plurality of ultrasonic emitters 8 are installed at the top of the defoaming device body 1, continuous multistage defoaming of high-viscosity fluid is realized through the continuous defoaming device of the high-viscosity fluid, and the device is adopted in the following embodiments.
The apparatus for continuously defoaming a high-viscosity fluid and the method for defoaming a polyamic acid dope according to the embodiments of the present invention will be described in further detail with reference to specific examples, and all of the apparatuses used in the following embodiments are the above-described apparatus for continuously defoaming a high-viscosity fluid, unless otherwise specified.
Example 1
In an aprotic polar solvent, dianhydride and diamine are polymerized under a low-temperature condition to obtain polyamic acid spinning solution with the viscosity of 20Pa & s;
injecting the polyamic acid spinning solution into the defoaming device body 3 through a fluid injection port 1 and a distributor 5 of a continuous vacuum defoaming kettle; starting vacuum in the defoaming device, wherein the set vacuum degree is 100 kPa;
the polyamic acid spinning solution is dispersed and flowed through the defoaming inner member 2 to form a film-shaped spinning solution film, and vacuum defoaming is completed to obtain spinnable polyamic acid spinning solution; the conical angle of the defoaming inner member 2 is 150 degrees, the distance between the bottom edge and the inner side wall of the defoaming device body 3 is 20mm, the diameter of each defoaming inner member support 22 is 1mm, the length is 250mm, and the wire spacing is 5 mm.
Filtering the obtained polyamic acid spinning solution by using a filter material, metering by using a metering pump, and performing wet spinning by using a spinning assembly to obtain polyamic acid nascent fiber;
introducing the obtained polyamic acid nascent fiber into thermal imidization equipment, and carrying out treatment in stages, wherein the thermal imidization temperature in the first stage is 120 ℃, the thermal imidization temperature in the second stage is 180 ℃, the thermal imidization temperature in the third stage is 250 ℃, the thermal imidization temperature in the fourth stage is 350 ℃, the thermal imidization temperature in the fifth stage is 450 ℃, nitrogen protection is adopted in the imidization process, and the treatment time is constant according to the process requirements;
and performing hot drafting on the obtained polyimide fibers, and then performing tube winding on the polyimide fibers at a yarn winding machine.
Three samples were taken for testing, and the test results are shown in table 1 below.
TABLE 1
Example 2
In an aprotic polar solvent, dianhydride and diamine are polymerized under a low-temperature condition to obtain polyamic acid spinning solution with the viscosity of 50Pa & s;
injecting the polyamic acid spinning solution into the defoaming device body 3 through a fluid injection port 1 and a distributor 5 of a continuous vacuum defoaming kettle; starting vacuum in the defoaming device, wherein the set vacuum degree is 100 kPa;
the polyamic acid spinning solution is dispersed and flowed through the defoaming inner member 2 to form a film-shaped spinning solution film, and vacuum defoaming is completed to obtain spinnable polyamic acid spinning solution; the conical angle of the defoaming inner member 2 is 150 degrees, the distance between the bottom edge and the side wall of the defoaming device body 3 is 20mm, the diameter of each defoaming inner member support 22 is 1mm, the length is 250mm, and the wire spacing is 5 mm.
Filtering the obtained polyamic acid spinning solution by using a filter material, metering by using a metering pump, and performing wet spinning by using a spinning assembly to obtain polyamic acid nascent fiber;
introducing the obtained polyamic acid nascent fiber into thermal imidization equipment, and carrying out treatment in stages, wherein the thermal imidization temperature in the first stage is 120 ℃, the thermal imidization temperature in the second stage is 180 ℃, the thermal imidization temperature in the third stage is 250 ℃, the thermal imidization temperature in the fourth stage is 350 ℃, the thermal imidization temperature in the fifth stage is 450 ℃, nitrogen protection is adopted in the imidization process, and the treatment time is constant according to the process requirements;
and performing hot drafting on the obtained polyimide fibers, and then performing tube winding on the polyimide fibers at a yarn winding machine.
Three samples were taken for testing, and the test results are shown in table 2 below.
TABLE 2
Example 3
In an aprotic polar solvent, dianhydride and diamine are polymerized under a low-temperature condition to obtain polyamic acid spinning solution with the viscosity of 100Pa & s;
injecting the polyamic acid spinning solution into the defoaming device body 3 through a fluid injection port 1 and a distributor 5 of a continuous vacuum defoaming kettle; starting vacuum in the defoaming device, wherein the set vacuum degree is 100 kPa;
the polyamic acid spinning solution is dispersed and flowed through the defoaming inner member 2 to form a film-shaped spinning solution film, and vacuum defoaming is completed to obtain spinnable polyamic acid spinning solution; the conical angle of the defoaming inner member 2 is 150 degrees, the distance between the bottom edge and the side wall of the defoaming device body 3 is 150mm, the diameter of each defoaming inner member support 22 is 1mm, the length is 250mm, and the wire spacing is 5 mm.
Filtering the obtained polyamic acid spinning solution by using a filter material, metering by using a metering pump, and performing wet spinning by using a spinning assembly to obtain polyamic acid nascent fiber;
introducing the obtained polyamic acid nascent fiber into thermal imidization equipment, and carrying out treatment in stages, wherein the thermal imidization temperature in the first stage is 120 ℃, the thermal imidization temperature in the second stage is 180 ℃, the thermal imidization temperature in the third stage is 250 ℃, the thermal imidization temperature in the fourth stage is 350 ℃, the thermal imidization temperature in the fifth stage is 450 ℃, nitrogen protection is adopted in the imidization process, and the treatment time is constant according to the process requirements;
and performing hot drafting on the obtained polyimide fibers, and then performing tube winding on the polyimide fibers at a yarn winding machine.
Three samples were taken for testing, and the test results are shown in table 3 below.
TABLE 3
Example 4
In an aprotic polar solvent, dianhydride and diamine are polymerized under a low-temperature condition to obtain polyamic acid spinning solution with the viscosity of 200Pa & s;
injecting the polyamic acid spinning solution into the defoaming device body 3 through a fluid injection port 1 and a distributor 5 of a continuous vacuum defoaming kettle; starting vacuum in the defoaming device, wherein the set vacuum degree is 100 kPa;
the polyamic acid spinning solution is dispersed and flowed through the defoaming inner member 2 to form a film-shaped spinning solution film, and vacuum defoaming is completed to obtain spinnable polyamic acid spinning solution; the conical angle of the defoaming inner member 2 is 150 degrees, the distance between the bottom edge and the side wall of the defoaming device body 3 is 20mm, the diameter of each defoaming inner member support 22 is 1mm, the length is 250mm, and the wire spacing is 5 mm.
Filtering the obtained polyamic acid spinning solution by using a filter material, metering by using a metering pump, and performing wet spinning by using a spinning assembly to obtain polyamic acid nascent fiber;
introducing the obtained polyamic acid nascent fiber into thermal imidization equipment, and carrying out treatment in stages, wherein the thermal imidization temperature in the first stage is 120 ℃, the thermal imidization temperature in the second stage is 180 ℃, the thermal imidization temperature in the third stage is 250 ℃, the thermal imidization temperature in the fourth stage is 350 ℃, the thermal imidization temperature in the fifth stage is 450 ℃, nitrogen protection is adopted in the imidization process, and the treatment time is constant according to the process requirements;
and performing hot drafting on the obtained polyimide fibers, and then performing tube winding on the polyimide fibers at a yarn winding machine.
Three samples were taken for testing, and the test results are shown in table 4 below.
TABLE 4
Example 5
In an aprotic polar solvent, dianhydride and diamine are polymerized under a low-temperature condition to obtain polyamic acid spinning solution with the viscosity of 100Pa & s;
injecting the polyamic acid spinning solution into the defoaming device body 3 through a fluid injection port 1 and a distributor 5 of a continuous vacuum defoaming kettle; starting vacuum in the defoaming device, wherein the vacuum degree is set to be 50 kPa;
the polyamic acid spinning solution is dispersed and flowed through the defoaming inner member 2 to form a film-shaped spinning solution film, and vacuum defoaming is completed to obtain spinnable polyamic acid spinning solution; the conical angle of the defoaming inner member 2 is 150 degrees, the distance between the bottom edge and the side wall of the defoaming device is 20mm, the diameter of each defoaming inner member support 22 is 1mm, the length is 250mm, and the wire spacing is 5 mm.
Filtering the obtained polyamic acid spinning solution by using a filter material, metering by using a metering pump, and performing wet spinning by using a spinning assembly to obtain polyamic acid nascent fiber;
introducing the obtained polyamic acid nascent fiber into thermal imidization equipment, and carrying out treatment in stages, wherein the thermal imidization temperature in the first stage is 120 ℃, the thermal imidization temperature in the second stage is 180 ℃, the thermal imidization temperature in the third stage is 250 ℃, the thermal imidization temperature in the fourth stage is 350 ℃, the thermal imidization temperature in the fifth stage is 450 ℃, nitrogen protection is adopted in the imidization process, and the treatment time is constant according to the process requirements;
and performing hot drafting on the obtained polyimide fibers, and then performing tube winding on the polyimide fibers at a yarn winding machine.
Three samples were taken for testing, and the test results are shown in table 5 below.
TABLE 5
Example 6
In an aprotic polar solvent, dianhydride and diamine are polymerized under a low-temperature condition to obtain polyamic acid spinning solution with the viscosity of 100Pa & s;
injecting the polyamic acid spinning solution into the defoaming device body 3 through a fluid injection port 1 and a distributor 5 of a continuous vacuum defoaming kettle; starting vacuum in the defoaming device, wherein the vacuum degree is set to be 50 kPa;
the polyamic acid spinning solution is dispersed and flowed through the defoaming inner member 2 to form a film-shaped spinning solution film, and vacuum defoaming is completed to obtain spinnable polyamic acid spinning solution; the conical angle of the defoaming inner member 2 is 120 degrees, the distance between the bottom edge and the side wall of the defoaming device is 40mm, the diameter of each defoaming inner member support 22 is 2mm, the length is 350mm, and the wire spacing is 5 mm.
Filtering the obtained polyamic acid spinning solution by using a filter material, metering by using a metering pump, and performing wet spinning by using a spinning assembly to obtain polyamic acid nascent fiber;
introducing the obtained polyamic acid nascent fiber into thermal imidization equipment, and carrying out treatment in stages, wherein the thermal imidization temperature in the first stage is 120 ℃, the thermal imidization temperature in the second stage is 180 ℃, the thermal imidization temperature in the third stage is 250 ℃, the thermal imidization temperature in the fourth stage is 350 ℃, the thermal imidization temperature in the fifth stage is 450 ℃, nitrogen protection is adopted in the imidization process, and the treatment time is constant according to the process requirements;
and performing hot drafting on the obtained polyimide fibers, and then performing tube winding on the polyimide fibers at a yarn winding machine.
Three samples were taken for testing, and the test results are shown in table 6 below.
TABLE 6
Example 7
In an aprotic polar solvent, dianhydride and diamine are polymerized under a low-temperature condition to obtain polyamic acid spinning solution with the viscosity of 200Pa & s;
injecting the polyamic acid spinning solution into the defoaming device body 3 through a fluid injection port 1 and a distributor 5 of a continuous vacuum defoaming kettle; starting vacuum in the defoaming device, wherein the vacuum degree is set to be 20 kPa;
the polyamic acid spinning solution is dispersed and flowed through the defoaming inner member 2 to form a film-shaped spinning solution film, and vacuum defoaming is completed to obtain spinnable polyamic acid spinning solution; the conical angle of the defoaming inner member 2 is 150 degrees, the distance between the bottom edge and the side wall of the defoaming device body 3 is 30mm, the diameter of each defoaming inner member support 22 is 3mm, the length is 550mm, and the wire spacing is 10 mm.
Filtering the obtained polyamic acid spinning solution by using a filter material, metering by using a metering pump, and performing wet spinning by using a spinning assembly to obtain polyamic acid nascent fiber;
introducing the obtained polyamic acid nascent fiber into thermal imidization equipment, and carrying out treatment in stages, wherein the thermal imidization temperature in the first stage is 120 ℃, the thermal imidization temperature in the second stage is 180 ℃, the thermal imidization temperature in the third stage is 250 ℃, the thermal imidization temperature in the fourth stage is 350 ℃, the thermal imidization temperature in the fifth stage is 450 ℃, nitrogen protection is adopted in the imidization process, and the treatment time is constant according to the process requirements;
and performing hot drafting on the obtained polyimide fibers, and then performing tube winding on the polyimide fibers at a yarn winding machine.
Three samples were taken for testing, and the test results are shown in table 7 below.
TABLE 7
Example 8
In an aprotic polar solvent, dianhydride and diamine are polymerized under a low-temperature condition to obtain polyamic acid spinning solution with the viscosity of 200Pa & s;
injecting the polyamic acid spinning solution into the defoaming device body 3 through a fluid injection port 1 and a distributor 5 of a continuous vacuum defoaming kettle; starting vacuum in the defoaming device, wherein the vacuum degree is set to be 20 kPa;
the polyamic acid spinning solution is dispersed and flowed through the defoaming inner member 2 to form a film-shaped spinning solution film, and vacuum defoaming is completed to obtain spinnable polyamic acid spinning solution; the conical angle of the defoaming inner member 2 is 90 degrees, the distance between the bottom edge and the side wall of the defoaming device body 3 is 30mm, the diameter of each defoaming inner member support 22 is 3mm, the length is 550mm, and the wire spacing is 10 mm.
Filtering the obtained polyamic acid spinning solution by using a filter material, metering by using a metering pump, and performing wet spinning by using a spinning assembly to obtain polyamic acid nascent fiber;
introducing the obtained polyamic acid nascent fiber into thermal imidization equipment, and carrying out treatment in stages, wherein the thermal imidization temperature in the first stage is 120 ℃, the thermal imidization temperature in the second stage is 180 ℃, the thermal imidization temperature in the third stage is 250 ℃, the thermal imidization temperature in the fourth stage is 350 ℃, the thermal imidization temperature in the fifth stage is 450 ℃, nitrogen protection is adopted in the imidization process, and the treatment time is constant according to the process requirements;
and performing hot drafting on the obtained polyimide fibers, and then performing tube winding on the polyimide fibers at a yarn winding machine.
Three samples were taken for testing, and the test results are shown in table 8 below.
TABLE 8
Comparative example 1
Obtaining polyimide spinning solution with the viscosity of 20Pa s;
fig. 6 shows a defoaming device which is frequently used, and includes a vacuum port, an injection port 9, a flow dividing module 10, a bubble grinding module 11, an external circulation control valve 12, a discharge port 13, and an external circulation module 14.
Using the defoaming device of fig. 6, injecting the polyimide spinning solution into the defoaming device through an injection port 9 of a continuous vacuum defoaming kettle; starting a vacuum module in the vacuum defoaming device, and setting the vacuum degree to be 100 kPa;
the polyimide spinning solution is dispersed and flowed through the flow dividing module 10 to form a film-shaped spinning solution layer, and vacuum defoaming is completed to obtain a spinnable polyimide spinning solution;
and transferring the fiber to a spinning assembly for wet spinning to obtain the polyimide fiber. Coagulating in a second coagulating bath, washing with water, drying, oiling, feeding into a tension adjusting device at a spinning speed of 10m/min, introducing the fiber into an imidization processor, and treating by stages, wherein the thermal imidization temperature in the first stage is 250 ℃, the thermal imidization temperature in the second stage is 300 ℃, the thermal imidization temperature in the third stage is 350 ℃, the thermal imidization temperature in the fourth stage is 400 ℃, and the treatment time is constant according to the process requirements;
and performing hot drafting on the obtained polyimide fibers, and then performing tube winding on the polyimide fibers at a yarn winding machine.
Three samples were taken for testing, and the test results are shown in table 9 below.
TABLE 9
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, numerous simple modifications can be made to the technical solution of the invention, including combinations of the specific features in any suitable way, and the invention will not be further described in relation to the various possible combinations in order to avoid unnecessary repetition. Such simple modifications and combinations should be considered within the scope of the present disclosure as well.
Claims (14)
1. The utility model provides a continuous deaeration device for high viscous fluid, includes deaeration device body (3), set up in fluid filling opening (1) at deaeration device body (3) top and set up in fluid discharge port (4) of deaeration device body (3) bottom, deaeration device body (3) internally mounted has multistage defoaming internals (2), adjacent two-stage it collects-redistributor (6) to install between defoaming internals (2).
2. The defoaming apparatus according to claim 1, wherein the upper part of the defoaming inner member (2) is a defoaming inner member tower body (21) with a conical structure, a plurality of defoaming inner member supports (22) are mounted at the lower part of the defoaming inner member tower body (21), the plurality of defoaming inner member supports (22) are vertically arranged at intervals along the circumferential direction of the defoaming inner member tower body (21) in an annular structure, and the top of the defoaming inner member tower body (21) is closed.
3. Defoaming apparatus according to claim 1, characterized in that a distributor (5) is mounted at the bottom of the injection port (1), and the bottom of the distributor (5) is connected to the top of the defoaming inner member (2) near the highest stage of the fluid injection port (1).
4. Debubbling apparatus according to claim 1, characterized in that the collection-redistributor (6) is a collection-redistributor tower (62) of hollow truncated cone, funnel structure.
5. The debubbling apparatus according to claim 4, wherein a ring grid plate (63) is arranged at the lower part of the collecting-redistributor tower body (62) along the circumferential direction, and the height of the ring grid plate (63) relative to the bottom edge of the collecting-redistributor tower body (62) is 0.1-50 mm, preferably 0.5-30 mm, and more preferably 1-10 mm.
6. Debubbling apparatus according to claim 5, wherein the bottom of the ring grid (63) is provided with a plurality of collecting-redistributor supports (61) vertically spaced along the circumferential direction, and the height of the collecting-redistributor supports (61) relative to the bottom of the collecting-redistributor tower (62) is 50-100 mm, preferably 5-80 mm, and more preferably 10-50 mm.
7. A defoaming device according to claim 1, characterized in that the maximum peripheral outline of the defoaming inner member (2) is 1-300mm, preferably 2-100mm, from the inner side wall of the defoaming device body (3).
8. A defoaming apparatus according to claim 2, characterized in that the cone angle of the defoaming inner tower (21) is between 15 ° and 165 °, preferably between 60 ° and 150 °, more preferably between 120 ° and 150 °;
the diameter of each defoaming inner member support piece (22) is 0.1-15mm, the length of each defoaming inner member support piece is 50-1500 mm, and/or the arrangement distance of each defoaming inner member support piece is 1-80 mm.
9. The defoaming device according to claim 1, wherein a plurality of ultrasonic generators (8) are uniformly distributed at the bottom of the defoaming device body (3); and/or
And a vacuumizing module (7) is arranged at the top of the defoaming device body (3).
10. Use of a degassing device according to any one of claims 1-9 for degassing highly viscous fluids.
11. The use of claim 10, wherein the high viscosity fluid comprises one or more of polyimide fibers, carbon fibers, aramid fibers, and high viscosity fluids produced during the production of high performance fibers; preferably, the viscosity of the high-viscosity fluid is 0.1 pas to 2000 pas.
12. A defoaming method of a polyamic acid dope, which is performed in the defoaming apparatus as set forth in any one of claims 1 to 9, comprising the steps of:
s1) in an aprotic polar solvent, polymerizing dianhydride and a diamine monomer to obtain a polyamic acid spinning solution;
s2), leading the polyamic acid spinning solution into a defoaming device body (3) through a fluid injection port (1), and forming a film-shaped spinning solution film on the defoaming inner member (2) through the defoaming inner member (2) with the defoaming inner member support (22) and the collecting-redistributor (6) in a dispersing and flowing manner to complete defoaming so as to obtain the spinnable polyamic acid spinning solution.
13. A defoaming method according to claim 12, wherein the film-like spinning solution has a film thickness of 0.1 to 25mm, preferably 0.5 to 15mm, and more preferably 1 to 10 mm.
14. The defoaming method according to claim 12, wherein a residence time of the polyamic acid spinning solution in the defoaming apparatus body (3) is 5 to 90 min.
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