CN103387670B - A kind of imidization method of vacuum imidization stove and polyamic acid fiber - Google Patents
A kind of imidization method of vacuum imidization stove and polyamic acid fiber Download PDFInfo
- Publication number
- CN103387670B CN103387670B CN201310319398.0A CN201310319398A CN103387670B CN 103387670 B CN103387670 B CN 103387670B CN 201310319398 A CN201310319398 A CN 201310319398A CN 103387670 B CN103387670 B CN 103387670B
- Authority
- CN
- China
- Prior art keywords
- vacuum
- imidization
- heater
- rack
- heating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention provides a kind of vacuum imidization stove, comprise burner hearth, external thermal insulation, vacuum-pumping tube, tightness system, heating unit, heating protecting device, rack and can end socket be opened; Described burner hearth is outside equipped with external thermal insulation; Described vacuum-pumping tube and describedly open the two ends that end socket is arranged at described burner hearth respectively, describedly opens the open end that end socket is arranged at described burner hearth, for the open and close of burner hearth; Described heating unit is arranged at the inside of described burner hearth, and described heating unit is 5 ~ 9; Described heating protecting device is arranged at outside described heating unit; Described rack is arranged at outside described heating protecting device, and described pending fibre sleeving is put in outside described rack; Described tightness system is arranged between described rack and burner hearth.Vacuum imidization stove provided by the invention can ensure the carrying out of the thermal cyclization of fiber, fiber can be made again to be oxidized, decompose and high temperature cabonization phenomenon, thus improve the mechanical property of the polyimide fiber obtained.
Description
Technical field
The present invention relates to technical field of polymer, particularly relate to a kind of imidization method of vacuum imidization stove and polyamic acid fiber.
Background technology
At present, along with scientific technological advance, various high technical fibre plays more and more important effect in national economy and social development.Polyimide fiber with excellent properties such as its radiation resistance, high thermal resistance, high strength and modulus, one of important kind having become current high technical fibre.
Prepare polyimide fiber by two-step approach, be first be that raw material obtains polyamic acid fiber through spinning with polyamic acid, obtain polyimide fiber through imidization more afterwards.Wherein, polyamic acid fibril needs to carry out imidization through heating installation, just can be transformed into polyimide fiber.Common process furnace still can not meet imidization condition, can make fiber imidization not exclusively or produce high temperature cabonization or form the phenomenons such as serious doubling.Chinese patent CN101986077B, CN201962442U disclose this kind of equipment, and weak point is the shortcomings such as the fibre property of preparation is low, intensity difference, lousiness are many.Although utilize vacuum drying oven can improve the drawback of normal stove, but, temperature control is there is and actual temperature is not inconsistent due to vacuum drying oven, there is serious hysteresis phenomenon in temperature, thermal radiation causes temperature uneven, the unfavorable factors such as the amount processing fiber is severely limited, therefore, common process furnace and vacuum drying oven all can not meet the demand of polyamic acid fiber imidization, prepare high-performance polyimide fiber, just must there is special imidization equipment, vacuum imidization stove provided by the invention has just catered to the demand of polyimide fiber development to specific installation, and, can produce in batches, be convenient to industrialization.
Summary of the invention
The object of the present invention is to provide a kind of imidization method of vacuum imidization stove and polyamic acid fiber, vacuum imidization stove provided by the invention is Special Equipment polyamic acid fiber being carried out to imidization, and the polyimide fiber obtained by this equipment imidization has higher mechanical property.
The invention provides a kind of vacuum imidization stove, comprising:
Body of heater, described body of heater one end is provided with can open end socket, for the open and close of body of heater; The other end of described body of heater is provided with vacuum-pumping tube;
Described furnace interior is provided with heating unit, and described heating unit is 5 ~ 9;
Described heating unit outer setting has heating protecting device;
Described heating protecting device outer setting has rack, and described rack is for placing pending fiber yarn;
Sealing ply is provided with between described rack and inboard wall of furnace body;
Described body of heater outer setting has thermal insulation layer.
Preferably, described body of heater is made up of a right cylinder and a hemisphere;
Described end socket of opening is hemisphere.
Preferably, described heating unit is heating tube;
The radial direction of the burner hearth that described heating tube surrounds along described body of heater is arranged;
One in the described heating tube axial centerline being arranged at the burner hearth that described body of heater surrounds;
Remaining heating tube is uniformly distributed in the axial centerline heating tube same footpath that is the center of circle circumferentially.
Preferably, the diameter of described body of heater cross section is 600mm ~ 1000mm;
Heating tube and the described same footpath distance circumferentially between heating tube of described axial centerline is 150mm ~ 250mm.
Preferably, described sealing ply is magnetic current sealing.
Preferably, the thermal insulation layer be arranged at outside described cylindrical body of heater is open-type muff.
Preferably, described rack is rotatable rack.
Preferably, described vacuum-pumping tube is arranged at described right cylinder and hemispheroidal interface, is communicated with described furnace interior.
The invention provides a kind of imidization method of polyamic acid fiber, comprise the following steps:
Be put in by pending polyamic acid fiber on the rack in the vacuum imidization stove described in technique scheme, imidization is carried out in heating, obtains polyimide fiber.
Preferably, the vacuum tightness of described imidization is 0.4mmHg ~ 0.5mmHg.
Preferably, the temperature of described heating is 300 DEG C ~ 600 DEG C.
Preferably, gradient-heated is heated to be described in;
The speed of described gradient-heated is less than or equal to 40 DEG C/min.
The invention provides a kind of vacuum imidization stove, comprise body of heater, described body of heater one end is provided with can open end socket, for the open and close of body of heater; The other end of described body of heater is provided with vacuum-pumping tube; Described furnace interior is provided with heating unit, and described heating unit is 5 ~ 9; Described heating unit outer setting has heating protecting device; Described heating protecting device outer setting has rack, and described rack is for placing pending fiber yarn; Sealing ply is provided with between described rack and inboard wall of furnace body; Described body of heater outer setting has thermal insulation layer.Vacuum imidization stove provided by the invention comprises vacuum-pumping tube, ensure that vacuum tightness when carrying out imidization; And be provided with 5 ~ 9 heating units in the burner hearth to surround at the body of heater of vacuum imidization stove, pending polyamic acid fiber is placed on the rack outside described heating unit, thus make to be heated evenly in the process of imidization, Heating temperature is easy to control.Therefore, carry out in the process of imidization process at employing vacuum imidization stove provided by the invention to polyamic acid, the carrying out of the thermal cyclization of fiber can either be ensured, can make again fiber that the phenomenon being oxidized or decomposing can not occur, also can not there is high temperature cabonization phenomenon, thus improve the mechanical property of the polyimide fiber obtained.Experimental result shows, compared with the vacuum drying oven that prior art is common, the intensity of the polyimide fiber obtained through vacuum imidization stove provided by the invention process improves 300%, and initial modulus improves 180%.
Accompanying drawing explanation
The profile structural representation of the vacuum imidization stove that Fig. 1 provides for the embodiment of the present invention;
The Structure of cross section schematic diagram of the vacuum imidization stove that Fig. 2 provides for the embodiment of the present invention.
Embodiment
The invention provides a kind of vacuum imidization stove, comprising:
Body of heater, described body of heater one end is provided with can open end socket, for the open and close of body of heater; The other end of described body of heater is provided with vacuum-pumping tube;
Described furnace interior is provided with heating unit, and described heating unit is 5 ~ 9;
Described heating unit outer setting has heating protecting device;
Described heating protecting device outer setting has rack, and described rack is for placing pending fiber yarn;
Sealing ply is provided with between described rack and inboard wall of furnace body;
Described body of heater outer setting has thermal insulation layer.
Be provided with vacuum-pumping tube in vacuum imidization stove provided by the invention, ensure that the vacuum tightness in imide process, avoid fiber and oxidation or decomposing phenomenon occur; And; the present invention is provided with 5 ~ 9 heating units in the burner hearth inside that body of heater surrounds; described heating unit is outside equipped with heating protecting device; rack is arranged at outside described heating protecting device; described pending polyamic acid fibre sleeving is put in outside described rack; by above-mentioned heating unit, thermal cyclization process is carried out to described polyamic acid fiber, complete the imidization of polyamic acid, obtain polyimide fiber.Vacuum imidization stove provided by the invention can either ensure the thermal cyclization temperature of polyamic acid fiber, fiber can be avoided again to occur to decompose or carbonization, obtain the polyimide fiber with higher force performance.
See the Structure of cross section schematic diagram of the vacuum imidization stove that Fig. 1, Fig. 1 provide for the embodiment of the present invention, wherein; 1 is heating protecting device; 2 is thermal insulation layer, and 3 take out pipe for vacuum, and 4 is open-type muff; 5 is heating unit; 6 is bracing frame, and 7 for can open end socket, and 8 is rack; 13 is body of heater, and 14 is magnetic current sealing.
Vacuum imidization stove provided by the invention comprises body of heater, and the burner hearth inside that the imidization process of polyamic acid fiber surrounds at described body of heater completes.The shape of the present invention to described body of heater does not have special restriction, and Proper Design can be become different shapes by those skilled in the art as required.In an embodiment of the present invention, described body of heater is made up of a right cylinder and a hemisphere, described hemisphere with can open right cylinder described in end socket and carry out end-blocking, define the structure of burner hearth.In an embodiment of the present invention, the diameter of burner hearth cross section that described body of heater surrounds can be 600mm ~ 1000mm; In the embodiment that the present invention is other, the diameter of the cross section of the burner hearth that described body of heater surrounds can also be 700mm ~ 900mm; In other examples, the diameter of the cross section of burner hearth that described body of heater surrounds also can be 600mm ~ 800mm;
Vacuum imidization stove provided by the invention comprises and can open end socket, and described end socket of opening is arranged at described body of heater one end, for the open and close of body of heater.In an embodiment of the present invention, described end socket of opening is the hemisphere bodily form, and described end socket of opening is outside equipped with thermal insulation layer, connects with the thermal insulation layer outside described body of heater; And, opening end socket and described body of heater joint described, being provided with tightness system, for keeping the vacuum tightness of furnace interior.In an embodiment of the present invention, described body of heater and the tightness system can opened between end socket can be sealing-ring well known to those skilled in the art.The present invention, for the ease of opening the opening and closing of end socket, arranges movable sleeve described unlatching on end socket, for opening end socket and described body of heater tight close, described movable sleeve and described unlatching between end socket is provided with snap close.
Outside described body of heater, vacuum imidization stove provided by the invention is provided with thermal insulation layer, and the material, thickness etc. of the present invention to described thermal insulation layer do not have special restriction, can adopt the thickness that lagging material well known to those skilled in the art and thermal insulation layer are arranged.In an embodiment of the present invention, the material of described thermal insulation layer can be light fibre, has higher heat insulation effect; Described thermal insulation layer is divided into two parts with chamber structure described in technique scheme, comprises the open-type muff outside intermediate cylindrical bodily form body of heater and the thermal insulation layer outside hemisphere body of heater.The present invention is provided with open-type muff 4 in described cylindrical upper of furnace body, can after completing the imidization process to polyamic acid fiber, open having started muff 4, fast the temperature in burner hearth can be down to room temperature, it also avoid the decomposition of polyimide fiber or the generation of carbonization under long-time hot conditions, thus further increase the mechanical property of the polyimide fiber obtained.In an embodiment of the present invention, the bottom of described cylindrical body of heater is provided with base, and the shape of the present invention to described base does not have special restriction, can realize the support to described burner hearth.In the present invention, the shape of cross section of described base is trapezoidal, and the shape of the face contacted with burner hearth and burner hearth is coincide.
Vacuum imidization stove provided by the invention comprises vacuum-pumping tube, and described vacuum-pumping tube is arranged at opens the relative the other end of end socket with described.In an embodiment of the present invention, described vacuum-pumping tube is arranged at the cylindrical of described body of heater and hemispheric seam crossing, and the burner hearth surrounded with described body of heater is communicated with, and for taking the air in burner hearth away, ensures vacuum tightness higher in imidization process.In an embodiment of the present invention, the diameter of described vacuum-pumping tube is 0.5 cun ~ 2 cun, and in other examples, the diameter of described vacuum-pumping tube can also be 1 cun ~ 1.5 cun.The vacuum-pumping tube that the present invention adopts, there is higher pumping efficiency, can make in the short period of time in burner hearth, to reach required vacuum tightness, avoid the decomposition of polyamic acid fiber or the generation of oxidative phenomena, thus further increase the mechanical property of the polyimide fiber obtained.
Vacuum imidization stove provided by the invention comprises heating unit, heating protecting device and rack, and described heating unit is arranged at the inside of described body of heater, and described heating unit is 5 ~ 9; Described heating protecting device is arranged at outside described heating unit; Described rack is arranged at outside described heating protecting device, and described pending fiber is positioned over outside described rack.In an embodiment of the present invention, described heating unit is heating tube, and along the radial direction setting of the burner hearth that body of heater surrounds, the hemisphere end of described body of heater is fixed in one end of described heating unit.In an embodiment of the present invention, described heating unit can be 6 ~ 8, and in other examples, described heating unit can also be 7.In an embodiment of the present invention, one in the described heating tube axial centerline being arranged at the burner hearth that described body of heater surrounds, remaining heating unit is uniformly distributed in the heating tube of the axial centerline same footpath that is the center of circle circumferentially, is circumferentially uniformly distributed described; Heating tube and the described same footpath distance circumferentially between heating tube of described axial centerline can be 150mm ~ 250mm; In other embodiments, heating tube and the described same footpath distance circumferentially between heating tube of described axial centerline can also be 100mm ~ 200mm; In a further embodiment, heating tube and the described same footpath distance circumferentially between heating tube of described axial centerline also can be 80mm ~ 180mm;
The kind of the present invention to described heating tube does not have special restriction, adopts heating tube well known to those skilled in the art.Embodiments of the invention preferably adopt powerful electrically heated coil pipe, and described heating power can reach 100KW, and heating rate is preferably less than or equal to 40 DEG C/min, are more preferably 5 DEG C/min ~ 30 DEG C/min; In the present invention, the temperature of described heating is preferably 300 DEG C ~ 600 DEG C, is more preferably 350 DEG C ~ 550 DEG C;
In the present invention, described heating unit is outside equipped with heating protecting device.In an embodiment of the present invention, described heating unit is heating tube, and described heating protecting device is heated protective pipe.The material of the present invention to described heating protecting device does not have special restriction, adopts heat conduction well known to those skilled in the art, high temperature material.In an embodiment of the present invention, the material of described heating protecting device is high-quality stainless steel, thus ensures at high temperature not creep;
In the present invention, described heating protecting device is outside equipped with rack, outside described rack, be placed with pending fiber.In an embodiment of the present invention, pending polyamic acid fiber winder, then the polyamic acid fiber of winder is positioned over outside described rack, thus achieve the heating to fiber by the heating unit described in technique scheme, make the thermal cyclization of polyamic acid fiber, obtain polyimide fiber.In order to enable to be placed on polyamic acid fiber on described rack evenly be heated, in an embodiment of the present invention, described rack is set to rotate along the central axis of described rack radial direction, the present invention does not have special restriction to the method realizing the rotation of described rack, those skilled in the art can adopt different technical schemes as required, as in an embodiment of the present invention, described rack is connected with motor, by rotating freely of rack described in driven by motor.In embodiment in the present invention, the rotating speed of described rack can be 1 ~ 2 turn/min, and in other embodiments of the invention, the rotating speed of described rack can also be 1.2 ~ 1.8 turns/min.
Hollow imidization stove provided by the invention comprises sealing ply, and described sealing ply is arranged between described rack and furnace interior, thus makes after being vacuumized by vacuum-pumping tube, can be maintained vacuum tightness, be conducive to the carrying out of imidization.The kind of the present invention to described sealing ply does not have special restriction, adopts tightness system well known to those skilled in the art.In an embodiment of the present invention, described sealing ply can be magnetic current sealing.Magnetic fluid is a kind of novel magnetic materials, and it is by the magnetic-particle of subdomain size, table and the overstable soliquid that promoting agent, liquid carrier form.Because it often keeps Brownian motion, under the effects such as magnetic field, gravity, centrifugal force, therefore keep its steady state.Described magnetic fluid seal is between turning axle and stationary housings, arrange a very strong gap magnetic field, this magnetic field applies a magnetic force to the magnetic fluid in gap, magnetic fluid in gap is flocked together, form liquid " O " the type ring with bearing capacity, thus reaching sealing purpose, it is made up of permanent magnet, magnetic loop, magnetic fluid and turning axle.In the present invention, this liquid airproof ring is completely soft, and mechanical is worn and torn, and certainly moistens Fen, zero leakage, therefore which overcome the weak point in common mechanical or dynamic pressure sealed structure, and it is simple to have structure, sealingly secure is reliable, can be high pressure resistant, life-span is long, easy to maintenance, has machinery and the feature both dynamic pressure sealing concurrently.
See the Structure of cross section schematic diagram of the vacuum imidization stove that Fig. 2, Fig. 2 provide for the embodiment of the present invention, wherein 8 is rack, and 9 is the first display galvanic couple, and 10 for controlling galvanic couple, and 11 is the second display galvanic couple, and 12 is base.
In an embodiment of the present invention, vacuum imidization stove provided by the invention also comprises the first display galvanic couple, the second display galvanic couple and controls galvanic couple, described first display galvanic couple is for showing the temperature on the upside of stove, be arranged in the upper inside walls of described burner hearth, described second display galvanic couple, for showing the temperature on the downside of stove, is arranged on the downside inwall of described burner hearth.The present invention is provided with display galvanic couple in the upper inside walls and downside inwall of burner hearth, for showing the temperature of stove the upper side and lower side, thus can be meticulousr the temperature in burner hearth is regulated, for the imidization process of polyamic acid fiber provides suitable temperature;
In an embodiment of the present invention, described vacuum imidization stove comprises control galvanic couple, and control the temperature in burner hearth according to the program of artificial setting, described control galvanic couple is arranged at outside axial centerline rack.The present invention obtains temperature information by described control galvanic couple, then the information transmission that obtains manually in temperature controlling system, thus can only be controlled according to the temperature of program to burner hearth of artificial setting to AI.The present invention adopts single-point temperature controller, utilizes AI artificial intelligence regulating algorithm to carry out temperature control; AI artificial intelligence regulating algorithm is a kind of New Algorithm adopting fuzzy rule to carry out P, I, D parameter regulation; when error is large; fuzzy algorithm is used to regulate; to eliminate the saturated integration of PID, power alarm defencive functions such as there is overtemperature simultaneously, owe temperature, be disconnected even, any one is reported to the police once produce; system can cut off electrical source of power immediately, product burning when losing efficacy to prevent temperature control system.When error hour, adopt improve after pid algorithm regulate, and can in adjustment automatic learning and memory controlled plant Partial Feature to make effect optimization.There is non-overshoot, high precision, parameter determine simply, to complex object also can obtain the features such as good control effects.AI artificial intelligence temperature controller also has parameter self-tuning function, when it uses for the first time, can start self-setting function to assist and determine the controling parameters such as M5, P, T.
The invention provides a kind of imidization method of polyamic acid fiber, comprise the following steps:
Be positioned over by pending polyamic acid fiber on the rack in the vacuum imidization stove described in technique scheme, imidization is carried out in heating, obtains polyimide fiber.
The present invention adopts the vacuum imidization stove described in technique scheme to carry out imidization to polyamic acid fiber, pending polyamic acid fiber is positioned on the rack in the vacuum imidization stove described in technique scheme, imidization is carried out in heating, obtains polyimide fiber.Fiber after winder, preferably by pending polyamic acid fiber winder, is then positioned on the rack in the vacuum imidization stove described in technique scheme, carries out imidization by the present invention.In the present invention, the temperature of described heating is preferably 300 DEG C ~ 600 DEG C, is more preferably 350 DEG C ~ 550 DEG C; Described heating is preferably gradient-heated, and the speed of described gradient-heated is preferably less than or equal to 40 DEG C/min, is more preferably 5 DEG C/min ~ 30 DEG C/min.The present invention does not have special restriction to described pending polyamic acid fiber, can prepare for the method for polyamic acid fiber well known to those skilled in the art, as diamine monomer and dianhydride monomer can be adopted to react in organic solvent, obtain polyamic acid solution; Described polyamic acid solution is carried out spinning moulding, obtains polyamic acid fiber.The present invention does not have special restriction to described diamine monomer and the reaction conditions of dianhydride monomer and the spinning processes of polyamic acid solution, adopts technical scheme prepared by polyamic acid fiber well known to those skilled in the art.
First the present invention opens movable sleeve snap close, is removed by movable sleeve, then opens and can open end socket 7, the fiber yarn of winder is set on rack 8, close and open end socket 7, then take out pipe 3 by vacuum and vacuumize, reach specified vacuum when spending, start heating schedule to heat, and open rotating machine, allow the rack 8 in furnace chamber rotate at a slow speed, rack rotarily drives fiber and rotates together, ensure that fiber is heated evenly in hot-imide process, degree of imidisation is complete.After completing intensification and insulation program, open open-type muff 4, fast cooling, drop to room temperature and take out fiber.
The invention provides a kind of vacuum imidization stove, comprise body of heater, described body of heater one end is provided with can open end socket, for the open and close of body of heater; The other end of described body of heater is provided with vacuum-pumping tube; Described furnace interior is provided with heating unit, and described heating unit is 5 ~ 9; Described heating unit outer setting has heating protecting device; Described heating protecting device outer setting has rack, and described rack is for placing pending fiber yarn; Sealing ply is provided with between described rack and inboard wall of furnace body; Described body of heater outer setting has thermal insulation layer.Vacuum imidization stove provided by the invention comprises vacuum-pumping tube, ensure that vacuum tightness when carrying out imidization; And be provided with 5 ~ 9 heating units in the burner hearth to surround at the body of heater of vacuum imidization stove, pending polyamic acid fiber is placed on the rack outside described heating unit, thus make to be heated evenly in the process of imidization, Heating temperature is easy to control.Therefore, carry out in the process of imidization process at employing vacuum imidization stove provided by the invention to polyamic acid, the carrying out of the thermal cyclization of fiber can either be ensured, can make again fiber that the phenomenon being oxidized or decomposing can not occur, also can not there is high temperature cabonization phenomenon, thus improve the mechanical property of the polyimide fiber obtained.Experimental result shows, compared with the vacuum drying oven that prior art is common, the intensity of the polyimide fiber obtained through vacuum imidization stove provided by the invention process improves 300%, and initial modulus improves 180%.
In order to further illustrate the present invention, being described in detail below in conjunction with the imidization method of embodiment to vacuum imidization stove provided by the invention and polyamic acid fiber, but they can not being interpreted as limiting the scope of the present invention.
In the following embodiments, the parameter of the vacuum imidization stove of employing is as follows
Top temperature: 650 DEG C;
Conventional temperature: 300 DEG C ~ 600 DEG C;
Scantlings of the structure: Φ 800mm × 1000mm;
Burner hearth material: burner hearth adopts SUS321 material;
Burner hearth quantity: 1, corresponding temperature 300 DEG C ~ 600 DEG C;
Measurement and control of temperature is counted: 2 points for measuring temperature and 1 temperature controlling point;
Control accuracy: ± 1 DEG C, adopts AI artificial intelligence temperature controlling system, pid parameter Self-tuning System, disconnected even, overtemperature alarm, power-off protection;
Temperature homogeneity :≤± 1 DEG C;
Vacuum tightness: 0.4 ~ 0.5mmHg;
Volume: 770L;
Safeguard protection: overtemperature, the disconnected even and alarm and protection such as intervention switch, overcurrent protection function;
Peak power: 100KW;
Insulation power: 70KW;
Temperature rise rate: 0 ~ 40 DEG C/min;
Heating unit: electric heating tube.
Embodiment 1
By pending polyamic acid fiber, adopt vacuum imidization stove provided by the invention to carry out imidization, vacuum tightness is about 0.4mmHg ~ 0.5mmHg, and hot imidization temperature rises to 350 DEG C from 20 DEG C, and heat-up rate is 25 DEG C/min.
Result shows, the intensity adopting the polyimide fiber of vacuum imidization stove provided by the invention process is 2.75GPa, and modulus is 23.98GPa, elongation is 43.12%, the polyimide fiber that relative and comparative example 1 obtains, intensity improves 98%, and modulus improves 111%.
Comparative example 1
The technical scheme of embodiment 1 is adopted to carry out imidization process to pending polyamic acid fiber, unlike, the imidization equipment that this comparative example adopts is a conventional oven.
Result shows, the intensity of the polyimide fiber that this comparative example obtains is 1.39GPa, and modulus is 11.38GPa, and elongation is 38.90%.
Embodiment 2
By pending polyamic acid fiber, adopt vacuum imide stove provided by the invention to carry out imidization, vacuum tightness is about 0.4mmHg ~ 0.5mmHg, and hot imidization temperature rises to 530 DEG C from 20 DEG C, and heat-up rate is 30 DEG C/min.
Result shows, the breaking tenacity 1.81GPa of the polyimide fiber that the present embodiment obtains, and modulus is 18.95GPa, and elongation at break is 9.32%.
Embodiment 3
By pending polyamic acid fiber, adopt vacuum imidization stove provided by the invention to carry out imidization, vacuum tightness is about 0.4mmHg ~ 0.5mmHg, and hot imidization temperature rises to 510 DEG C from 20 DEG C, and heat-up rate is 15 DEG C/min.
Result shows, the breaking tenacity of the polyimide fiber that the present embodiment obtains is 5.0GPa, and initial modulus is 180GPa, compared with the polyimide fiber obtained with comparative example 2, the breaking tenacity of the polyimide fiber that the present embodiment obtains improves 300%, and initial modulus improves 180%.
Comparative example 2
The technical scheme of embodiment 3 is adopted to carry out imidization process to pending polyamic acid fiber, unlike, the breaking tenacity of the polyimide fiber that this comparative example obtains is 1.25GPa, and initial modulus is 64.28GPa.
As seen from the above embodiment, the invention provides a kind of vacuum imidization stove, comprise body of heater, described body of heater one end is provided with can open end socket, for the open and close of body of heater; The other end of described body of heater is provided with vacuum-pumping tube; Described furnace interior is provided with heating unit, and described heating unit is 5 ~ 9; Described heating unit outer setting has heating protecting device; Described heating protecting device outer setting has rack, and described rack is for placing pending fiber yarn; Sealing ply is provided with between described rack and inboard wall of furnace body; Described body of heater outer setting has thermal insulation layer.Vacuum imidization stove provided by the invention comprises vacuum-pumping tube, ensure that vacuum tightness when carrying out imidization; And be provided with 5 ~ 9 heating units in the burner hearth to surround at the body of heater of vacuum imidization stove, pending polyamic acid fiber is placed on the rack outside described heating unit, thus make to be heated evenly in the process of imidization, Heating temperature is easy to control.Therefore, carry out in the process of imidization process at employing vacuum imidization stove provided by the invention to polyamic acid, the carrying out of the thermal cyclization of fiber can either be ensured, can make again fiber that the phenomenon being oxidized or decomposing can not occur, also can not there is high temperature cabonization phenomenon, thus improve the mechanical property of the polyimide fiber obtained.Experimental result shows, compared with the vacuum drying oven that prior art is common, the intensity of the polyimide fiber obtained through vacuum imidization stove provided by the invention process improves 300%, and initial modulus improves 180%.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (8)
1. a vacuum imidization stove, comprising:
Body of heater, described body of heater one end is provided with can open end socket, for the open and close of body of heater; The other end of described body of heater is provided with vacuum-pumping tube, and described body of heater is made up of a right cylinder and a hemisphere, and described end socket of opening is hemisphere;
Described furnace interior is provided with heating unit, and described heating unit is 5 ~ 9, and described heating unit is heating tube; The radial direction of the burner hearth that described heating tube surrounds along described body of heater is arranged; One in the described heating tube axial centerline being arranged at the burner hearth that described body of heater surrounds; Remaining heating tube is uniformly distributed in the axial centerline heating tube same footpath that is the center of circle circumferentially;
Described heating unit outer setting has heating protecting device;
Described heating protecting device outer setting has rack, and described rack is for placing pending fiber yarn, and described rack is rotatable rack;
Sealing ply is provided with between described rack and inboard wall of furnace body;
Described body of heater outer setting has thermal insulation layer, and described thermal insulation layer is open-type muff.
2. vacuum imidization stove according to claim 1, is characterized in that, the diameter of described body of heater cross section is 600mm ~ 1000mm;
Heating tube and the described same footpath distance circumferentially between heating tube of described axial centerline is 150mm ~ 250mm.
3. vacuum imidization stove according to claim 1, is characterized in that, described sealing ply is magnetic current sealing.
4. vacuum imidization stove according to claim 1, is characterized in that, described vacuum-pumping tube is arranged at described right cylinder and hemispheroidal interface, is communicated with described furnace interior.
5. an imidization method for polyamic acid fiber, comprises the following steps:
Be put in by pending polyamic acid fiber on the rack in the vacuum imidization stove described in described Claims 1 to 4 any one, imidization is carried out in heating, obtains polyimide fiber.
6. method according to claim 5, is characterized in that, the vacuum tightness of described imidization is 0.4mmHg ~ 0.5mmHg.
7. method according to claim 5, is characterized in that, the temperature of described heating is 300 DEG C ~ 600 DEG C.
8. method according to claim 5, is characterized in that, described in be heated to be gradient-heated;
The speed of described gradient-heated is less than or equal to 40 DEG C/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310319398.0A CN103387670B (en) | 2013-07-26 | 2013-07-26 | A kind of imidization method of vacuum imidization stove and polyamic acid fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310319398.0A CN103387670B (en) | 2013-07-26 | 2013-07-26 | A kind of imidization method of vacuum imidization stove and polyamic acid fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103387670A CN103387670A (en) | 2013-11-13 |
| CN103387670B true CN103387670B (en) | 2015-12-02 |
Family
ID=49532101
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310319398.0A Active CN103387670B (en) | 2013-07-26 | 2013-07-26 | A kind of imidization method of vacuum imidization stove and polyamic acid fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103387670B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103628215B (en) * | 2013-12-05 | 2016-02-10 | 江苏奥神新材料股份有限公司 | A kind of polyamic acid fiber cyclization method |
| CN104328525B (en) * | 2014-11-13 | 2016-06-22 | 徐东 | Imidizate device of polyimide fiber and preparation method thereof |
| CN104829837B (en) * | 2015-05-22 | 2017-01-04 | 黑龙江省科学院石油化学研究院 | A kind of method using magnetic particle sensing to add hot preparation soluble polyimide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1419308A (en) * | 1972-02-23 | 1975-12-31 | Ugine Infra | Heat treatment furnace |
| CN101338462A (en) * | 2008-08-20 | 2009-01-07 | 中国科学院长春应用化学研究所 | Method for preparing polyimide fiber |
| CN101986077A (en) * | 2010-08-09 | 2011-03-16 | 合肥日新高温技术有限公司 | Pilot line thermal imidization furnace |
-
2013
- 2013-07-26 CN CN201310319398.0A patent/CN103387670B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1419308A (en) * | 1972-02-23 | 1975-12-31 | Ugine Infra | Heat treatment furnace |
| CN101338462A (en) * | 2008-08-20 | 2009-01-07 | 中国科学院长春应用化学研究所 | Method for preparing polyimide fiber |
| CN101986077A (en) * | 2010-08-09 | 2011-03-16 | 合肥日新高温技术有限公司 | Pilot line thermal imidization furnace |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103387670A (en) | 2013-11-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103387670B (en) | A kind of imidization method of vacuum imidization stove and polyamic acid fiber | |
| CN103215666B (en) | Novel centrifugal melt electrostatic spinning device | |
| CN101314869B (en) | Apparatus for preparing macromolecule nano-fibre and spinning method thereof | |
| CN206783318U (en) | A kind of equipment that can be continuously produced graphene heat conduction film | |
| CN208379052U (en) | A kind of bonder of silicon carbide seed piece | |
| CN104532353A (en) | Chromium-doped zinc selenide monocrystal Bridgman growth device and method | |
| CN102965724A (en) | Single crystal furnace with double-layer quartz tube sealing structure by crystal pulling method | |
| CN103451753A (en) | Device and method for multi-jet electrostatic spinning of high-viscosity polymer melts | |
| CN104710106B (en) | A kind of induction furnace for preform collapsing | |
| CN107840567A (en) | A kind of melting electrostatic device for spinning for glass material | |
| CN205255306U (en) | Raw materials heating and melting device of polytetrafluoroethylene raw material area production | |
| CN211972511U (en) | Fibrous heat treatment reaction unit and heat treatment system | |
| CN208121236U (en) | A kind of monocrystaline silicon stove | |
| CN203474969U (en) | Melt electrostatic spinning device used for high-viscosity polymer multi-jet-flow | |
| CN111364109B (en) | Fiber heat treatment reaction device, heat treatment system and heat treatment method | |
| CN111961882B (en) | Sodium metal remelting and forming machine | |
| CN104760953A (en) | Total reflection axis focused carbon fibre graphitization furnace for laser tunnel | |
| CN215909663U (en) | Graphite crucible for extracting carbon element and horizontal induction heating graphitization furnace | |
| CN205874377U (en) | Little biological cellulose apparatus for producing | |
| CN103984374A (en) | High temperature system for small punch test method | |
| CN205529005U (en) | Organic material evaporation plant | |
| CN201532964U (en) | Zone-melting recrystallization device | |
| CN103601366A (en) | Cooling water jacket of glass fiber kiln electrode | |
| CN109423627B (en) | Disposable full-surface vapor deposition furnace for disc parts | |
| CN206089953U (en) | Chemical fiber spun yarn line hot stretching device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |