CN103387670A - Vacuum imidizing furnace and imidizing method of polyamide acid fiber - Google Patents
Vacuum imidizing furnace and imidizing method of polyamide acid fiber Download PDFInfo
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- CN103387670A CN103387670A CN2013103193980A CN201310319398A CN103387670A CN 103387670 A CN103387670 A CN 103387670A CN 2013103193980 A CN2013103193980 A CN 2013103193980A CN 201310319398 A CN201310319398 A CN 201310319398A CN 103387670 A CN103387670 A CN 103387670A
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Abstract
The invention provides a vacuum imidizing furnace comprising a hearth, an external heat insulating layer, a vacuumizing tube, a sealing device, 5-9 heating devices, a heating protective device, a net frame and an openable end enclosure, wherein the external heat insulating layer is arranged outside the hearth, the vacuumizing tube and the openable end enclosure are respectively arranged at the two ends of the hearth, the openable end enclosure is arranged at the open end of the hearth and is used for opening and closing the hearth, the heating devices are arranged in the hearth, the heating protective device is arranged outside the heating devices, the net frame is arranged outside the heating protective device, a fiber to be treated is sleeved outside the net frame, and the sealing device is arranged between the net frame and the hearth. By utilizing the vacuum imidizing furnace, the fiber can be thermally cyclized but cannot be oxidized, decomposed or carbonized at a high temperature, so that the mechanical performances of the prepared polyamide acid fiber can be improved.
Description
Technical field
The present invention relates to technical field of polymer, relate in particular to a kind of imidization method of vacuum imidization stove and polyamic acid fiber.
Background technology
At present, along with scientific technological advance, various hi-tech fibers are being brought into play 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, has become one of important kind of current hi-tech fiber.
Preparing polyimide fiber by two-step approach, is at first to make the polyamic acid fiber take polyamic acid as raw material through spinning, obtains polyimide fiber through imidization more afterwards.Wherein, the polyamic acid fibril need to carry out imidization through heating installation, just can be transformed into polyimide fiber.Common process furnace still can not meet the imidization condition, can make the fiber imidization not exclusively or produce high temperature cabonization or form the phenomenon such as serious doubling.Chinese patent CN101986077B, CN201962442U disclose this kind equipment, and weak point is the shortcomings such as low, the intensity difference of fibre property, the lousiness of preparation is many.although utilize vacuum drying oven can improve the drawback of common stove, but, because existing temperature control and actual temperature, vacuum drying oven is not inconsistent, there is serious hysteresis phenomenon in temperature, thermal radiation causes temperature uneven, the unfavorable factors such as the amount of 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 the high-performance polyimide fiber, special imidization equipment just must be arranged, 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 the polyamic acid fiber to be carried out the Special Equipment of imidization, and the polyimide fiber that obtains 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, is used for the open and close of body of heater; The other end of described body of heater is provided with vacuum-pumping tube;
Described body of heater inside 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 used for placing pending fiber yarn;
Be provided with sealing ply 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 comprised of a right cylinder and a hemisphere;
The described end socket of opening is hemisphere.
Preferably, described heating unit is heating tube;
The radially setting of the burner hearth that described heating tube surrounds along described body of heater;
In described heating tube one is arranged at the central axis position of the burner hearth that described body of heater surrounds;
Remaining heating tube is uniformly distributed on same footpath circumference take central axis position heating tube as the center of circle.
Preferably, the diameter of described body of heater cross section is 600mm～1000mm;
Distance on the heating tube of described central axis position and described same footpath circumference between heating tube is 150mm～250mm.
Preferably, described sealing ply is magnetic current sealing.
Preferably, being arranged at the outer thermal insulation layer of described cylindrical body of heater is the open-type muff.
Preferably, described rack is rotatable rack.
Preferably, described vacuum-pumping tube is arranged at described right cylinder and hemispheroidal interface, with described body of heater internal communication.
The invention provides a kind of imidization method of polyamic acid fiber, comprise the following steps:
Pending polyamic acid fiber is put on rack in the described vacuum imidization of technique scheme stove, and 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 ℃～600 ℃.
Preferably, the described gradient-heated that is heated to be;
The speed of described gradient-heated is less than or equal to 40 ℃/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, is used for the open and close of body of heater; The other end of described body of heater is provided with vacuum-pumping tube; Described body of heater inside 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 used for placing pending fiber yarn; Be provided with sealing ply 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, the vacuum tightness while having guaranteed to carry out imidization; And be provided with 5～9 heating units in the burner hearth that the body of heater of vacuum imidization stove surrounds, pending polyamic acid fiber is placed on the outer rack of described heating unit, be heated evenly thereby make in the process of imidization, Heating temperature is easy to control.Therefore, in employing vacuum imidization stove provided by the invention carries out the process of imidization processing to polyamic acid, can either guarantee the carrying out of the thermal cyclization of fiber, can make again fiber the phenomenon of oxidation or decomposition can not occur, the high temperature cabonization phenomenon can not occur, thereby improved the mechanical property of the polyimide fiber that obtains yet.Experimental result shows, with the vacuum drying oven that prior art is common, compares, and the intensity of processing the polyimide fiber that obtains through vacuum imidization stove provided by the invention has improved 300%, and initial modulus has improved 180%.
Description of drawings
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, is used for the open and close of body of heater; The other end of described body of heater is provided with vacuum-pumping tube;
Described body of heater inside 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 used for placing pending fiber yarn;
Be provided with sealing ply 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, guaranteed the vacuum tightness in the imide process, avoided fiber generation oxidation or decomposing phenomenon; 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, described polyamic acid fiber is carried out thermal cyclization and process, complete the imidization of polyamic acid, obtain polyimide fiber.Vacuum imidization stove provided by the invention can either guarantee the thermal cyclization temperature of polyamic acid fiber, can avoid again fiber to occur to decompose or carbonization, obtains having higher force and learns the polyimide fiber of performance.
Referring to Fig. 1, the Structure of cross section schematic diagram of the vacuum imidization stove that Fig. 1 provides 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 the 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 imidization of polyamic acid fiber is processed and completed in the burner hearth inside that described body of heater surrounds.The present invention does not have special restriction to the shape of described body of heater, and those skilled in the art can become Proper Design different shapes as required.In an embodiment of the present invention, described body of heater is comprised of a right cylinder and a hemisphere, described hemisphere with can open the described right cylinder of end socket and carry out end-blocking, surrounded the structure of burner hearth.In an embodiment of the present invention, the diameter of the burner hearth cross section that surrounds of described body of heater can be 600mm～1000mm; In the other embodiment of the present invention, the diameter of the cross section of the burner hearth that described body of heater surrounds can also be 700mm～900mm; In other embodiment, the diameter of the cross section of the burner hearth that described body of heater surrounds also can be 600mm～800mm;
Vacuum imidization stove provided by the invention comprises can open end socket, and the described end socket of opening is arranged at described body of heater one end, is used for the open and close of body of heater.In an embodiment of the present invention, the described end socket of opening is the hemisphere bodily form, and the described end socket of opening is outside equipped with thermal insulation layer, and the thermal insulation layer outer with described body of heater joins; And,, in described end socket and the described body of heater joint of opening, be provided with tightness system, be used for keeping the vacuum tightness of body of heater inside.In an embodiment of the present invention, described body of heater and the tightness system that can open 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 the unlatching on end socket, is used for opening end socket and described body of heater tight close, at described movable sleeve and described the 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 present invention does not have special restriction to the material of described thermal insulation layer, thickness etc., the thickness that can adopt lagging material well known to those skilled in the art and thermal insulation layer to arrange.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 the described chamber structure of technique scheme, comprises open-type muff and the outer thermal insulation layer of hemisphere body of heater that intermediate cylindrical bodily form body of heater is outer.The present invention is provided with open-type muff 4 in described cylindrical upper of furnace body, can be after the imidization processing of completing the polyamic acid fiber, to start muff 4 opens, can fast the temperature in burner hearth be down to room temperature, also avoid the decomposition of polyimide fiber under long-time hot conditions or the generation of carbonization, thereby further improved the mechanical property of the polyimide fiber that obtains.In an embodiment of the present invention, the bottom of described cylindrical body of heater is provided with base, and the present invention does not have special restriction to the shape of described base, can realize the support of described burner hearth is got final product.In the present invention, the shape of cross section of described base is trapezoidal, and the shape of the face that contacts 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 and the described relative the other end of end socket of opening.In an embodiment of the present invention, described vacuum-pumping tube is arranged at cylindrical and the hemispheric seam crossing of described body of heater, and the burner hearth that surrounds with described body of heater is communicated with, and is used for taking away the air in burner hearth, guarantees higher vacuum tightness in the 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 embodiment, the diameter of described vacuum-pumping tube can also be 1 cun～1.5 cun.The vacuum-pumping tube that the present invention adopts, has higher pumping efficiency, can make in the short period of time in burner hearth the vacuum tightness that reaches required, avoid the decomposition of polyamic acid fiber or the generation of oxidative phenomena, thereby further improve the mechanical property of the polyimide fiber that obtains.
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, the radially setting of the burner hearth that surrounds along body of heater, and an end of described heating unit is fixed in the hemisphere end of described body of heater.In an embodiment of the present invention, described heating unit can be 6～8, and in other embodiment, described heating unit can also be 7.In an embodiment of the present invention, in described heating tube one is arranged at the central axis position of the burner hearth that described body of heater surrounds, remaining heating unit is uniformly distributed in heating tube take the central axis position on the same footpath circumference in the center of circle, is uniformly distributed on described circumference; Distance on the heating tube of described central axis position and described same footpath circumference between heating tube can be 150mm～250mm; In other embodiments, on the heating tube of described central axis position and described same footpath circumference, the distance between heating tube can also be 100mm～200mm; In a further embodiment, on the heating tube of described central axis position and described same footpath circumference, the distance between heating tube also can be 80mm～180mm;
The present invention does not have special restriction to the kind of described heating tube, adopts heating tube well known to those skilled in the art to get final product.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 ℃/min, more preferably 5 ℃/min～30 ℃/min; In the present invention, the temperature of described heating is preferably 300 ℃～600 ℃, more preferably 350 ℃～550 ℃;
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 the heated protective pipe.The present invention does not have special restriction to the material of described heating protecting device, adopts heat conduction well known to those skilled in the art, high temperature material to get final product.In an embodiment of the present invention, the material of described heating protecting device is the high-quality stainless steel, thereby guarantees at high temperature not creep;
In the present invention, described heating protecting device is outside equipped with rack, is placed with pending fiber outside described rack.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, thereby by the described heating unit of technique scheme, realized heating to fiber, make the thermal cyclization of polyamic acid fiber, obtain polyimide fiber.For the polyamic acid fiber that is placed on described rack can be heated more uniformly, in an embodiment of the present invention, described rack is set to can be along the central axis rotation radially of described rack, the present invention does not have special restriction to the method that realizes described rack rotation, 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 the described rack of driven by motor.In embodiment in the present invention, the rotating speed of described rack can turn/min for 1～2, and in other embodiments of the invention, the rotating speed of described rack can also turn/min for 1.2～1.8.
Hollow imidization stove provided by the invention comprises sealing ply, and described sealing ply is arranged between described rack and body of heater inside, thereby makes after by vacuum-pumping tube, vacuumizing, and can be maintained vacuum tightness, is conducive to the carrying out of imidization.The present invention does not have special restriction to the kind of described sealing ply, adopts tightness system well known to those skilled in the art to get final product.In an embodiment of the present invention, described sealing ply can be magnetic current sealing.Magnetic fluid is a kind of novel magnetic material, 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, therefore keep its steady state under the effects such as magnetic field, gravity, centrifugal force.Described magnetic fluid seal is that a very strong gap magnetic field is set between turning axle and stationary housings, this magnetic field applies a magnetic force to the magnetic fluid in gap, make the magnetic fluid in gap flock together, formation has liquid " O " the type ring of bearing capacity, thereby reach sealing purpose, it is to consist of permanent magnet, magnetic loop, magnetic fluid and turning axle.In the present invention, this liquid airproof ring is fully soft, and the machinery-free wearing and tearing, moisten Fen certainly, zero leakage, therefore it has overcome the weak point in common machinery or dynamic pressure sealed structure, and has simple in structurely, and sealingly secure is reliable, can be high pressure resistant, life-span is long, and is easy to maintenance, has machinery and dynamic pressure concurrently and seals both characteristics.
Referring to Fig. 2, the Structure of cross section schematic diagram of the vacuum imidization stove that Fig. 2 provides for the embodiment of the present invention, wherein 8 is rack, and 9 is first to show galvanic couple, and 10 for controlling galvanic couple, and 11 is second to show galvanic couple, 12 is base.
In an embodiment of the present invention, vacuum imidization stove provided by the invention also comprises that first shows that galvanic couple, second shows galvanic couple and controls galvanic couple, described first shows that galvanic couple is used for showing the temperature of stove upside, be arranged on the upper inside walls of described burner hearth, described second shows that galvanic couple is used for showing the temperature of stove downside, is arranged on the downside inwall of described burner hearth.The present invention is provided with the demonstration galvanic couple on the upper inside walls of burner hearth and downside inwall, be used for showing the temperature of stove upside and downside, thereby the temperature in burner hearth that can be meticulousr 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 the control galvanic couple, according to the program of artificial setting, the temperature in burner hearth is controlled, and described control galvanic couple is arranged at outside the rack of central axis position.The present invention obtains temperature information by described control galvanic couple, the information transmission that then will obtain to AI manually can only temperature controlling system in, thereby can control the temperature of burner hearth according to the program of artificial setting.The present invention adopts the single-point temperature controller, utilizes AI artificial intelligence regulating algorithm to carry out temperature control; AI artificial intelligence regulating algorithm is to adopt fuzzy rule to carry out a kind of New Algorithm of P, I, D parameter regulation; when error is large; use fuzzy algorithm to regulate; to eliminate the saturated integration of PID, have simultaneously overtemperature, owe temperature, the disconnected power alarm defencive function such as even, any warning is in case produce; system can be cut off electrical source of power immediately, product burning when preventing that temperature control system lost efficacy.When error hour, the pid algorithm after adopt improving is regulated, and can be in adjusting the Partial Feature of automatic learning and memory controlled plant so that the effect optimization.Have non-overshoot, high precision, parameter determine simple, also can obtain to control preferably the characteristics such as effect to complex object.AI artificial intelligence temperature controller also has the parameter self-tuning function, when it uses for the first time, can start self-setting function and assist to determine that M5, P, T etc. control parameter.
The invention provides a kind of imidization method of polyamic acid fiber, comprise the following steps:
Pending polyamic acid fiber is positioned on rack in the described vacuum imidization of technique scheme stove, and imidization is carried out in heating, obtains polyimide fiber.
The present invention adopts the described vacuum imidization of technique scheme stove to carry out imidization to the polyamic acid fiber, pending polyamic acid fiber is positioned on rack in the described vacuum imidization of technique scheme stove, imidization is carried out in heating, obtains polyimide fiber.The present invention, preferably with pending polyamic acid fiber winder, then is positioned over the fiber after winder on the rack in the described vacuum imidization of technique scheme stove, carries out imidization.In the present invention, the temperature of described heating is preferably 300 ℃～600 ℃, more preferably 350 ℃～550 ℃; Described heating is preferably gradient-heated, and the speed of described gradient-heated is preferably less than or equal to 40 ℃/min, more preferably 5 ℃/min～30 ℃/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 adopting diamine monomer and dianhydride monomer to react, obtain polyamic acid solution in organic solvent; Described polyamic acid solution is carried out spinning moulding, obtain the polyamic acid fiber.The present invention does not have special restriction to the reaction conditions of described diamine monomer and dianhydride monomer and the spinning processes of polyamic acid solution, adopts the technical scheme of polyamic acid fiber preparation well known to those skilled in the art to get final product.
At first the present invention opens the movable sleeve snap close, and movable sleeve is removed, and 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 by vacuum, take out pipe 3 and vacuumize, when reaching specified vacuum and spending, starting heating schedule heats, and the unlatching rotating machine, allow the interior rack 8 of furnace chamber rotate at a slow speed, rack rotarily drives fiber and rotates together, guaranteed that fiber is heated evenly in the hot-imide process, degree of imidisation is complete.After having completed 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, is used for the open and close of body of heater; The other end of described body of heater is provided with vacuum-pumping tube; Described body of heater inside 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 used for placing pending fiber yarn; Be provided with sealing ply 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, the vacuum tightness while having guaranteed to carry out imidization; And be provided with 5～9 heating units in the burner hearth that the body of heater of vacuum imidization stove surrounds, pending polyamic acid fiber is placed on the outer rack of described heating unit, be heated evenly thereby make in the process of imidization, Heating temperature is easy to control.Therefore, in employing vacuum imidization stove provided by the invention carries out the process of imidization processing to polyamic acid, can either guarantee the carrying out of the thermal cyclization of fiber, can make again fiber the phenomenon of oxidation or decomposition can not occur, the high temperature cabonization phenomenon can not occur, thereby improved the mechanical property of the polyimide fiber that obtains yet.Experimental result shows, with the vacuum drying oven that prior art is common, compares, and the intensity of processing the polyimide fiber that obtains through vacuum imidization stove provided by the invention has improved 300%, and initial modulus has improved 180%.
, in order to further illustrate the present invention, below in conjunction with embodiment, the imidization method of vacuum imidization stove provided by the invention and polyamic acid fiber is described in detail, but they can not be interpreted as restriction to protection domain of the present invention.
In the following embodiments, the parameter of the vacuum imidization stove of employing is as follows
Top temperature: 650 ℃;
Temperature commonly used: 300 ℃～600 ℃;
Scantlings of the structure: Φ 800mm * 1000mm;
The burner hearth material: burner hearth adopts the SUS321 material;
Burner hearth quantity: 1,300 ℃～600 ℃ of corresponding temperatures;
Measurement and control of temperature is counted: 2 points for measuring temperature and 1 temperature controlling point;
Control accuracy: ± 1 ℃, adopt AI artificial intelligence temperature controlling system, pid parameter is from adjusting, and is disconnected even, overtemperature alarm, power-off protection;
Temperature homogeneity :≤± 1 ℃;
Vacuum tightness: 0.4～0.5mmHg;
Volume: 770L;
Safeguard protection: the alarm and protection functions such as overtemperature, disconnected idol and intervention switch, overcurrent protection;
Peak power: 100KW;
Insulation power: 70KW;
Temperature rise rate: 0～40 ℃/min;
Heating unit: electric heating tube.
With 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 the hot imidization temperature rises to 350 ℃ from 20 ℃, and heat-up rate is 25 ℃/min.
Result shows, adopting the intensity of the polyimide fiber that vacuum imidization stove provided by the invention processes is 2.75GPa, and modulus is 23.98GPa, elongation is 43.12%, the polyimide fiber relative and comparative example 1 obtains, intensity has improved 98%, and modulus has improved 111%.
Comparative example 1
Adopt the technical scheme of embodiment 1 to carry out the imidization processing to pending polyamic acid fiber, different is that 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%.
With 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 the hot imidization temperature rises to 530 ℃ from 20 ℃, and heat-up rate is 30 ℃/min.
Result shows, the breaking tenacity 1.81GPa of the polyimide fiber that the present embodiment obtains, and modulus is 18.95GPa, elongation at break is 9.32%.
Embodiment 3
With 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 the hot imidization temperature rises to 510 ℃ from 20 ℃, and heat-up rate is 15 ℃/min.
Result shows, the breaking tenacity of the polyimide fiber that the present embodiment obtains is 5.0GPa, and initial modulus is 180GPa, with the polyimide fiber that comparative example 2 obtains, compares, the breaking tenacity of the polyimide fiber that the present embodiment obtains has improved 300%, and initial modulus has improved 180%.
Comparative example 2
Adopt the technical scheme of embodiment 3 to carry out imidization to pending polyamic acid fiber and process, different is, 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, is used for the open and close of body of heater; The other end of described body of heater is provided with vacuum-pumping tube; Described body of heater inside 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 used for placing pending fiber yarn; Be provided with sealing ply 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, the vacuum tightness while having guaranteed to carry out imidization; And be provided with 5～9 heating units in the burner hearth that the body of heater of vacuum imidization stove surrounds, pending polyamic acid fiber is placed on the outer rack of described heating unit, be heated evenly thereby make in the process of imidization, Heating temperature is easy to control.Therefore, in employing vacuum imidization stove provided by the invention carries out the process of imidization processing to polyamic acid, can either guarantee the carrying out of the thermal cyclization of fiber, can make again fiber the phenomenon of oxidation or decomposition can not occur, the high temperature cabonization phenomenon can not occur, thereby improved the mechanical property of the polyimide fiber that obtains yet.Experimental result shows, with the vacuum drying oven that prior art is common, compares, and the intensity of processing the polyimide fiber that obtains through vacuum imidization stove provided by the invention has improved 300%, and initial modulus has improved 180%.
The above is only the preferred embodiment of the present invention; 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 (12)
1. vacuum imidization stove comprises:
Body of heater, described body of heater one end is provided with can open end socket, is used for the open and close of body of heater; The other end of described body of heater is provided with vacuum-pumping tube;
Described body of heater inside 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 used for placing pending fiber yarn;
Be provided with sealing ply between described rack and inboard wall of furnace body;
Described body of heater outer setting has thermal insulation layer.
2. vacuum imidization stove according to claim 1, is characterized in that, described body of heater is comprised of a right cylinder and a hemisphere;
The described end socket of opening is hemisphere.
3. vacuum imidization stove according to claim 2, is characterized in that, described heating unit is heating tube;
The radially setting of the burner hearth that described heating tube surrounds along described body of heater;
In described heating tube one is arranged at the central axis position of the burner hearth that described body of heater surrounds;
Remaining heating tube is uniformly distributed on same footpath circumference take central axis position heating tube as the center of circle.
4. the described vacuum imidization of any one stove according to claim 3, is characterized in that, the diameter of described body of heater cross section is 600mm～1000mm;
Distance on the heating tube of described central axis position and described same footpath circumference between heating tube is 150mm～250mm.
5. vacuum imidization stove according to claim 1, is characterized in that, described sealing ply is magnetic current sealing.
6. vacuum imidization stove according to claim 2, is characterized in that, being arranged at the outer thermal insulation layer of described cylindrical body of heater is the open-type muff.
7. vacuum imidization stove according to claim 1, is characterized in that, described rack is rotatable rack.
8. vacuum imidization stove according to claim 2, is characterized in that, described vacuum-pumping tube is arranged at described right cylinder and hemispheroidal interface, with described body of heater internal communication.
9. the imidization method of a polyamic acid fiber comprises the following steps:
Pending polyamic acid fiber is put on rack in the described vacuum imidization of described claim 1～8 any one stove, and imidization is carried out in heating, obtains polyimide fiber.
10. method according to claim 9, is characterized in that, the vacuum tightness of described imidization is 0.4mmHg～0.5mmHg.
11. method according to claim 9, is characterized in that, the temperature of described heating is 300 ℃～600 ℃.
12. method according to claim 9, is characterized in that, the described gradient-heated that is heated to be;
The speed of described gradient-heated is less than or equal to 40 ℃/min.
Priority Applications (1)
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Cited By (3)
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| CN103628215A (en) * | 2013-12-05 | 2014-03-12 | 江苏奥神新材料有限责任公司 | Efficient polyamide acid fiber cyclizing method |
| CN104328525A (en) * | 2014-11-13 | 2015-02-04 | 徐东 | Imidization device of polyimide fibers and preparation method of polyimide fibers |
| CN104829837A (en) * | 2015-05-22 | 2015-08-12 | 黑龙江省科学院石油化学研究院 | Method for preparing soluble polyimide by adopting magnetic particle induction heating |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103628215A (en) * | 2013-12-05 | 2014-03-12 | 江苏奥神新材料有限责任公司 | Efficient polyamide acid fiber cyclizing method |
| 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 |
| CN104328525A (en) * | 2014-11-13 | 2015-02-04 | 徐东 | Imidization device of polyimide fibers and preparation method of polyimide fibers |
| CN104328525B (en) * | 2014-11-13 | 2016-06-22 | 徐东 | Imidizate device of polyimide fiber and preparation method thereof |
| CN104829837A (en) * | 2015-05-22 | 2015-08-12 | 黑龙江省科学院石油化学研究院 | Method for preparing soluble polyimide by adopting magnetic particle induction heating |
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| CN103387670B (en) | 2015-12-02 |
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