CN101812732A - Comb-shaped high-strength high-modulus polyethylene unwrapping and extruding spinning device - Google Patents
Comb-shaped high-strength high-modulus polyethylene unwrapping and extruding spinning device Download PDFInfo
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- CN101812732A CN101812732A CN200910046370A CN200910046370A CN101812732A CN 101812732 A CN101812732 A CN 101812732A CN 200910046370 A CN200910046370 A CN 200910046370A CN 200910046370 A CN200910046370 A CN 200910046370A CN 101812732 A CN101812732 A CN 101812732A
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Abstract
The invention relates to a high-strength high-modulus polyethylene dissolving and spinning device with a comb-shaped unwrapping device, which comprises a swelling kettle, a transition tank, a double-screw extruder, a spinneret plate, a condensation pond and a bobbin winding device. The device is characterized in that a comb-shaped unwrapping device is connected between the double-screw extruder and the spinneret plate; the output port of the double-screw extruder is connected with the input port of the comb-shaped unwrapping device; and the output port of the comb-shaped unwrapping device is connected with the input port of the spinneret plate. The comb-shaped unwrapping device consists of a speed adjusting dynamic component, a cylinder and a screw, wherein a heating ring capable of controlling temperature in a partitioned manner is arranged on the cylinder. Spiral conical structures are distributed on the body of the screw and among lands. An exhaust hole is reserved on the tail part of the cylinder of the comb-shaped unwrapping device. The device has the advantages that qualified filament can be formed by quick dissolving and unwrapping by the comb-shaped unwrapping and extruding device and pressurized extruding through spinning components and cooling, so that continuous preparation process of uniform spinning solution can be realized more simply and more quickly.
Description
Technical field
The present invention relates to a kind of high-strength high-modulus polyethylene dissolving and device for spinning that has the pectinate unwinding device.
Background technology
As everyone knows, the organic macromolecule main chain is owing to molecular link rotates freely, in the macromolecular chain conformation, be anti conformation entirely and be that the probability that left gauche form conformation occurs is very little entirely, the overwhelming majority presents is conformation between the trans and gauche, promptly neither stretch the conformation that to curl fully fully, and because warm-up movement, these conformations are also in continuous vibration, in the change, make long-chain show more or less flexibility, especially some nonrigid macromolecular chains make it show as the random coil (see figure 1) on the whole, and this is the stable conformation of most of line style non-polar high polymers, and numerous macromolecular chains flocks together, mutually mat.
For the PE of super high molecular weight, the main chain rotation potential energy of at first considering the PE molecule is very low, therefore flexibility is very big, is a kind of of flexible maximum in present all high polymers, improving constantly along with molecular weight simultaneously, the quantity that single strand produces the topology entanglement rises rapidly, therefore, though such high polymer material has fusing point, at the melt temperature place, the viscosity of system is still very big, to such an extent as to can't carry out spinning.
Gel spinning is to make high-module high-strength polyethylene fibre successful method the most at present.It is that flexible chain high polymer material with super high molecular weight is dissolved in the solvent with lower concentration, the purpose of making solution is to utilize solvent to break the super high molecular weight strand of mutual mat to a certain extent, prevent to produce new entanglement simultaneously, in increase system flowability, when the system spinnability is provided, offer the suitable spun filament structure of gelatine silk, be beneficial to the expansion of super times hot-stretch, form the high-intensity fiber structural form of high crystallization, high orientation.And the key of gel spinning is: the dissolving of super high molecular polyethylene solution, the branch subsolution twines the maintenance of state greatly.
Dissolving is that a certain amount of ultra-high molecular weight polyethylene raw material is dissolved in corresponding solvent with certain concentration, through heating and long period insulating process and the thermal decomposition that causes, be implemented in the macromolecular chain of breaking mutual mat to a certain extent, prevent to produce new entanglement simultaneously, and by even mixing and this behavior of shearing promotion as modes such as stirrings, according to about the experiment and treatise, be dissolved with following characteristic:
A. by to the solution Determination of Modulus, can recognize that half weak solution lacks much really than big molecular entanglement in the concentrated solution.But the rheological behavior of half weak solution is similar to concentrated solution basically, belongs to typical pseudoplastic fluid.
B. shear rate is bigger to the influence of apparent viscosity, and just the entanglement point in the stoste is broken under less shear stress easily, and these characteristics require to reduce shear stress.
C. big molecule half weak solution of flexible chain has higher elasticity, and the elastic turbulence phenomenon takes place when applying big shear stress easily.
So, improve spinning speed and make good as-spun fibre, at first must also to comprehensively take in simultaneously from good dissolving to aspects such as relative molecular mass and distribution, solvent property, spinning temperature, spinneret orifice road draw ratio and duct import department precentrum angles.And dissolving needs to solve three big key issues:
(1) economical and efficient production and thermal oxidative degradation contradictory problems: because the entanglement point in the solution applies less shear stress and more help breaking, and the elastic turbulence phenomenon takes place easily when applying big shear stress, so should adopt less shear stress.And ultra-high molecular weight polyethylene contacts with oxygen at high temperature thermal oxidative degradation easily takes place, and causes molecular weight sharply to descend and the color and luster flavescence, and dissolution velocity is slow excessively, not only is easy to generate thermal degradation but also obviously can't carries out efficiently large-scale production.Thereby control of process condition such as dissolution equipment that must be by particular design and temperature, time suppresses and avoids this phenomenon as far as possible.
(2) deaeration problem: in the course of dissolution and after the dissolving end, the viscosity of spinning solution is very high, but there is a large amount of bubbles in the spinning solution, the existence of bubble can make spun gel strand become cavity filament, strand breaks when causing drawing-off, can't obtain the qualified finished fiber of performance, therefore will carry out deaeration spinning solution.
(3) solution transportation problem: after dissolving finished, the viscosity of spinning solution was very high, thereby carried very difficulty, and mode of movement also is necessary easily.
In sum: it is the key of making high-quality spun filament that the dissolving reconciliation twines, and this process generally will be by dissolution equipment particular design and control of process condition such as temperature, time suppress and avoid this phenomenon as far as possible, simultaneously, also must guarantee full-bodied solution-stabilizedly extrude smoothly.
The US4 of U.S. Allied house journal, 413,1109, the JP.86-73743 of Japan Kuraray company, Chinese patent 97106768 is in the prior art of representative, how with twin-screw (be included as improve dissolved efficiency and adopt as dissolution kettle, twin-spiral mixer, at a high speed assist in dissolving equipment such as drum-type blender) serve as mainly to dissolve to extrude means, there is following problem in these modes:
A) twin-screw pulsation problem: as the double screw extruder that is mainly used in plastic industry in the past, though good melting effect is arranged, but its peculiar pulsation characteristic, pressure can produce pulsatile change when spinning, thereby greatly influences the stability of spinning and the decline of spinning quality.
B) high-efficiency and economic production problem: because the endless that can not do of twin-screw, thereby, if will improve output, will pick up speed or increase other assist in dissolving means, and pick up speed, will cause the time of staying of solution in screw rod to shorten, cause the deficiency of dissolving, thereby can't make qualified spun filament.If reduce the speed of dissolving, will reduce output greatly, can't realize economical production.
C) problem brought of mixing elements increase: can reach abundant homogenization through efficient mixing for guaranteeing material, must increase the quantity of mediating piece, left-hand thread piece and other mixing elementses, make the time of staying lengthening of material in double screw extruder, but the left-hand thread number of blocks is added the fan-out capability and the head pressure that can influence extruder, the more important thing is the overlong time that the High molecular weight polyethylene raw material stops in screw rod, can cause degrading excessive and its colour changed into yellow, influence the performance of finished fiber.
The US4 of U.S. Allied house journal, it is dissolving and extrusion way spinning that 413,1109 (see figure 2)s, the patents such as JP.86-73743 (see figure 3) of Japanese Kuraray company all adopt twin-screw, deficiency for the dissolving that remedies twin-screw, be that the time of staying of feed liquid in double screw extruder is comparatively of short duration, need to increase twin-spiral mixer, high speed drum mixer, devices such as dissolving tank, purpose is to accelerate the uniformity and the dissolved efficiency of dissolving, thereby obtains big production capacity, realizes the order ground of economical production.Since the dissolving measure that these are auxiliary, the equipment complexity, the cost height is difficult to carry out continuously, the deaeration difficulty, and the solution after dissolving is because viscosity is very big, and carrying also is very big difficulty.
Chinese patent 97106768 (see figure 4)s adopt that the twin-screw of big L/D ratio is once finished from suspension to the swelling, uniform dissolution, deaeration, the scheme extruded, what in fact twin-screw can not be made in the industrial processes is long especially, and the course of dissolution of ultra-high molecular weight polyethylene in solvent can be divided into two stages: swelling and dissolving.In the swelling stage, mainly show as solvent and in ultra-high molecular weight polyethylene, permeate and diffusion, it is the key of dissolving mixing.Yet swelling is a slow process, and reason is that the super high molecular weight condensate of high crystallization has hindered the infiltration of solvent.If the time that mixed liquor stops in screw rod is short, then may cause the swelling dissolving not enough, can't make high-quality spun filament, if the time of staying is oversize, then may cause the oxidative degradation of solution, also can greatly influence output simultaneously, can't reach economical production.
Chinese patent 200910045198.4 proposes to utilize the pectinate unwinding dissolver identical with the present invention to overcome the above problems, and uses as extruder but handle has the twin-screw of better blend function, comes pulsation in the spinning process together with belt transect, influences spinning quality.
Summary of the invention
The objective of the invention is to solve the available technology adopting twin-screw and be dissolving and the existing the problems referred to above of extrusion way spinning, provide a kind of dissolving that has the super high molecular polyethylene solution of pectinate unwinding extrusion device to conciliate and twine device for spinning.The present invention's design has the high-strength high-modulus polyethylene dissolving and the device for spinning of pectinate unwinding device, comprise swelling still, transition jar, double screw extruder, spinnerets, condensation pond, winding device, it is characterized in that: between double screw extruder and spinnerets, be connected with a pectinate unwinding device, the delivery outlet of double screw extruder connects the input port of pectinate unwinding device, and the delivery outlet of pectinate unwinding device connects the input port of spinnerets.The pectinate unwinding device is made up of can regulate the speed Power Component, machine barrel and screw rod, on machine barrel, have can subregion the heating collar of control temperature.Be densely covered with helical form awl shape structure on the body of rod of screw rod and between the land.The machine barrel afterbody of pectinate unwinding device has steam vent.Advantage of the present invention is to have adopted ultra-high molecular weight polyethylene to carry out appropriate swelling in alkane solvents, make the suspension of ultra-high molecular weight polyethylene, continuously, feed quantitatively and finish predissolve, deaeration process in the double screw extruder, feed the pectinate unwinding extrusion device then, dissolve fast to separate by the pectinate unwinding extrusion device and twine, pressurization is extruded then, through filament spinning component and cooling, form He Ge De Silk bar, thereby realize the uniform spinning solution process of preparation continuously more quickly and easily.
Description of drawings
Fig. 1 is the schematic diagram of organic macromolecule main chain,
Fig. 2---Fig. 4 is the prior art constructions schematic diagram,
Fig. 5 is a structural representation of the present invention,
Fig. 6 is the structural representation of pectinate unwinding extrusion device of the present invention,
Fig. 7 is the A portion enlarged drawing of Fig. 6.
Below in conjunction with example the present invention is elaborated.
The specific embodiment:
Comprise swelling still 1, transition jar 2, double screw extruder 3, pectinate unwinding extrusion device 4, spinnerets 5, condensation pond 6, winding device 7, it is characterized in that: twin-screw extrude and machine 3 and spinnerets 5 between be connected with a pectinate unwinding device 4, twin-screw is extruded the input port that connects pectinate unwinding device 4 with the delivery outlet of machine 3, and the delivery outlet of pectinate unwinding device 4 connects spinnerets 5.Pectinate unwinding device 4 is made up of the Power Component 10 of can regulating the speed, machine barrel 11 and screw rod 12, on machine barrel 11, have can subregion the heating collar 13 of control temperature.Be densely covered with helical form awl shape structure 14 on the body of rod of screw rod 12 and between the land.Machine barrel 11 afterbodys of pectinate unwinding device 4 have steam vent 15.The present invention has adopted ultra-high molecular weight polyethylene to carry out swelling in alkane solvents, the pectinate unwinding device 4 of feeding indication of the present invention, because this structure adopts little draw ratio manufacturing, it has the propulsion plant of similar screw rod 12 on the one hand, the steam vent 15 that afterbody after the acicular texture of similar carding machine structure is arranged again simultaneously, because less shear stress more helps the solution that viscosity is very big and separates and twine, and the special construction of the designed pectinate unwinding device of the present invention can greatly improve and separate the effect that twines under slower rotating speed; Utilize the bigger head and the pressure differential of input simultaneously, most of bubble is discharged by exhaust outlet automatically backward; The 3rd, can utilize the subregion control temperature technology and the rotating speed of similar screw rod to adjust function, effectively the temperature and the speed of control dissolving.Realization utilizes the heating-up temperature of different sections, finishes the limit and advances, and the continuous process that twines with deaeration is conciliate in the limit dissolving.Thereby solve to use the common dissolution kettle groove etc. can't exhaust and release a difficult problem such as difficulty well.The spinning solution of separating after twining has the metering and the device of relief function by one, be delivered directly to and finish further dissolving, deaeration process in the double screw extruder, connect follow-up device for spinning then, thereby realize the uniform spinning solution process of preparation continuously more quickly and easily.
Organic cooperation by pectinate unwinding device 4 and double screw extruder 3, give full play to the advantage of the two, realize a kind of quick, efficient and the energy-conservation continuous method for preparing the condensate spinning solution, realize the economical production of high quality fiber, overcome the complexity that adopts in the technology in the past thus, loaded down with trivial details uniform dissolution is conciliate and is twined a difficult problem, solved the pulsation problem that produces when using twin-screw as the dissolving extrusion device, also solved in the past only with attending to one thing and lose sight of another that twin-screw produced simultaneously, be difficult to take into account, problem, increase substantially output, realize energy-conserving and environment-protective, promote the purpose of product quality.
The present invention is illustrated with the following example, but patent claim of the present invention is not subjected to the limitation of example condition.
Embodiment:
With weight average molecular weight is 3～5 * 10
5Ultra-high molecular weight polyethylene 80kg, antioxidant 1.3kg, the solution input that white oil (boiling point is 185-300 ℃) 920kg is mixed with 8% concentration has in the 1000L reactor of stirring, with the heating of this solution, makes the suspension of ultra-high molecular weight polyethylene.By heating and stirring, this solution is carried out swelling treatment.Under stirring, equably the gained slurry is input to continuously to dissolve in this pectinate unwinding device for spinning to conciliate by flow valve and twines, squeeze into subsequently double screw extruder by Melt Pump then, finish the continuous process of spinning through filament spinning component etc., specific as follows:
1, double screw extruder diameter and draw ratio: Φ 2 * 108mm, L/D=48,
2, the rotating speed of double screw extruder: 90-250r.p.m.,
3, slurry time of staying in double screw extruder: 2～10 minutes,
4, the form of double screw extruder: the cocurrent and parallel double screw extruder,
5, the screwing element form of double screw extruder: carry, mixing, knead, screwing element such as metering,
6, the diameter of pectinate unwinding extrusion device and draw ratio are Φ 150mm, L/D=7～15.
7, to separate the rotating speed that twines extrusion device be 60～90r.p.m. in dressing,
8, the barrel temperature that twines extrusion device is separated in dressing: 135 ℃ of feeding sections, 155 ℃ of interludes, 185 ℃ of deferent segments.
9, the slurry of predissolve is about 1～10 minute in the time of pectinate unwinding extrusion device
Cooperation with above-mentioned condition can realize per hour can obtaining 500～800 kilograms of homogeneous transparent, bubble-free ultra-high molecular weight polyethylene strands, and output is about one times that only uses twin-screw.
Above-mentioned gel fiber is carried out continuous extraction, drying and ultra-drawing, can make intensity is high-strength, the high-modulus polyethylene fiber of 33g/d.
Claims (4)
1. the high-strength high-modulus polyethylene dissolving and the device for spinning that have the pectinate unwinding device, comprise swelling still, transition jar, double screw extruder, spinnerets, condensation pond, winding device, it is characterized in that: between double screw extruder and spinnerets, be connected with a pectinate unwinding device, the delivery outlet of double screw extruder connects the input port of pectinate unwinding device, and the delivery outlet of pectinate unwinding device connects the input port of spinnerets.
2. by described high-strength high-modulus polyethylene dissolving and the device for spinning that has the pectinate unwinding device of claim 1, it is characterized in that: the pectinate unwinding device is made up of can regulate the speed Power Component, machine barrel and screw rod, on machine barrel, have can subregion the heating collar of control temperature.
3. by described high-strength high-modulus polyethylene continuous-dissolution and the device for spinning that has the pectinate unwinding device of claim 1, it is characterized in that: be densely covered with helical form awl shape structure on the body of rod of screw rod and between the land.
4. by described high-strength high-modulus polyethylene continuous-dissolution and the device for spinning that has the pectinate unwinding device of claim 1, it is characterized in that: the machine barrel afterbody of pectinate unwinding device has steam vent.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021202091A1 (en) | 2020-03-30 | 2021-10-07 | Exxonmobil Chemical Patents Inc. | Comb-block copolymers and methods thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021202091A1 (en) | 2020-03-30 | 2021-10-07 | Exxonmobil Chemical Patents Inc. | Comb-block copolymers and methods thereof |
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Application publication date: 20100825 |