CN1300395C - Manufacturing method of high strength polyethylene fiber - Google Patents
Manufacturing method of high strength polyethylene fiber Download PDFInfo
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- CN1300395C CN1300395C CNB031563007A CN03156300A CN1300395C CN 1300395 C CN1300395 C CN 1300395C CN B031563007 A CNB031563007 A CN B031563007A CN 03156300 A CN03156300 A CN 03156300A CN 1300395 C CN1300395 C CN 1300395C
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Abstract
The present invention discloses a method for manufacturing high strength polyethylene fiber, which comprises the solution dry spinning process and thermal stretching process of ultrahigh molecular weight polyethylene. The present invention is characterized in that solution extruded from a spinneret plate is longitudinally stretched for fluid deformation and solidified to form dry filament containing proper macromolecule intertwist points in the process of dry spinning. The fracture strength of the high-tenacity polyethylene fibre obtained by the manufacturing method of the present invention is from 15 to 45 g/d, and the modulus is from 500 to 1500 g/d. The adoption of the combined technology of the longitudinal stretching for fluid deformation and solidification of the present invention ensures good mechanical performance of fiber, shortens technical process, enhances production efficiency, reduces investment for equipment and production cost and realizes stable and safe industrialization production.
Description
Technical field
The present invention relates to a kind of manufacture method of high-tenacity polyethylene fibre.
Background technology
At present in the world with ultra-high molecular weight polyethylene, carbon fiber and aramid fiber and be called three big high performance fibre material, wherein superhigh molecular weight polyethylene fibers has high strength, high-modulus, low-density characteristics, in the advanced lightweight composite, demonstrate great advantage, bringing into play important role aspect modernized war and defend equipment, aerospace and the aviation, also obtaining application more and more widely at civil area.
Now gel spinning-super times heat stretching process that adopt prepare high-performance polyethylene fibres more, this method is to become spinning solution with the dissolution with solvents ultrahigh molecular weight polyethylene earlier, make flexible macromolecular chain under the dilution of solvent, remove excessive entanglement, solution is extruded after air (dry method) or water (wet method) quenching are solidified through spinneret orifice, obtain containing the hygrometric state precursor (not removing the precursor of solvent) of the big molecular entanglement point of appropriateness, obtain having the high-tenacity polyethylene fibre of extended-chain configuration again through desolventizing and super times hot-stretch.
The ultra-high molecular weight polyethylene strand is the random shape of curling and is scattered in the solvent under solution state, during dry spinning, solution is after spinnerets is extruded, volatilization along with solvent in the solution thread, the strand distance furthers gradually, interaction between the big molecule strengthens, and the physical crosslinking point between the big molecule can increase thereupon; Simultaneously, along with the volatilization of solvent, the strand distance furthers, and can be tangled again by the big molecule that runs through mutually of solvent dilution under solution state, and the entanglement point between the big molecule can increase thereupon.Physical crosslinking point wherein is reversible, can eliminate by heating, and to be big molecule run through the mutually formation of the point of entanglement wherein, because the ultra-high molecular weight polyethylene molecular chain length, slack time is long, even therefore heating also is difficult to eliminate entanglement.The point that tangles too much can make the hot-stretch difficulty, and draw ratio descends, and occurs lousiness easily, and fibrous mechanical property descends.Therefore, in the dry spinning process, the volatilization that solution needs to limit solvent after spinnerets is extruded forms the hygrometric state precursor, takes then removing solvent behind the cooling curing, before the hot-stretch or remove solvent in the hot-stretch process.Removing the length that solvent has increased technological process behind the cooling curing, before the hot-stretch, reduced production efficiency; In the hot-stretch process, remove solvent, increased the solvent recovery difficulty, also have simultaneously and easily cause the spinning adhesion, degradation deficiency under the quality.
Japanese patent laid-open 7-238416 disclose a kind of in the dry spinning process actively solvent flashing to prepare the method for high-performance polyethylene fibres, concrete technology is: 5～50% ultra-high molecular weight polyethylene and the dissolving of 95～50% volatile solvent, add hot-extrudable after, through a spinning tube, the method of feeding thermal current makes the solvent evaporates more than 40% in the spinning tube, and residual solvent is removed in the process of hot-stretch.
This Japan Patent forms half-dried attitude precursor by actively remove partial solvent in spinning process, solved the problem of spinning adhesion, but because solvent all has volatilization in spinning and hot-stretch process, therefore this patent need be carried out fire-proof and explosion-proof processing and solvent recovery respectively on spinning section and stretcher, so just increase the difficulty of equipment investment and solvent recovery, be unfavorable for large-scale industrial production.
Researcher of the present invention is in application number is 01123737.6 patent, a kind of manufacture method of high-tenacity polyethylene fibre is disclosed, be included in the spinning technique process of preparation superhigh molecular weight polyethylene fibers, one semi-enclosed temperature-controlled area is set below spinnerets, and make the raw molecule amount, spinning solution concentration or spinning melt, the aperture of spinneret orifice, draw ratio and rate of extrusion are complementary, it is characterized in that by regulating the longitudinal stretching rheology after spinning solution or spinning melt are extruded, the precursor of removing the big molecular entanglement point of part and obtaining having suitable supramolecular structure, through after the road stretching obtain high-tenacity polyethylene fibre.
For 01123737.6 patent application, this patent mainly is to obtain the big molecular entanglement point of appropriateness by the coupling that adopts longitudinal stretching rheology and multiple parameter, obtain the high-strength polyethylene fiber of extended-chain configuration after the decahydronaphthalene solvent evaporates drying in the gel fiber again through hot-stretch, what wherein the volatile dry of solvent adopted in the gel fiber is prior art, does not therefore specifically describe dry mode and process.
Preparation technology for superhigh molecular weight polyethylene fibers, owing to form inflammable and explosive gas during the solvent for use volatilization, consider from safety and economic angle, must under sealing or condition of negative pressure, carry out solvent evaporates and recovery, and can reclaim solvent fast also be the problem that suitability for industrialized production faces.Simultaneously high-strength polyethylene fiber preparation technology's development trend also is guaranteeing under the high performance prerequisite, how shortened process, reduce production costs, to reach stable, safe suitability for industrialized production.
Summary of the invention
The object of the present invention is to provide a kind of manufacture method of new high-tenacity polyethylene fibre, this method has overcome above-mentioned deficiency, adopt longitudinal stretching rheology and the curing technology that combines, in the dry spinning process, form the dry state precursor that contains the big molecular entanglement point of appropriateness, make high-performance polyethylene fibres through hot-stretch again, when guaranteeing the excellent mechanical property of fiber, reduced the solvent evaporates operation, shortened technological process, enhance productivity, reduce equipment investment and production cost, and realize stable, safe suitability for industrialized production.
In order to realize purpose of the present invention, the manufacture method of a kind of high-tenacity polyethylene fibre of the present invention, comprise super high molecular polyethylene solution dry spinning process and hot-stretch process, it is characterized in that in the dry spinning process, after extruding from spinnerets, solution, forms the dry state precursor that contains the big molecular entanglement point of appropriateness through longitudinal stretching rheology and curing.
Described curing is under the double action of solvent evaporates and cooling, makes solution viscosity reach mobile limiting value and is solidified into silk.
Described super high molecular polyethylene solution dry spinning process is: ultra-high molecular weight polyethylene and is extruded into silk after solvent swell, dissolving, pass through longitudinal stretching rheology and curing again, forms the dry state precursor.
Furtherly, the dry spinning process is: ultra-high molecular weight polyethylene is carried out swelling in solvent, dissolving forms spinning solution; Extrude through spinnerets then and obtain the solution thread; The solution thread again through the longitudinal stretching rheology of first temperature controlled region and the curing of second temperature controlled region, is formed the dry state precursor.
Dry state precursor of the present invention is for almost removing the precursor of whole solvents, and its solvent evaporates amount is more than 95% of total solvent amount.
The present invention adopts longitudinal stretching rheology and the curing technology of combining to prepare high-tenacity polyethylene fibre, promptly under the double action of solvent evaporates and cooling, make solution viscosity reach mobile limiting value and when solidifying, formation contains the dry state precursor of the big molecular entanglement point of appropriateness, obtains having the high-tenacity polyethylene fibre of extended-chain configuration through hot-stretch with assurance.
Specifically, the longitudinal stretching deformation main purpose of first temperature controlled region is: utilize and to spin in the journey elongational flow of fiber axis before solidifying and be out of shape and remove part molecular entanglement point greatly, the macromolecular structure that runs through of part is removed in longitudinal stretching rheology after promptly extruding by spinning solution, reduce the entanglement point, thus had " the big molecular entanglement point of appropriateness " extend simultaneously and refinement the shish-kebab structure precursor.
Described " appropriateness big molecular entanglement point " described in detail in application number is 01123737.6 patent application, the formation that how much directly influences extended-chain configuration of big molecular entanglement point, just can't transmit tensile stress when point is very few if tangle in the precursor, and cause big molecular folding chain can not obtain stretching and orientation is stretched by the tie molecule between chain-folded lamellae; But the entanglement in the precursor is put and can be limited the development of macromolecular orientation and extended-chain configuration when too much, so need before hot-stretch, form precursor with the big molecular entanglement dot structure of appropriateness.
The curing of second temperature controlled region is in order to make the big molecular entanglement dot structure of the appropriateness that forms when the longitudinal stretching rheology reach mobile limiting value along with solution viscosity and to fix, owing to solidify the method that has adopted solvent evaporates and cooling to carry out simultaneously, therefore both can make solvent fully volatilization in spinning process, can guarantee that again the solution thread fully cools off, avoid big molecule to return and twine the new entanglement point of formation.
By above-mentioned technology, in spinning process, formed the dry state precursor that contains the big molecular entanglement point of appropriateness that is suitable for hot-stretch, having solved existing technology needs to carry out the problem of solvent evaporates after spinning process, shortened flow process, improved production efficiency, simultaneously because solvent is that the total solvent amount is more than 95% at the spinning process volatile quantity, even more than 99%, therefore only need to carry out solvent recovery in spinning process, solved the problem that existing process solvent reclaims difficulty, help carrying out the solvent recovery of economical and efficient, reduce capital expenditure and production cost, and realize stable, the suitability for industrialized production of safety.
Researcher of the present invention gropes through theory analysis and technology, the temperature of finding first temperature controlled region is controlled at that the solution temperature of ultra-high molecular weight polyethylene is above, below the autoignition temperature (the two is got than low value) of decomposition point or solvent, to be lower than its solution temperature following for well and the temperature of second temperature controlled region is controlled at, obtain the big molecular entanglement point of appropriateness in first temperature controlled region by the longitudinal stretching rheology, make solution viscosity be issued to mobile limiting value and solidify in the acting in conjunction of solvent evaporates and cooling in second temperature controlled region.
The present invention carries out longitudinal stretching in first temperature controlled region, the first temperature controlled region temperature is controlled at ultra-high molecular weight polyethylene solution temperature (T
s)～ultra-high molecular weight polyethylene decomposition temperature (T
d) in low 10 ℃ the scope, or be controlled at ultra-high molecular weight polyethylene solution temperature (T
s)～solvent autoignition temperature (T
f) in low 10 ℃ the scope, ceiling temperature is got in the two than low value; The first temperature controlled region length is 10～40cm; The longitudinal stretching rheology multiple of first temperature controlled region is 3～30 times.
Be cured in second temperature controlled region, the second temperature controlled region temperature is controlled at 30 ℃～ultra-high molecular weight polyethylene solution temperature (T
s) scope in, length is 1～6m, is preferably 3～5m; Second temperature controlled region can adopt one section temperature control or the control of multistage temperature; When adopting one section temperature control, the second temperature controlled region temperature is controlled at 50 ℃～120 ℃; When adopting the control of multistage temperature, the control of multistage temperature can be temperature control more than 2 sections or 2 sections, is preferably 2～4 sections, and the control of each section temperature can descend 10～30 ℃ piecemeal along the tow direction, or raises 10～30 ℃ piecemeal along the tow direction.
First temperature controlled region and second temperature controlled region are optional with electrical heating or thermal medium heating, and feed the inert gas that shields therein, as carbon dioxide or nitrogen etc.
Through after the above-mentioned spinning process, the solvent evaporates amount is more than 95% of total solvent amount, and is preferred more than 99%.Residual solvent can play plasticising in the hot-stretch process, reduce lousiness and end breakage rate, and what help stretching carries out smoothly; Along with the carrying out of hot-stretch, solvent volatilizees fully, does not contain solvent in the finished fiber.
The weight average molecular weight of ultra-high molecular weight polyethylene of the present invention can be 1 * 10
6～6 * 10
6, be preferably 3.5 * 10
6～5 * 10
6
The present invention adopts dry spinning, is guaranteeing that the boiling point of solvent and volatility are to select the major consideration of solvent for use under the deliquescent prerequisite, because the boiling point of solvent is too high, solvent is difficult to evaporate from fiber, influences spinning speed; Boiling point is low excessively, and solvent evaporates speed is too fast, influences fiberizing.Solvent of the present invention is preferably decahydronaphthalene for the carbon atom number is the hydrocarbon of 6-14.
The present invention's ultra-high molecular weight polyethylene in the dry spinning process need carry out swelling in solvent, dissolving forms spinning solution, and temperature is controlled between 60 ℃～100 ℃ when adopting described swelling, stirred 1～3 hour, described swelling can be carried out in reactor or other containers.
The mode of interior stirring of still or double screw extruder plasticizing dissolving is adopted in described dissolving, and temperature is controlled between 130 ℃～200 ℃ during dissolving; Easily produce rod-climbing effect owing to stir in the still, influence the uniformity that ultra-high molecular weight polyethylene dissolves in solvent, so should adopt double screw extruder when concentration is high, the twin-screw draw ratio is 30/1～60/1, rotating speed is 30～300r/min, is preferably 40/1～55/1,50～200r/min.
The weight percent concentration of super high molecular polyethylene solution of the present invention is 4～20%, and is preferred 4～16%, and the concentration of spinning solution can be regulated by the addition of solvent.
Described spinnerets draw ratio is 6/1～30/1, and the aperture is 0.6～1mm, and rate of extrusion is 0.5～50m/min, preferred 0.5～20m/min, more preferably 0.5～10m/min.Rate of extrusion is fast, and the velocity gradient of solution cross-sectional direction is big, is easy to generate the shear induced crystallization effect, make the degree of crystallinity of precursor higher, go out lousiness or broken end in the hot-stretch process easily, but rate of extrusion is slow, production efficiency is low, so need to select suitable rate of extrusion.
Described hot-stretch can select for use hot case or hot-rolling to stretch, and temperature is 120～150 ℃, and through 2～5 grades of stretchings, draw ratio is 4～20 times.Along with carrying out step by step of stretching, the crystallization of fiber and orientation are further perfect, and fusing point progressively improves, so draft temperature can raise step by step.
Recycling for the ease of solvent, the present invention can adopt solvent recovery unit in preparation process, be provided with this device in dry spinning section (comprising first temperature controlled region and second temperature controlled region), the principle that this retracting device adopts compression condensation-film to separate is this area common equipment.
In order to prevent the oxidative degradation of ultra-high molecular weight polyethylene, also be convenient to simultaneously processing, generally also need in raw material, to add with respect to the antioxidant of ultra-high molecular weight polyethylene weight 0.1～1% and 0.1～1% lubricant, described antioxidant is selected sterically hindered big phenols for use, be preferably 2, the 6-BHT, described lubricant is the fatty acid metal salt, is preferably aluminum stearate.
In order further to enhance productivity, adapt to industrialized development need, preparation method of the present invention can preferably adopt the processing technology of one-step method, be super high molecular polyethylene solution extrude-longitudinal stretching rheology-whole process of curing-hot-stretch carries out continuously, one step finished, and had so just reduced coiling, unwinding and feeding unit, can further enhance productivity, cut down finished cost, make the technology simple economy.Specifically, the one-step technology process is: ultra-high molecular weight polyethylene is carried out swelling in solvent, dissolving forms spinning solution; Extrude through spinnerets then and obtain the solution thread; The solution thread continuously through the longitudinal stretching rheology of first temperature controlled region and the curing of second temperature controlled region, is directly obtained high-tenacity polyethylene fibre through hot-stretch then.
The present invention adopts longitudinal stretching rheology and the curing technology of combining to prepare high-tenacity polyethylene fibre, and its fracture strength reaches 15～45g/d; Modulus is 500～1500g/d.
The method of testing that high-tenacity polyethylene fibre of the present invention adopts is as follows: fracture strength, modulus are with reference to JISL1013-1992.
The preparation method of high-tenacity polyethylene fibre of the present invention, on the basis of the disclosed longitudinal stretching deformation techniques of 01123737.6 patent application, under the acting in conjunction of solvent evaporates and cooling, finish solidification process when having increased the solution thread after second temperature controlled region makes the longitudinal stretching rheology, formation has the dry state precursor of the big molecular entanglement dot structure of appropriateness, obtains high-tenacity polyethylene fibre through hot-stretch again; The present invention adopts second temperature controlled region to finish the spinning solidification process, has reduced the solvent evaporates technical process after the dry spinning process, has shortened technological process, is easy to suitability for industrialized production.
The present invention compares with Japanese patent laid-open 7-238416, only need before hot-stretch, to carry out solvent recovery, solvent recovery unit is set, therefore the present invention is when guaranteeing the excellent mechanical property of fiber, not only shortened technological process, improve production efficiency, reduced equipment investment and production cost simultaneously, and can realize stable, safe suitability for industrialized production.
The high-tenacity polyethylene fibre of gained of the present invention has excellent mechanical property, can be applied to protection and defend equipment material, as shellproof, anti-stab, anti-cutting, safty shield, composite armour etc., and all kinds of rope, cable, sea farming net cage, fish for trawlnet, communication cable supporting material, superconducting insulation material, shock resistance container, extraordinary building reinforcing material, non-weaving cloth and paper reinforcing material, fiber reinforced composite board etc.
Preparation method of the present invention also can be applicable to the processing of other super high molecular weight polymers, as the spinning process of ultra-high molecular weight polyethylene alcohol.
Description of drawings
Fig. 1 is a high-tenacity polyethylene fibre manufacturing process flow diagram of the present invention
The specific embodiment
Further describe the present invention with embodiment below, help understanding, but described embodiment only is used to illustrate the present invention rather than restriction the present invention the present invention and advantage thereof, better effects if.
Embodiment 1
Selecting molecular weight for use is 1 * 10
6Ultra-high molecular weight polyethylene 200 gram, with itself and 800 gram decahydronaphthalene solvent (technical grades, B.P185～195 ℃) add in the stainless steel cauldron, open and stir, be heated to 60 ℃, swelling 1.5 hours, through the double screw extruder dissolving, the draw ratio of double screw extruder is 30/1 then, and screw speed is 60r/min, screw rod lysing segment temperature is 180 ℃, and formation concentration is 20% spinning solution; (draw ratio is 10/1 from spinneret orifice again, the aperture is 1mm) extrude with the speed of 1m/min, through a length is that first temperature controlled region (the inside center regional temperature is 150 ℃) of 20cm is carried out longitudinal stretching, mode of heating is electrical heating, draw ratio is 10 times, is second temperature-controlled area (the inside center regional temperature is 60 ℃) of 3m through length then, is cured, form the dry state precursor, solvent evaporates accounts for solvent total amount 95%; The dry state precursor carries out two-stage and stretches in 130 ℃ and 135 ℃ of hot casees, draw ratio is 10 times; Obtaining fracture strength is 25g/d, and modulus is the fiber of 1000g/d.
Embodiment 2
Selecting molecular weight for use is 3 * 10
6Ultra-high molecular weight polyethylene 80 gram, with itself and 920 gram decahydronaphthalene solvent (technical grades, B.P185～195 ℃) add in the stainless steel cauldron, open and stir, be heated to 90 ℃, swelling 2 hours, through double screw extruder plasticizing dissolving, the draw ratio of double screw extruder is 40/1 then, and screw speed is 50r/min, screw rod lysing segment temperature is 170 ℃, and formation concentration is 8% spinning solution; (draw ratio is 15/1 from spinneret orifice again, the aperture is 0.8mm) extrude with the speed of 3m/min, be that first temperature controlled region (the inside center regional temperature is 200 ℃) of 30cm is carried out longitudinal stretching continuously then through a length, mode of heating is electrical heating, draw ratio is 5 times (draw speed is 15m/min), is second temperature-controlled area (the inside center regional temperature is 50 ℃) of 4m through length again, is cured, form the dry state precursor, solvent evaporates accounts for 96% of total solvent amount; The dry state precursor directly carries out three grades of hot-stretchs in the hot case of 125 ℃, 130 ℃ and 135 ℃, draw ratio is 20 times (draw speed is 300m/min); Obtaining fracture strength is 45g/d; Modulus is the fiber of 1500g/d.
Embodiment 3
Selecting molecular weight for use is 5 * 10
6Ultra-high molecular weight polyethylene 50 gram, with itself and 950 gram decahydronaphthalene solvent (technical grades, B.P185～195 ℃) add in the stainless steel cauldron, open and stir, be heated to 100 ℃, swelling 2.5 hours, through double screw extruder plasticizing dissolving, the draw ratio of double screw extruder is 50/1 then, and screw speed is 30r/min, screw rod lysing segment temperature is 160 ℃, and formation concentration is 5% spinning solution; (draw ratio is 25/1 from spinneret orifice again, the aperture is 0.9mm) extrude with the speed of 0.5m/min, through a length is that first temperature controlled region (the inside center regional temperature is 220 ℃) of 40cm is carried out longitudinal stretching, hot jacket adopts the heating of high temperature biphenyl, draw ratio is 30 times, is second temperature-controlled area (the inside center regional temperature is 80 ℃) of 5m through length then, is cured, form the dry state precursor, solvent evaporates accounts for 98% of total solvent amount; The dry state precursor is to carry out 5 grades of stretchings in 140 ℃ of hot casees in temperature, and draw ratio is 8 times; Obtaining fracture strength is 35g/d; Modulus is the fiber of 1000g/d.
Embodiment 4
Selecting molecular weight for use is 3.5 * 10
6Ultra-high molecular weight polyethylene 160 gram, with itself and 840 gram decahydronaphthalene solvent (technical grades, B.P185-195 ℃) add in the stainless steel cauldron, open and stir, be heated to 100 ℃, swelling 3 hours, through double screw extruder plasticizing dissolving, the draw ratio of double screw extruder is 30/1 then, and screw speed is 60r/min, screw rod lysing segment temperature is 190 ℃, and formation concentration is 16% spinning solution; (draw ratio is 6/1 from spinneret orifice again, the aperture is 0.9mm) extrude with the speed of 5m/min, through a length is that first temperature controlled region (the inside center regional temperature is 195 ℃) of 25cm is carried out longitudinal stretching, and mode of heating is electrical heating, and draw ratio is 15 times, be second temperature-controlled area (two sections temperature controls of 5m then through length, gradient cooling, inside center regional temperature are respectively 110 ℃, 85 ℃), be cured, form the dry state precursor, solvent evaporates is 99% of a total solvent amount; The dry state precursor is to carry out 2 grades of stretchings in 130 ℃ of hot casees in temperature, and draw ratio is 5 times; Obtaining fracture strength is 25g/d; Modulus is the fiber of 750g/d.
Embodiment 5
With embodiment 1, different is also to add 2 of 0.5 gram in the ultra-high molecular weight polyethylene, the aluminum stearate of 6-BHT and 0.5 gram, and obtaining fracture strength is 29g/d; Modulus is the fiber of 1050g/d.
Embodiment 6
Selecting molecular weight for use is 6 * 10
6Ultra-high molecular weight polyethylene 40 gram, 0.4 gram 2, the aluminum stearate of 6-BHT and 0.4 gram adds itself and 960 gram decahydronaphthalenes in the stainless steel cauldrons, open and stir, be heated to 80 ℃, swelling 3 hours, be warming up to 140 ℃ of dissolvings then, formation concentration is 4% spinning solution; (draw ratio is 20/1 from spinneret orifice again, the aperture is 0.6mm) extrude with the speed of 2m/min, through a length is that first temperature-controlled area (the inside center regional temperature is 185 ℃) of 35cm carries out longitudinal stretching, and mode of heating is electrical heating, and draw ratio is 7 times, be second temperature-controlled area (three sections temperature controls of 5m then through length, gradient increased temperature, inside center regional temperature are respectively 60 ℃, 90 ℃, 120 ℃), be cured, form the dry state precursor, solvent evaporates is 96% of a total solvent amount; The dry state precursor is to carry out 2 grades of stretchings in 120 ℃ of hot casees in temperature, and draw ratio is 20 times; Obtaining fracture strength is 45g/d; Modulus is the fiber of 1500g/d.
Embodiment 7
With embodiment 2, different is that spinning solution is extruded from spinnerets with the speed of 50m/min, and vertically the draw piece multiple is 3 times (draw speed is 150m/min), and the dry state precursor is through three grades of stretchings, draw ratio is 10 times (draw speed is 1500m/min), and obtaining fracture strength is 25g/d; Modulus is the fiber of 700g/d.
Embodiment 8
With embodiment 2, different is that spinning solution is extruded from spinnerets with the speed of 30m/min, and the longitudinal stretching multiple is 5 times (draw speed is 150m/min), and the dry state precursor stretches through Pyatyi, draw ratio is 20 times (draw speed is 3000m/min), and obtaining fracture strength is 28g/d; Modulus is the fiber of 1000g/d.
Embodiment 9～13
| Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | ||
| Ultra-high molecular weight polyethylene | 2×10 6 | 2.5×10 6 | 4×10 6 | 1.5×10 6 | 5.5×10 6 | |
| Solvent | Decahydronaphthalene | Decahydronaphthalene | Decahydronaphthalene | Decahydronaphthalene | Decahydronaphthalene | |
| Antioxidant | 0.1%2, the 6-BHT | 0.6%2, the 6-BHT | 0.8%2, the 6-BHT | 1%2, the 6-BHT | ||
| Lubricant | 0.2% calcium stearate | 0.5% aluminum stearate | 1% barium stearate | 0.8% aluminum stearate | ||
| Swelling | Temperature (℃) | 70 | 70 | 85 | 65 | 95 |
| Time (h) | 1.5 | 2 | 3 | 2 | 2.5 | |
| Dissolving | Draw ratio | 35/1 | 45/1 | 50/1 | 55/1 | |
| Temperature (℃) | 145 (dissolvings in the still) | 150 | 185 | 180 | 200 | |
| Rotating speed (rpm) | 200 | 150 | 300 | 100 | ||
| Spinning solution concentration (%) | 11 | 9 | 7 | 14 | 4 | |
| Spinnerets | Draw ratio | 12/1 | 20/1 | 30/1 | 15/1 | 25/1 |
| Aperture (mm) | 0.9 | 0.8 | 0.7 | 1 | 0.6 | |
| Rate of extrusion (m/min) | 8 | 10 | 20 | 6 | 2 | |
| First temperature | Temperature (℃) | 130 | 180 | 230 | 240 | 100 |
| Length (cm) | 40 | 10 | 20 | 30 | 20 | |
| The control zone | Draw ratio | 20 | 15 | 10 | 25 | 3 |
| Second temperature-controlled area | Temperature (℃) | 50 | 90 | 80,100,120 (3 sections) | 120 | 120,90,60,30 (4 sections) |
| Length (m) | 3 | 2 | 4.5 | 1 | 6 | |
| Solvent evaporates amount (%) | 95 | 96 | 99 | 99 | 98 | |
| Hot-stretch | Temperature (℃) | 130 | 135 | 145 | 120 | 150 |
| Draw ratio | 5 | 8 | 15 | 4 | 20 | |
| Fiber | Fracture strength (g/d) | 20 | 28 | 30 | 15 | 42 |
| Modulus (g/d) | 800 | 800 | 1100 | 500 | 1400 |
Although the present invention has been done detailed explanation and has quoted some instantiations as proof, for a person skilled in the art, only otherwise leave that the spirit and scope of the present invention can be done various variations or correction is obvious.
Claims (10)
1, a kind of manufacture method of high-tenacity polyethylene fibre, comprise super high molecular polyethylene solution dry spinning process and hot-stretch process, it is characterized in that, described super high molecular polyethylene solution dry spinning process is: ultra-high molecular weight polyethylene is carried out swelling in solvent, dissolving forms spinning solution; Extrude through spinnerets then and obtain the solution thread; The solution thread again through the longitudinal stretching rheology of first temperature controlled region and the curing of second temperature controlled region, is formed the dry state precursor; Described being solidificated in second temperature controlled region carried out, and the second temperature controlled region temperature is controlled in the scope of 30 ℃～ultra-high molecular weight polyethylene solution temperature, and length is 1～6m; Second temperature controlled region adopts one section temperature control or the control of multistage temperature.
2, preparation method according to claim 1 is characterized in that, the described second temperature controlled region length is 3～5m.
3, preparation method according to claim 1 is characterized in that, when second temperature controlled region adopted one section temperature control, the second temperature controlled region temperature was controlled at 50 ℃～120 ℃.
4, preparation method according to claim 1 is characterized in that, described multistage temperature is controlled to be the control of 2～4 sections temperature, and the control of each section temperature can descend 10～30 ℃ piecemeal along the tow direction, or raises 10～30 ℃ piecemeal along the tow direction.
According to each described preparation method of claim 1-4, it is characterized in that 5, the weight average molecular weight of described ultra-high molecular weight polyethylene is 1 * 10
6～6 * 10
6Described solvent is 6～14 hydrocarbon for the carbon atom number; The weight percent concentration of described super high molecular polyethylene solution is 4～20%.
6, preparation method according to claim 5 is characterized in that, the weight average molecular weight of described ultra-high molecular weight polyethylene is 3.5 * 10
6～5 * 10
6Described solvent is a decahydronaphthalene; The weight percent concentration of described super high molecular polyethylene solution is 4～16%.
According to each described preparation method of claim 1-4, it is characterized in that 7, described spinnerets draw ratio is 6/1～30/1, the aperture is 0.6～1mm; Described spinnerets rate of extrusion is 0.5～50m/min.
8, preparation method according to claim 7 is characterized in that, described spinnerets rate of extrusion is 0.5～20m/min.
9, preparation method according to claim 8 is characterized in that, described spinnerets rate of extrusion is 0.5～10m/min.
10, according to each described preparation method of claim 1-4, it is characterized in that, described longitudinal stretching rheology is carried out in first temperature controlled region, the first temperature controlled region temperature is controlled in the scope of low 10 ℃ of ultra-high molecular weight polyethylene solution temperature～ultra-high molecular weight polyethylene decomposition temperature, or be controlled in the scope of low 10 ℃ of ultra-high molecular weight polyethylene solution temperature～solvent autoignition temperature, ceiling temperature is got in the two than low value; The first temperature controlled region length is 10～40cm, and the longitudinal stretching rheology multiple of first temperature controlled region is 3～30 times.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031563007A CN1300395C (en) | 2003-09-03 | 2003-09-03 | Manufacturing method of high strength polyethylene fiber |
Applications Claiming Priority (1)
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| CN100395386C (en) * | 2005-05-10 | 2008-06-18 | 东华大学 | Method of improving surface cohesion performance of relative molecular weight polyethylene |
| JP2010525184A (en) * | 2007-05-01 | 2010-07-22 | ディーエスエム アイピー アセッツ ビー．ブイ． | UHMWPE fiber and method for producing the same |
| CN101122051B (en) * | 2007-09-24 | 2010-04-14 | 湖南中泰特种装备有限责任公司 | Method for preparing low-titer high-strength high-modulus polyethylene fibre |
| EP2347041B1 (en) * | 2008-11-20 | 2013-05-08 | DSM IP Assets B.V. | Gel spun polyethylene fiber |
| US7964518B1 (en) * | 2010-04-19 | 2011-06-21 | Honeywell International Inc. | Enhanced ballistic performance of polymer fibers |
| CN101962820B (en) * | 2010-10-14 | 2012-01-18 | 刘阜东 | Superhigh molecular weight polyethylene monofilament and hot drawing processing method thereof |
| CN102653888B (en) * | 2011-03-02 | 2014-06-04 | 中国石油化工股份有限公司 | High-strength polyethylene fiber slurry allocation automatic control method |
| CN102226300B (en) * | 2011-06-07 | 2012-08-08 | 江苏六甲高分子材料有限公司 | Preparation method of high strength polyethylene fiber and special device thereof |
| CN103031615B (en) * | 2012-12-27 | 2014-12-03 | 中国纺织科学研究院 | High-strength polyethylene monofilament and preparation method thereof |
| CN104419996A (en) * | 2013-08-20 | 2015-03-18 | 中国石油化工股份有限公司 | Production method of ultrahigh molecular weight polyethylene fiber |
| CN104911722B (en) * | 2015-05-15 | 2017-09-15 | 上海化工研究院有限公司 | The method of precursor curing molding during ultra-high molecular weight polyethylene dry spinning |
| CN106555240B (en) * | 2016-11-23 | 2020-04-07 | 中国纺织科学研究院有限公司 | Preparation method of high-performance polyethylene fiber and fiber |
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| CN1077923C (en) * | 1999-08-19 | 2002-01-16 | 陈成泗 | Production process of high-strength high-modulus polyethylene fibre |
| CN1400342A (en) * | 2001-07-30 | 2003-03-05 | 中国石油化工股份有限公司 | Production method of high strength polyethylene fibre and fibre |
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| CN1077923C (en) * | 1999-08-19 | 2002-01-16 | 陈成泗 | Production process of high-strength high-modulus polyethylene fibre |
| CN1400342A (en) * | 2001-07-30 | 2003-03-05 | 中国石油化工股份有限公司 | Production method of high strength polyethylene fibre and fibre |
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