CN109853069A - A kind of melt-spinning preparation method of ultra high molecular weight polyethylene fiber - Google Patents
A kind of melt-spinning preparation method of ultra high molecular weight polyethylene fiber Download PDFInfo
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Abstract
The present invention relates to a kind of melt-spinning preparation methods of ultra high molecular weight polyethylene fiber, and a certain amount of solvent naphtha is added in a dispersion medium, and polymerization obtains the polyvinyl resin with super-high molecular weight containing solvent naphtha；By the polyvinyl resin with super-high molecular weight containing solvent naphtha directly through being equipped with melting extrusion under the three-screw extruder low temperature of spinneret, the slow-speed of revolution, melt extrusion obtains ultra high molecular weight polyethylene fiber through cooling, second level hot gas spring.Obtained ultra high molecular weight polyethylene fiber breaking strength 15cN/dtex-30cN/dtex, elongation at break 5%-10%.Compared with prior art, production procedure of the present invention is short, energy conservation and environmental protection, manufacturing cost are low, high-intensitive ultra high molecular weight polyethylene fiber can be prepared under the low temperature slow-speed of revolution, product can be widely applied to the weavings fields such as all kinds of rope braidings, fishing net braiding, industry cloth, industry band, it can also be used to defence and military and labor protection field.
Description
Technical field
The invention belongs to technical field of fibre production, the melting more particularly, to a kind of ultra high molecular weight polyethylene fiber is spun
Silk preparation method.
Background technique
Ultra high molecular weight polyethylene fiber is to be spinned by average molecular mass in 1,000,000 or more polyethylene
Fiber.It is another high-intensitive, high-modulus the high-performance fiber occurred after carbon fiber and aramid fiber, and with aramid fiber,
Carbon fiber is simultaneously known as current " the big tec fiber in the world three ", is important strategic materials and High-tech Material.
Currently, producing the main gel spinning of method of ultra high molecular weight polyethylene fiber in the world, including dry route is (main
Will be using decahydronaphthalene as solvent) and wet route (mainly using white oil as solvent) technique, two kinds of techniques all need solvent by supra polymer
Weight ethylene resin uniform dissolution, then spinning squeezes out, then by solvent removal, prepares high-strength high-modulus polyethylene fiber.Production stream
Journey is long, complex process, and energy consumption is high, has a degree of pollution to environment.
Have many patents and discloses the preparation method of ultra high molecular weight polyethylene fiber melt spinning.It is main to use addition
Low-molecular-weight polyolefin flow ability modifying agent carries out melt spinning by the effect of high temperature or high shear, and it is high to be unfavorable for preparation
Strong fiber.Chinese patent CN102002769B discloses method for preparing ultra-high molecular weight polyethylene fibers, by low density polyethylene (LDPE),
Linear low density polyethylene, polyolefin elastomer etc. are mixed with ultra-high molecular weight polyethylene carries out melt spinning, and this method increases
The molecular weight distribution width of ultra-high molecular weight polyethylene, although mixture mobility increases, the fiber ends defect of spinning
Increase, is difficult to obtain high-intensity fiber.Chinese patent CN101230501B and CN104862800A use 150-300 DEG C and 300- respectively
360 DEG C of high temperature is melted, and supermolecule weight northylen is easily degraded under high temperature and high screw speed shear action, influences fibre
Tie up performance.
Summary of the invention
The purpose of the present invention is to solve the above-mentioned problems and provides a kind of melting of ultra high molecular weight polyethylene fiber
Spinning preparation method, this method can achieve the purpose that melting, solution are twined and prepared under low temperature low sheraing.
The purpose of the present invention is achieved through the following technical solutions:
A kind of melt-spinning preparation method of ultra high molecular weight polyethylene fiber, method includes the following steps:
A. reaction kettle is heated and is dried, decentralized medium and co-catalyst is added after inert gas (such as argon gas) displacement, leads to
Enter ethylene and carry out first time stirring, later Venting ethylene, catalysts and solvents oil is added, is passed through ethylene while stirring for the second time
It is reacted, is cooled after reaction, filtered, be dried to obtain the polyvinyl resin with super-high molecular weight containing solvent naphtha；
B. by resin obtained in step a directly through three-screw extruder melting extrusion；
C. the melt air section water-bath cooling that will be squeezed out in step b, preliminary draft obtain as-spun fibre, carry out level-one later
Drawing-off, then second level drawing-off is carried out, obtain ultra high molecular weight polyethylene fiber.
Preferably, the solvent naphtha in the step a be selected from one of white oil, paraffin oil, kerosene or alkene mineral oil or
It is a variety of.Solvent naphtha is introduced in polymerization can uniformly mix with ultra-high molecular weight polyethylene on molecular scale, in supra polymer
Small molecule solvent oil is introduced between weight northylen macromolecular chain, can promote macromolecular chain disentanglement, during melt spinning,
Resin melts under low temperature, low sheraing effect, solution twines, molecularly oriented, easily prepared high intensity ultra high molecular weight polyethylene fiber.
Above-mentioned selected solvent naphtha is short-chain olefin class mixture, and molecular structure is similar with ultra-high molecular weight polyethylene, according to " phase patibhaga-nimitta
It is molten " principle, selected solvent naphtha is the solvent of ultra-high molecular weight polyethylene.It is few in ultra-high molecular weight polyethylene process
Lubricating action is played in the presence of amount small molecule solvent oil, is dispersed between ultra-high molecular weight polyethylene macromolecular chain, reduces big
The interaction force of molecule interchain, and then improve its mobility.It is further preferred that solvent naphtha is white oil, white oil forms substantially
For saturated hydrocarbon structure, the substances such as aromatic hydrocarbon, nitrogen, oxygen, sulphur are similar to zero, have good thermal stability and oxidation stability.Coal
Containing substances such as aromatic hydrocarbon, sulphur, nitrogen in oil, mineral oil, paraffin oil main component is the various n-alkanes composition of C10 to C18
Mixture, thermal stability is worse than white oil.
Preferably, the decentralized medium in the step a is selected from toluene, n-decane, n-hexane, dimethylbenzene, normal heptane or vapour
One of oil is a variety of.
Preferably, the co-catalyst in the step a is selected from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum
Or one of methylaluminoxane or a variety of, the catalyst are selected from metallocene catalyst or Nonmetallocene single-site catalyzed
One of agent is a variety of.Ultra-high molecular weight polyethylene prepared by metallocene catalyst, Nonmetallocene single site catalysts
Has the characteristics that narrow molecular weight distribution, the fiber ends defect of preparation is few, is more advantageous to spinning high strength fibre.
Preferably, the ethylene in the step a, decentralized medium, solvent naphtha, catalyst quality ratio are 100:(80-210):
(5-15): (0.001-0.005)；Co-catalyst, catalyst quality ratio are (0.005-0.015): 1.
Preferably, the heating temperature range of reaction kettle is 50-100 DEG C in the step a, dry for vacuum drying, drying
Time is 1-4h, and argon gas displacement number is 3 times, and first time mixing speed is 100-2000r/min, mixing time 0.5-5h,
Second of mixing speed is 300-1500r/min, and reaction time 1-8h cools to 0-20 DEG C, the ethylene being passed through twice
Pressure is 0.1-1.0MPa.
Preferably, the viscous of the polyvinyl resin with super-high molecular weight containing solvent naphtha being prepared in the step a is divided equally
Son amount is 1,000,000-600 ten thousand, molecular weight distribution 1-2.5.
Preferably, the draw ratio of three-screw extruder is (20-60) in the step b: 1, screw zones temperature is 140-
250 DEG C, screw speed 50-250r/min, screw extruder end flow channel length is 5-20cm, and spinneret draw ratio is (15-
30): 1.
It is further preferred that the three-screw extruder is three screw rod of parallel three screw rod or triangle disposition.Melt is in three spiral shells
Melt residence time is long in bar extruder, flow regime is increasingly complex, it is easier to which the macromolecule that preparation is uniformly dissolved, solution twines is molten
Body, and the three-screw extruder of low draw ratio can reach the melting of the double screw extruder of high length-diameter ratio, solution twines effect.Superelevation
Molecular weight polyethylene is easy degradation under high temperature high shear, influences properties of product.The present invention contains the super high molecular weight of solvent naphtha
Polyethylene is easy to melt-processed, can be 140-250 DEG C in screw zones temperature, under the conditions of screw speed is 50-250r/min
Melt spinning avoids excessive degradation phenomenon, the mechanical performance for keeping high molecular weight polyethylene fiber excellent.Superhigh molecular weight polyethylene
Alkene melt elasticity is significant, melt shear flow in screw rod, squeezes out from spinneret and is easy melt fracture.The present invention is by Screw Extrusion
It is 5-20cm that machine end flow channel length, which increases, and it is (15-30) that spinneret draw ratio, which increases: 1, make ultra-high molecular weight polyethylene melt
The elastic potential energy of storage discharges as far as possible, and the melt squeezed out from spinneret is avoided to rupture, and guarantees that strand surface is smooth, with
Convenient for further stretching.
Preferably, the length of melt air section is 1-5cm in the step c, and bath temperature is 10-90 DEG C, preliminary draft times
Number is 5-20 times, and level-one drawing temperature is 90-120 DEG C, and drafting multiple is 3-5 times, and second level drawing temperature is 110-140 DEG C, is led
Stretching multiple is 1-3 times.The ultra-high molecular weight polyethylene melt that solution twines squeezes out the solidification that should cool down rapidly through spinneret, and solution is twined orientation
Macromolecular " latching ", if air section is too long, it may occur that disorientation phenomenon.
Compared with prior art, the invention has the following advantages that
(1) solvent naphtha is introduced in ultra-high molecular weight polyethylene polymerization process first, solvent naphtha small molecule is dispersed in
Inside polyvinyl resin with super-high molecular weight, increase distance between strand, reduces model ylid bloom action power, and rise in molecule interchain
To lubricating action, Resin crystallization degree is reduced.
(2) supra polymer containing solvent naphtha prepared using metallocene catalyst or Nonmetallocene single site catalysts
Weight northylen viscosity average molecular weigh is in 1,000,000-600 ten thousand, molecular weight distribution 1-2.5, with soluble, mobile performance is high, divides greatly
Subchain legibility such as twines at the characteristics.
(3) ultra-high molecular weight polyethylene containing solvent naphtha is entered into three screw low-temperatures, under low speed state through long runner and
The spinneret of big L/D ratio squeezes out, is cooling, stretching the high-intensitive ultra high molecular weight polyethylene fiber of preparation.
(4) present invention reduces that degradation in ultra-high molecular weight polyethylene process, production procedure is short, energy conservation and environmental protection, system
It makes at low cost, high-intensitive ultra high molecular weight polyethylene fiber can be prepared under the low temperature slow-speed of revolution, product can be widely applied to all kinds of
The weaving fields such as rope braiding, fishing net braiding, industry cloth, industry band, it can also be used to defence and military and labor protection field.
Specific embodiment
The present invention is described in detail combined with specific embodiments below, but should be in no way restrictive.
Embodiment 1
A. reaction kettle is heated to 100 DEG C, is dried in vacuo 4h, then argon gas is replaced 3 times, be added 80 parts of gasoline,
0.0000075 part of methylaluminoxane is passed through ethylene 100r/min stirring 5h, ethylene pressure 1.0MPa, and Venting ethylene, is added later
0.001 part of metallocene catalyst, 5 parts of white oils are passed through 100 parts of ethylene, ethylene pressure under the stirring condition of 1500r/min
1.0MPa reacts 8h, cools to 20 DEG C, filtered, be dried to obtain the ultra-high molecular weight polyethylene containing solvent naphtha；
B. the three-screw extruder melting extrusion that resin step a obtained is directly 60:1 through draw ratio, screw zones
140-250 DEG C of temperature, screw speed 250r/min, screw extruder end flow channel length is 20cm, and spinneret draw ratio is
30:1；
C. the melt air segment length squeezed out in step b through spinneret is 5cm, into 60 DEG C of water-bath cooling, preliminary draft
Multiple is 20 times, obtains as-spun fibre；As-spun fibre carries out level-one drawing-off at 100 DEG C, and drafting multiple is 3 times, at 115 DEG C
Second level drawing-off is carried out, drafting multiple is 1.5 times, obtains ultra high molecular weight polyethylene fiber.
Resin and fibre property are as shown in table 1.
Embodiment 2
A. reaction kettle is heated to 50 DEG C, is dried in vacuo 1h, then argon gas is replaced 3 times, be added 210 parts of n-hexanes,
0.000025 part of triethyl aluminum is passed through ethylene 2000r/min stirring 0.5h, ethylene pressure 0.1MPa, and Venting ethylene, is added later
0.005 part of Nonmetallocene single site catalysts, 15 parts of kerosene are passed through 100 parts of ethylene, second under the stirring condition of 300r/min
Alkene pressure 0.1MPa reacts 1h, cools to 5 DEG C, filtered, be dried to obtain the superhigh molecular weight polyethylene containing solvent naphtha
Alkene；
B. the three-screw extruder melting extrusion that resin step a obtained is directly 20:1 through draw ratio, screw zones
140-250 DEG C of temperature, screw speed 50r/min, screw extruder end flow channel length be 5cm, spinneret draw ratio 15:
1；
C. the melt air segment length squeezed out in step b through spinneret is 1cm, into 20 DEG C of water-bath cooling, preliminary draft
Multiple is 5 times, obtains as-spun fibre；As-spun fibre carries out level-one drawing-off at 115 DEG C, and drafting multiple is 5 times, at 135 DEG C
Second level drawing-off is carried out, drafting multiple is 3 times, obtains ultra high molecular weight polyethylene fiber.
Resin and fibre property are as shown in table 1.
Embodiment 3
A. reaction kettle is heated to 80 DEG C, is dried in vacuo 2h, then argon gas is replaced 3 times, be added 120 portions of normal heptanes,
0.00003 part of methylaluminoxane is passed through ethylene 500r/min stirring 3h, ethylene pressure 0.5MPa, and Venting ethylene, is added later
0.003 part of metallocene catalyst, 10 parts of paraffin oils are passed through 100 parts of ethylene, ethylene pressure under the stirring condition of 1000r/min
1.0MPa reacts 4h, cools to 10 DEG C, filtered, be dried to obtain the ultra-high molecular weight polyethylene containing solvent naphtha；
B. the three-screw extruder melting extrusion that resin step a obtained is directly 50:1 through draw ratio, screw zones
140-250 DEG C of temperature, screw speed 150r/min, screw extruder end flow channel length is 10cm, and spinneret draw ratio is
20:1；
C. the melt air segment length squeezed out in step b through spinneret is 3cm, into 30 DEG C of water-bath cooling, preliminary draft
Multiple is 15 times, obtains as-spun fibre；As-spun fibre carries out level-one drawing-off at 110 DEG C, and drafting multiple is 3 times, at 125 DEG C
Second level drawing-off is carried out, drafting multiple is 2 times, obtains ultra high molecular weight polyethylene fiber.
Resin and fibre property are as shown in table 1.
Embodiment 4
A. reaction kettle is heated to 70 DEG C, is dried in vacuo 2h, then argon gas is replaced 3 times, and 150 parts of gasoline, 0.00004 are added
Part trimethyl aluminium is passed through ethylene 1000r/min stirring 3h, ethylene pressure 1.0MPa, and Venting ethylene, is added 0.005 part of cyclopentadienyl later
Metallic catalyst, 9 parts of white oils are passed through 100 parts of ethylene under the stirring condition of 1200r/min, and ethylene pressure 0.8MPa reacts 4h,
It cools to 15 DEG C, is filtered, is dried to obtain the ultra-high molecular weight polyethylene containing solvent naphtha；
B. the three-screw extruder melting extrusion that resin step a obtained is directly 30:1 through draw ratio, screw zones
140-250 DEG C of temperature, screw speed 100r/min, screw extruder end flow channel length is 15cm, and spinneret draw ratio is
25:1；
C. the melt air segment length squeezed out in step b through spinneret is 2cm, into 30 DEG C of water-bath cooling, preliminary draft
Multiple is 15 times, obtains as-spun fibre；As-spun fibre carries out level-one drawing-off at 100 DEG C, and drafting multiple is 4 times, at 125 DEG C
Second level drawing-off is carried out, drafting multiple is 2 times, obtains ultra high molecular weight polyethylene fiber.
Resin and fibre property are as shown in table 1.
Embodiment 5
A. reaction kettle is heated to 100 DEG C, is dried in vacuo 3h, then argon gas is replaced 3 times, and 80 parts of gasoline, 0.00004 are added
Part methylaluminoxane is passed through ethylene 1500r/min stirring 6h, ethylene pressure 1.0MPa, and Venting ethylene, is added 0.005 part later
Metallocene catalyst, 12 parts of white oils are passed through 100 parts of ethylene, ethylene pressure 0.7MPa, reaction under the stirring condition of 800r/min
5h cools to 20 DEG C, is filtered, is dried to obtain the ultra-high molecular weight polyethylene containing solvent naphtha；
B. the three-screw extruder melting extrusion that resin step a obtained is directly 40:1 through draw ratio, screw zones
140-250 DEG C of temperature, screw speed 80r/min, screw extruder end flow channel length is 20cm, and spinneret draw ratio is
20:1；
C. the melt air segment length squeezed out in step b through spinneret is 2cm, into 40 DEG C of water-bath cooling, preliminary draft
Multiple is 15 times, obtains as-spun fibre；As-spun fibre carries out level-one drawing-off at 110 DEG C, and drafting multiple is 4 times, at 125 DEG C
Second level drawing-off is carried out, drafting multiple is 2 times, obtains ultra high molecular weight polyethylene fiber.
Resin and fibre property are as shown in table 1.
Embodiment 6
A. reaction kettle is heated to 80 DEG C, is dried in vacuo 4h, then argon gas is replaced 3 times, be added 100 parts of gasoline,
0.000015 part of methylaluminoxane is passed through ethylene 800r/min stirring 2h, ethylene pressure 1.0MPa, and Venting ethylene, is added later
0.001 part of metallocene catalyst, 10 parts of white oils are passed through 100 parts of ethylene, ethylene pressure under the stirring condition of 1500r/min
1.0MPa reacts 8h, cools to 10 DEG C, filtered, be dried to obtain the ultra-high molecular weight polyethylene containing solvent naphtha；
B. the three-screw extruder melting extrusion that resin step a obtained is directly 30:1 through draw ratio, screw zones
140-250 DEG C of temperature, screw speed 100r/min, screw extruder end flow channel length is 20cm, and spinneret draw ratio is
20:1；
C. the melt air segment length squeezed out in step b through spinneret is 3cm, into 50 DEG C of water-bath cooling, preliminary draft
Multiple is 15 times, obtains as-spun fibre；As-spun fibre carries out level-one drawing-off at 110 DEG C, and drafting multiple is 3 times, at 130 DEG C
Second level drawing-off is carried out, drafting multiple is 2 times, obtains ultra high molecular weight polyethylene fiber.
Resin and fibre property are as shown in table 1.
Embodiment 7
A. reaction kettle is heated to 80 DEG C, is dried in vacuo 4h, then argon gas is replaced 3 times, is added 100 parts by toluene, the positive last of the ten Heavenly stems
Mixture, the 0.0000075 part of mixture being made of triisobutyl aluminium and trioctylaluminum of alkane and dimethylbenzene composition, are passed through ethylene
1200r/min stirs 2h, ethylene pressure 1.0MPa, and Venting ethylene, is added 0.001 part of metallocene catalyst, 10 parts of alkene later
Mineral oil, 100 parts of ethylene are passed through under the stirring condition of 1500r/min, and ethylene pressure 1.0MPa reacts 8h, cools to 0
DEG C, it filtered, be dried to obtain the ultra-high molecular weight polyethylene containing solvent naphtha；
B. the three-screw extruder melting extrusion that resin step a obtained is directly 30:1 through draw ratio, screw zones
140-250 DEG C of temperature, screw speed 100r/min, screw extruder end flow channel length is 20cm, and spinneret draw ratio is
20:1；
C. the melt air segment length squeezed out in step b through spinneret is 3cm, into 50 DEG C of water-bath cooling, preliminary draft
Multiple is 15 times, obtains as-spun fibre；As-spun fibre carries out level-one drawing-off at 110 DEG C, and drafting multiple is 3 times, at 130 DEG C
Second level drawing-off is carried out, drafting multiple is 1 times, obtains ultra high molecular weight polyethylene fiber.
Resin and fibre property are as shown in table 1.
Embodiment 8
A. reaction kettle is heated to 80 DEG C, is dried in vacuo 4h, then argon gas is replaced 3 times, be added 100 parts of gasoline,
0.000015 part of methylaluminoxane is passed through ethylene 800r/min stirring 2h, ethylene pressure 1.0MPa, and Venting ethylene, is added later
0.001 part of metallocene catalyst, 10 parts of white oils are passed through 100 parts of ethylene, ethylene pressure under the stirring condition of 1500r/min
1.0MPa reacts 8h, cools to 10 DEG C, filtered, be dried to obtain the ultra-high molecular weight polyethylene containing solvent naphtha；
B. the three-screw extruder melting extrusion that resin step a obtained is directly 30:1 through draw ratio, screw zones
140-250 DEG C of temperature, screw speed 100r/min, screw extruder end flow channel length is 20cm, and spinneret draw ratio is
20:1；
C. the melt air segment length squeezed out in step b through spinneret is 3cm, into 10 DEG C of water-bath cooling, preliminary draft
Multiple is 15 times, obtains as-spun fibre；As-spun fibre carries out level-one drawing-off at 90 DEG C, and drafting multiple is 3 times, at 110 DEG C
Second level drawing-off is carried out, drafting multiple is 2 times, obtains ultra high molecular weight polyethylene fiber.
Resin and fibre property are as shown in table 1.
Embodiment 9
A. reaction kettle is heated to 80 DEG C, is dried in vacuo 4h, then argon gas is replaced 3 times, be added 100 parts of gasoline,
0.000015 part of methylaluminoxane is passed through ethylene 800r/min stirring 2h, ethylene pressure 1.0MPa, and Venting ethylene, is added later
0.001 part of metallocene catalyst, 10 parts of white oils are passed through 100 parts of ethylene, ethylene pressure under the stirring condition of 1500r/min
1.0MPa reacts 8h, cools to 10 DEG C, filtered, be dried to obtain the ultra-high molecular weight polyethylene containing solvent naphtha；
B. the three-screw extruder melting extrusion that resin step a obtained is directly 30:1 through draw ratio, screw zones
140-250 DEG C of temperature, screw speed 100r/min, screw extruder end flow channel length is 20cm, and spinneret draw ratio is
20:1；
C. the melt air segment length squeezed out in step b through spinneret is 3cm, into 90 DEG C of water-bath cooling, preliminary draft
Multiple is 15 times, obtains as-spun fibre；As-spun fibre carries out level-one drawing-off at 120 DEG C, and drafting multiple is 3 times, at 140 DEG C
Second level drawing-off is carried out, drafting multiple is 2 times, obtains ultra high molecular weight polyethylene fiber.
Resin and fibre property are as shown in table 1.
Embodiment 10
A. reaction kettle is heated to 80 DEG C, is dried in vacuo 4h, then argon gas is replaced 3 times, be added 100 parts of gasoline,
0.000015 part of methylaluminoxane is passed through ethylene 800r/min stirring 2h, ethylene pressure 1.0MPa, and Venting ethylene, is added later
0.001 part of metallocene catalyst, 10 parts of white oils are passed through 100 parts of ethylene, ethylene pressure under the stirring condition of 1500r/min
1.0MPa reacts 8h, cools to 10 DEG C, filtered, be dried to obtain the ultra-high molecular weight polyethylene containing solvent naphtha；
B. the three-screw extruder melting extrusion that resin step a obtained is directly 30:1 through draw ratio, screw zones
140-250 DEG C of temperature, screw speed 100r/min, screw extruder end flow channel length is 20cm, and spinneret draw ratio is
20:1；
C. the melt air segment length squeezed out in step b through spinneret is 3cm, into 10 DEG C of water-bath cooling, preliminary draft
Multiple is 15 times, obtains as-spun fibre；As-spun fibre carries out level-one drawing-off at 100 DEG C, and drafting multiple is 3 times, at 130 DEG C
Second level drawing-off is carried out, drafting multiple is 1.5 times, obtains ultra high molecular weight polyethylene fiber.
Resin and fibre property are as shown in table 1.
The resin and fibre property list that 1 embodiment 1-10 of table is prepared
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. a kind of melt-spinning preparation method of ultra high molecular weight polyethylene fiber, which is characterized in that be added in a dispersion medium
A certain amount of solvent naphtha, polymerization obtain the polyvinyl resin with super-high molecular weight containing solvent naphtha；By the supra polymer containing solvent naphtha
Weight ethylene resin is directly through being equipped with melting extrusion under the three-screw extruder low temperature of spinneret, the slow-speed of revolution, and melt extrusion is through cold
But, second level hot gas spring obtains ultra high molecular weight polyethylene fiber.
2. a kind of melt-spinning preparation method of ultra high molecular weight polyethylene fiber according to claim 1, feature exist
In, comprising the following steps:
A. reaction kettle is heated and is dried, decentralized medium and co-catalyst are added after inert gas replacement, be passed through ethylene and carry out the
Primary stirring, Venting ethylene, is added catalysts and solvents oil and stir for the second time, while being passed through ethylene and being reacted later,
It cools after reaction, is filtered, is dried to obtain the polyvinyl resin with super-high molecular weight containing solvent naphtha；
B. resin step a obtained is directly through three-screw extruder melting extrusion；
C. melt air section water-bath cooling step b squeezed out, obtains as-spun fibre, successively carries out level-one drawing-off, two later
Grade drawing-off, obtains ultra high molecular weight polyethylene fiber.
3. a kind of melt-spinning preparation method of ultra high molecular weight polyethylene fiber according to claim 2, feature exist
In solvent naphtha described in step a is selected from one of white oil, paraffin oil, kerosene or alkene mineral oil or a variety of.
4. a kind of melt-spinning preparation method of ultra high molecular weight polyethylene fiber according to claim 2, feature exist
In, decentralized medium described in step a be selected from one of toluene, n-decane, n-hexane, dimethylbenzene, normal heptane or gasoline or
It is a variety of.
5. a kind of melt-spinning preparation method of ultra high molecular weight polyethylene fiber according to claim 2, feature exist
In co-catalyst described in step a is selected from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum or methylaluminoxane
One of or it is a variety of, the catalyst be selected from one of metallocene catalyst or Nonmetallocene single site catalysts or
Two kinds.
6. a kind of melt-spinning preparation method of ultra high molecular weight polyethylene fiber according to claim 2, feature exist
In ethylene described in step a, decentralized medium, solvent naphtha, catalyst quality ratio are 100:(80-210): (5-15):
(0.001-0.005)；Co-catalyst, catalyst quality ratio are (0.005-0.015): 1.
7. a kind of melt-spinning preparation method of ultra high molecular weight polyethylene fiber according to claim 2, feature exist
In the heating temperature of reaction kettle is 50-100 DEG C in step a, and dry to be dried in vacuo, drying time 1-4h is stirred for the first time
Speed is 100-2000r/min, and mixing time 0.5-5h, second of mixing speed is 300-1500r/min, and the reaction time is
1-8h cools to 0-20 DEG C, and the ethylene pressure being passed through twice is 0.1-1.0MPa.
8. a kind of melt-spinning preparation method of ultra high molecular weight polyethylene fiber according to claim 2, feature exist
In the viscosity average molecular weigh for the polyvinyl resin with super-high molecular weight containing solvent naphtha being prepared in step a is 1,000,000-600
Ten thousand, molecular weight distribution 1-2.5.
9. a kind of melt-spinning preparation method of ultra high molecular weight polyethylene fiber according to claim 2, feature exist
In the draw ratio of three-screw extruder described in step b is (20-60): 1, screw zones temperature is 140-250 DEG C, and screw rod turns
Speed is 50-250r/min, and screw extruder end flow channel length is 5-20cm, and spinneret draw ratio is (15-30): 1.
10. a kind of melt-spinning preparation method of ultra high molecular weight polyethylene fiber according to claim 2, feature exist
It is 1-5cm in, the length of melt air section described in step c, bath temperature is 10-90 DEG C, and pre-draft multiple is 5-20 times, one
Grade drawing temperature is 90-120 DEG C, and drafting multiple is 3-5 times, and second level drawing temperature is 110-140 DEG C, and drafting multiple is 1-3 times.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111101217A (en) * | 2020-01-19 | 2020-05-05 | 上海化工研究院有限公司 | High-thermal-conductivity ultra-high molecular weight polyethylene fiber and preparation method thereof |
| CN111206296A (en) * | 2020-03-17 | 2020-05-29 | 东方交联电力电缆有限公司 | Preparation method of ultra-high molecular weight polyethylene and isotactic polypropylene blend ultra-tensile strength fiber |
| CN111733465A (en) * | 2020-06-24 | 2020-10-02 | 上海化工研究院有限公司 | High-strength polyethylene fiber melt spinning method and device |
| CN114293276A (en) * | 2021-12-27 | 2022-04-08 | 山东爱地高分子材料有限公司 | Method, fiber and fabric for reducing doubling rate of ultra-high molecular weight polyethylene fiber in manufacturing process |
| CN114805868A (en) * | 2022-04-06 | 2022-07-29 | 浙江中聚材料有限公司 | Polyolefin fiber reinforced layer and application thereof in solar cell adhesive film |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731697A (en) * | 2011-04-07 | 2012-10-17 | 中国石油化工股份有限公司 | Method for preparing polyethylene resin being easy to process and with ultra-high molecular weight |
| CN103305954A (en) * | 2013-07-01 | 2013-09-18 | 浙江大学 | Method for preparing ultra-high molecular weight polyethylene fiber |
| CN104846451A (en) * | 2015-06-09 | 2015-08-19 | 淄博美标高分子纤维有限公司 | Method for directly preparing ultra-high molecular weight polyethylene fibers |
| CN106117756A (en) * | 2016-08-05 | 2016-11-16 | 上海化工研究院 | A kind of preparation method of injection grade ultra-high molecular weight polyethylene |
| CN108754638A (en) * | 2018-05-11 | 2018-11-06 | 九力绳缆有限公司 | A kind of preparation method of ultra high molecular polyethylene fiber |
-
2019
- 2019-03-26 CN CN201910234628.0A patent/CN109853069B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731697A (en) * | 2011-04-07 | 2012-10-17 | 中国石油化工股份有限公司 | Method for preparing polyethylene resin being easy to process and with ultra-high molecular weight |
| CN103305954A (en) * | 2013-07-01 | 2013-09-18 | 浙江大学 | Method for preparing ultra-high molecular weight polyethylene fiber |
| CN104846451A (en) * | 2015-06-09 | 2015-08-19 | 淄博美标高分子纤维有限公司 | Method for directly preparing ultra-high molecular weight polyethylene fibers |
| CN106117756A (en) * | 2016-08-05 | 2016-11-16 | 上海化工研究院 | A kind of preparation method of injection grade ultra-high molecular weight polyethylene |
| CN108754638A (en) * | 2018-05-11 | 2018-11-06 | 九力绳缆有限公司 | A kind of preparation method of ultra high molecular polyethylene fiber |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111101217A (en) * | 2020-01-19 | 2020-05-05 | 上海化工研究院有限公司 | High-thermal-conductivity ultra-high molecular weight polyethylene fiber and preparation method thereof |
| CN111206296A (en) * | 2020-03-17 | 2020-05-29 | 东方交联电力电缆有限公司 | Preparation method of ultra-high molecular weight polyethylene and isotactic polypropylene blend ultra-tensile strength fiber |
| CN111733465A (en) * | 2020-06-24 | 2020-10-02 | 上海化工研究院有限公司 | High-strength polyethylene fiber melt spinning method and device |
| CN114293276A (en) * | 2021-12-27 | 2022-04-08 | 山东爱地高分子材料有限公司 | Method, fiber and fabric for reducing doubling rate of ultra-high molecular weight polyethylene fiber in manufacturing process |
| CN114805868A (en) * | 2022-04-06 | 2022-07-29 | 浙江中聚材料有限公司 | Polyolefin fiber reinforced layer and application thereof in solar cell adhesive film |
| CN114805868B (en) * | 2022-04-06 | 2024-05-14 | 浙江中聚材料有限公司 | Polyolefin fiber reinforced layer and application thereof in solar cell adhesive film |
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