CN111270329B - Coarse monofilament ultra-high molecular weight polyethylene fiber and preparation method and application thereof - Google Patents
Coarse monofilament ultra-high molecular weight polyethylene fiber and preparation method and application thereof Download PDFInfo
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
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Abstract
The invention provides a preparation method of thick monofilament ultra-high molecular weight polyethylene fibers, which comprises the following steps: a) mixing solvent oil and ultrahigh molecular weight polyethylene powder to obtain spinning stock solution; the swelling ratio of the spinning solution is 1.1-1.8; b) spinning, nozzle drafting and quick cooling are carried out on the spinning stock solution obtained in the step a) in sequence to obtain a gelatinized pre-oriented tow; the drafting multiple of the spray head is 5-30 times; c) carrying out hot drawing on the gelatinized pre-oriented tows obtained in the step b) to obtain coarse monofilament ultra-high molecular weight polyethylene fibers; the multiple of the hot drawing is 25 to 46.25 times. The preparation method provided by the invention obviously improves the mechanical property of the finished fiber on the basis of ensuring that the product meets the requirement of the coarse monofilament by controlling the swelling ratio of the spinning solution and matching with the subsequent process conditions of firstly amplifying the drafting multiple and then reducing the drafting multiple; the obtained product has very high strength and modulus at the same time, and meets the performance requirements of the fiber used as a bulletproof special material.
Description
Technical Field
The invention relates to the technical field of ultra-high molecular weight polyethylene fibers, in particular to a thick monofilament ultra-high molecular weight polyethylene fiber and a preparation method and application thereof.
Background
Ultra-high molecular weight polyethylene fiber was produced in 1979 and is the third highest performance fiber appearing after carbon fiber and aramid fiber. The ultrahigh molecular weight polyethylene fiber has a molecular structure of (-CH) 2 -CH 2 -) n -) very simple ultra-high molecular weight polyethylene (UHMWPE) is used as raw material, and a novel jelly spinning method is adopted to make the fiber form a special aggregation state structure, so that the strength of the fiber is 15 times of that of a steel wire under the same weight; the key technical core is that the method removes the serious entanglement of macromolecules in the spinning solution by controlling the entanglement point density of UHMWPE and keeps the macromolecules in the gel forming processAnd in an unwrapped state, thereby realizing the super-stretch of the jelly glue fiber and forming the fiber with high crystallinity and high orientation mainly based on a straight chain crystalline structure.
Since the fiber appeared to the 90 s of the last century, only DSM Dyneema company and United states Honeywell company in the Netherlands have mass production technology internationally, but technical blockade has been implemented in China for a long time, and the two companies do not export technology and equipment to China and do not sell high-end products to China market like carbon fiber. The DSM Dyneema company in the netherlands has evolved over nearly 40 years from the original commercial SK25 series, gradually deriving SK60, SK65, SK75, SK76, SK78, SK90 to the now highest SK99 series. The performance is continuously improved, the yield is continuously enlarged, and the device is in monopoly in the international market. In addition, for better occupation of the American and Asian markets, the Dyneema fiber production line is established in the United states by DSM Dyneema company in 1994, and is established with Dongyuan textile (Toyoba) which is the largest textile enterprise in Japan, the Osaka capital in Japan, and the Dyneema fiber production line of the company is about 10000 tons at present. The Honeywell company in the United states purchases the patent of the Dutch company in the early period, invests huge capital and has own patent technology through secondary development, the Spectra900 starts to gradually push out the Spectra1000 and the Spectra2000, and the capacity of the company is about 3000 tons at present. With the continuous expansion of the application field, the requirements on the mechanical properties of UHMWPE fibers are higher and higher. Particularly, the proportion of the protective material in the application field is more than 50 percent, and most of the field is occupied by foreign enterprises.
Although the gel spinning process is basically adopted in China since the development and production of UHMWPE fibers are carried out in the late nineties, products with the performance similar to Dyneema SK75 can be produced through continuous development and technical innovation in recent years, the product performance, particularly the fibers serving as special bulletproof materials, cannot reach the level of the strength of not less than 35cN/dtex and the modulus of not less than 1200cN/dtex due to the limitations of equipment precision, production stability, key technology and other conditions.
Disclosure of Invention
In view of this, the present invention aims to provide a coarse monofilament ultra-high molecular weight polyethylene fiber, a preparation method and an application thereof, and the coarse monofilament ultra-high molecular weight polyethylene fiber obtained by the preparation method provided by the present invention has very high strength and modulus, and meets the performance requirements of the fiber as a special material for bulletproof.
The invention provides a preparation method of coarse monofilament ultra-high molecular weight polyethylene fibers, which comprises the following steps:
a) mixing solvent oil and ultrahigh molecular weight polyethylene powder to obtain spinning stock solution; the swelling ratio of the spinning solution is 1.1-1.8;
b) spinning, nozzle drafting and quick cooling are carried out on the spinning stock solution obtained in the step a) in sequence to obtain a gelatinized pre-oriented tow; the drafting multiple of the spray head is 5-30 times;
c) carrying out hot drawing on the gelatinized pre-oriented tows obtained in the step b) to obtain coarse monofilament ultra-high molecular weight polyethylene fibers;
the hot drawing multiple is 25 to 46.25 times.
Preferably, the ultra-high molecular weight polyethylene powder in step a) has an intrinsic viscosity of 19dl/g to 35dl/g, a molecular weight of 400 ten thousand g/mol to 900 ten thousand g/mol, a particle size of 75 μm to 100 μm, and a bulk density of 0.4g/cm 3 ～0.5g/cm 3 。
Preferably, the mixing mode in the step a) is stirring; the stirring speed is 20rpm to 80rpm, the temperature is 100 ℃ to 120 ℃, and the time is 30min to 120 min.
Preferably, the spinning process in step b) is specifically:
b1) shearing, uniformly mixing and extruding the spinning solution obtained in the step a) in a double-screw extruder to obtain a first spinning solution; the screw rotating speed of the double-screw extruder is 200 rpm-300 rpm, and the melting temperature is 280 ℃ to 330 ℃;
b2) extruding the first spinning solution obtained in the step b1) through a spinneret plate to obtain a second spinning solution; the aperture of the spinneret orifice on the spinneret plate is 0.8 mm-2 mm.
Preferably, the quick cooling time in the step b) is 0.1 s-0.3 s, and the temperature difference is 255-305 ℃.
Preferably, the hot drawing process in step c) is specifically:
c1) standing the gelatinized pre-oriented tows obtained in the step b), and sequentially performing pre-drafting, extraction and drying to obtain dry gel yarns;
c2) and d) sequentially carrying out positive drafting and negative drafting on the xerogel filaments obtained in the step c1) to obtain the thick monofilament ultrahigh molecular weight polyethylene fibers.
Preferably, the pre-draft in step c1) is 3.1 to 6.1 times.
Preferably, said positive draft in step c2) comprises a three-stage draft; the temperature of the first stage of drafting is 121-130 ℃, and the multiple is 3.5-5 times; the temperature of the second-stage drafting is 131-140 ℃, and the multiple is 1.2-1.8 times; the temperature of the third stage of drafting is 141-150 ℃, and the multiple is 1.3-1.4 times;
the temperature of the negative drafting is 95-105 ℃, and the multiple is 0.89-0.91.
The invention also provides a thick monofilament ultra-high molecular weight polyethylene fiber prepared by the preparation method of the technical scheme.
The invention also provides an application of the thick monofilament ultra-high molecular weight polyethylene fiber in the technical scheme as a bulletproof special material.
The invention provides a preparation method of thick monofilament ultra-high molecular weight polyethylene fibers, which comprises the following steps: a) mixing solvent oil and ultrahigh molecular weight polyethylene powder to obtain spinning stock solution; the swelling ratio of the spinning solution is 1.1-1.8; b) spinning, nozzle drafting and quick cooling are carried out on the spinning stock solution obtained in the step a) in sequence to obtain a gelatinized pre-oriented tow; the drafting multiple of the spray head is 5-30 times; c) carrying out hot drawing on the gelatinized pre-oriented tows obtained in the step b) to obtain coarse monofilament ultra-high molecular weight polyethylene fibers; the multiple of the hot drawing is 25 to 46.25 times. Compared with the prior art, the preparation method provided by the invention has the advantages that by controlling the swelling ratio of the spinning solution and matching with the subsequent process conditions of firstly amplifying the drafting multiple and then reducing the drafting multiple, the mechanical property of the finished fiber is obviously improved on the basis of ensuring that the product meets the requirement of coarse monofilaments; the obtained coarse monofilament ultra-high molecular weight polyethylene fiber has very high strength and modulus, and meets the performance requirements of the fiber serving as a bulletproof special material. Experimental results show that the monofilament titer of the coarse monofilament ultrahigh molecular weight polyethylene fiber obtained by the preparation method provided by the invention is greater than 3D, the strength is more than 36cN/dtex, and the modulus is more than 1300 cN/dtex.
In addition, the preparation method provided by the invention has high efficiency and good stability, and is suitable for large-scale production.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below with reference to embodiments of the present invention, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention provides a preparation method of thick monofilament ultra-high molecular weight polyethylene fibers, which comprises the following steps:
a) mixing solvent oil and ultrahigh molecular weight polyethylene powder to obtain spinning stock solution; the swelling ratio of the spinning solution is 1.1-1.8;
b) spinning, nozzle drafting and quick cooling are carried out on the spinning stock solution obtained in the step a) in sequence to obtain a gelatinized pre-oriented tow; the drafting multiple of the spray head is 5-30 times;
c) carrying out hot drawing on the gelatinized pre-oriented tows obtained in the step b) to obtain coarse monofilament ultra-high molecular weight polyethylene fibers;
the multiple of the hot drawing is 25 to 46.25 times.
The invention firstly mixes the solvent oil and the ultra-high molecular weight polyethylene powder to obtain the spinning solution. In the invention, the solvent oil is preferably composed of 70-95% of cycloalkane containing 25-50 carbon atoms and 5-30% of chain hydrocarbon containing 25-50 carbon atoms, more preferably composed of 85-90% of cycloalkane containing 25-50 carbon atoms and 10-15% of chain hydrocarbon containing 25-50 carbon atoms, and more preferably white oil. In the present invention, the solvent oil can dissolve the ultra-high molecular weight polyethylene powder to obtain a spinning dope; the source of the solvent oil is not particularly limited in the present invention, and commercially available products of 5# white oil, 7# white oil, 10# white oil, 15# white oil, 22# white oil, 26# white oil, 32# white oil, 46# white oil, 68# white oil, 70# white oil, 100# white oil and 150# white oil known to those skilled in the art may be used. In the present invention, the amount (mass) of the solvent oil is preferably 6 to 19 times, and more preferably 7 to 17 times the amount (mass) of the ultrahigh molecular weight polyethylene powder.
In the present invention, the intrinsic viscosity of the ultra-high molecular weight polyethylene powder is preferably 19dl/g to 35dl/g, more preferably 21dl/g to 32dl/g, more preferably 28 dl/g; the molecular weight of the ultra-high molecular weight polyethylene powder is preferably 400-900 ten thousand g/mol, more preferably 600-800 ten thousand g/mol, so that the finished fiber has higher molecular weight; the powder particle diameter of the ultra-high molecular weight polyethylene powder is preferably 75-100 mu m, and the proportion>78％，Mw/Mn<5, ensuring that the particle size distribution is concentrated and reducing the process span in the spinning stage; the bulk density of the ultra-high molecular weight polyethylene powder is preferably 0.4g/cm 3 ～0.5g/cm 3 More preferably 0.45g/cm 3 Ensuring proper molecular chain entanglement, facilitating pre-spinning unwrapping and improving solid content.
In the present invention, the mixing process may preferably be further added with other additives capable of improving the production efficiency and product properties, such as antioxidants well known to those skilled in the art to facilitate mass production and to control degradation; the additive does not affect the monofilament fineness and the mechanical property of the finished fiber. In the present invention, the amount (mass) of the antioxidant is preferably 0.1% to 2%, more preferably 0.5%, of the amount (mass) of the ultrahigh molecular weight polyethylene powder.
In the present invention, the mixing is preferably performed by stirring; the method of stirring is not particularly limited in the present invention, and manual stirring or mechanical stirring known to those skilled in the art may be employed. In the present invention, the stirring speed is preferably 20rpm to 80rpm, more preferably 50rpm to 60 rpm; the stirring temperature is preferably 100-120 ℃, and more preferably 105-116 ℃; the stirring time is preferably 30 to 120min, and more preferably 40 to 60 min.
In the present invention, the swelling ratio of the spinning dope is 1.1 to 1.8, preferably 1.3 to 1.4, more preferably 1.33 to 1.38, and more preferably 1.36 to 1.38. In the present invention, when the swelling ratio exceeds 1.8, the viscosity of the material will be very high in actual production, and the shear degradation after entering the screw is very serious. According to the invention, by controlling the swelling ratio of the spinning solution and matching with a subsequent process, the mechanical property of the finished fiber is obviously improved on the basis of ensuring that the product meets the requirement of a coarse monofilament.
After the spinning solution is obtained, the obtained spinning solution is sequentially subjected to spinning, nozzle drafting and quick cooling to obtain the gelatinized pre-oriented filament bundle. In the present invention, the spinning process preferably includes:
b1) shearing, uniformly mixing and extruding the spinning solution obtained in the step a) in a double-screw extruder to obtain a first spinning solution;
b2) extruding the first spinning solution obtained in the step b1) through a spinneret to obtain a second spinning solution.
The obtained spinning solution is sheared, uniformly mixed and extruded in a double-screw extruder to obtain a first spinning solution. In the invention, the melting temperature of the double-screw extruder needs to be controlled in a proper temperature range, the melting temperature is too high, the material is too thin, and the subsequent nozzle is easy to break after being drawn; too low, insufficient dissolution and macromolecule disentanglement, and poor subsequent drawability. In the present invention, the screw rotation speed of the twin-screw extruder is preferably 200rpm to 300rpm, more preferably 220 rpm; the melting temperature of the twin-screw extruder is preferably 280 ℃ to 330 ℃, more preferably 300 ℃ to 310 ℃.
After the first spinning solution is obtained, the obtained first spinning solution is extruded through a spinneret plate to obtain a second spinning solution. In the invention, the aperture of the spinneret orifice on the spinneret plate is preferably 0.8 mm-2 mm, more preferably 1.2mm, and the spinneret orifice with the specific aperture is adopted, so that the spinneret orifice plays an important role in the filament number, the drawability and the mechanical property of a product; more importantly, the spinneret orifices with specific apertures enable the product not to generate adverse effects on the filament number of the finished fiber due to the drafting magnification of the subsequent spray head.
In the present invention, the temperature of the extrusion is preferably 299 to 309 ℃, more preferably 302 to 303 ℃; the rate of extrusion is preferably from 2m/min to 10m/min, more preferably 3 m/min.
After the second spinning solution is obtained, the obtained second spinning solution is subjected to nozzle drafting and rapid cooling in sequence to obtain the gelatinized pre-oriented filament bundle. In the present invention, the draft ratio of the nozzle is 5 to 30 times, preferably 8 to 15 times, and more preferably 9 to 13 times. The invention firstly amplifies the drafting multiple, improves the spinnability of the gel silk, and further can reduce the subsequent drafting multiple, thereby improving the production efficiency and the stability on the basis that the total drafting multiple meets the requirement of preparing the crude monofilament finished fiber; more importantly, the fiber can be matched with spinning solution with specific swelling ratio to prepare finished fiber with excellent mechanical property.
The invention adopts the nozzle drafting of the specific times, the dry coil weight (the weight of solid PE in unit length) of the gel silk can be controlled below 12000D, the dry coil weight is large and small, the degree of the nozzle drafting is reflected, and the times of the subsequent hot drafting are also determined; the larger the dry roll weight is, the smaller the draft multiple of the spray head is, the larger the multiple of the subsequent hot draft is, the product fiber with proper fineness can be obtained, and the invention improves the multiple of the spray head draft, thereby reducing the multiple of the hot draft.
In the present invention, the time for the rapid cooling is preferably 0.1s to 0.3s, more preferably 0.2 s; the temperature difference of the rapid cooling is preferably 255-305 ℃, and more preferably 277-278 ℃. After the spray head with the specific multiple is adopted for drafting, the uniform lamellar crystal structure can be formed by high-power pre-drafting of the disentangled and pre-fetched macromolecule chains before gelation; the crystal structure can be preserved through the specific time (too short time, incomplete crystal formation, too long time, further stretching to destroy the crystal and become discontinuous) and the rapid cooling process of temperature difference.
After the gelatinized pre-oriented filament bundle is obtained, the gelatinized pre-oriented filament bundle is subjected to hot drawing to obtain the coarse monofilament ultrahigh molecular weight polyethylene fiber. In the present invention, the heat draft is 25 to 46.25 times, preferably 35 to 45 times, and more preferably 41.1 to 42.7 times. The invention adopts the thermal drafting with specific times, on one hand, the solvent oil is removed, on the other hand, the product is ensured to meet the requirement of the coarse monofilament, and the mechanical property of the finished fiber is obviously improved. In the present invention, the specific multiple of hot drawing is realized by dividing the drawing multiple in each process step.
In the present invention, the hot drawing process is preferably embodied as follows:
c1) standing the gelatinized pre-oriented tows obtained in the step b), and sequentially performing pre-drafting, extraction and drying to obtain dry gel yarns;
c2) and c1), sequentially carrying out positive drafting and negative drafting on the xerogel yarn obtained in the step c) to obtain the thick monofilament ultra-high molecular weight polyethylene fiber.
The obtained gelatinized pre-oriented filament bundle is stood, and then is subjected to pre-drafting, extraction and drying in sequence to obtain the dry gel filament. In the present invention, the purpose of the resting is to balance the dry coil weight; the standing time is preferably 5 to 40 hours, and more preferably 36 hours.
In the present invention, the draft is preferably 3.1 to 6.1 times, and more preferably 3 to 4 times.
The extraction mode is not particularly limited in the invention, and the technical scheme of extracting by using hydrocarbon cleaning agent which is well known to those skilled in the art can be adopted. In the present invention, the draft ratio in the extraction process is preferably 1 to 2.5 times, more preferably 1.15 to 2 times.
The drying method is not particularly limited, and the technical scheme of secondary drying known to those skilled in the art can be adopted. In the present invention, the drying temperature is preferably 45 to 60 ℃, and more preferably 50 to 55 ℃. In the present invention, the draft ratio in the drying process is preferably 1.2 to 1.25 times, and more preferably 1.21 times.
By adopting the pre-drawing, extracting and drying processes (the first step of hot drawing), the oil content of the obtained dry gel filament can be controlled within 3 per thousand, the phenomenon that the PE molecular chains slide due to residual solvent oil with high content during drawing to influence the formation of a crystal region is avoided, and the production speed cannot be obviously reduced.
After the dry gel filaments are obtained, the dry gel filaments are subjected to positive drafting and negative drafting in sequence to obtain the coarse monofilament ultra-high molecular weight polyethylene fibers. In the present invention, the positive draft preferably includes three-stage draft; the temperature of the first stage drawing is preferably 121-130 ℃, and more preferably 125 ℃; the multiple of the first stage drafting is preferably 3.5 to 5 times, and more preferably 4 to 4.6 times; the temperature of the second stage drawing is preferably 131-140 ℃, and more preferably 135 ℃; the multiple of the second-stage drafting is preferably 1.2 to 1.8 times, and more preferably 1.46 to 1.57 times; the temperature of the third stage drawing is preferably 141-150 ℃, and more preferably 145 ℃; the multiple of the third-stage drafting is preferably 1.3 to 1.4 times, and more preferably 1.35;
in the present invention, the negative draft is preferably a primary draft; the temperature of the negative drafting is preferably 95-105 ℃, and more preferably 100 ℃; the negative draft is preferably 0.89 to 0.91 times, and more preferably 0.89 to 0.9 times.
The preparation method provided by the invention controls the swelling ratio of the spinning solution, and is matched with the subsequent process conditions of firstly amplifying the drafting multiple and then reducing the drafting multiple, and the total drafting multiple under the process conditions is more than 370 times, so that the mechanical property of the finished fiber can completely reach the standard, and the finished fiber can meet the requirement of the monofilament fineness of a coarse monofilament.
The invention also provides a thick monofilament ultra-high molecular weight polyethylene fiber prepared by the preparation method of the technical scheme. In the invention, the coarse monofilament ultra-high molecular weight polyethylene fiber has very high strength and modulus at the same time, and meets the performance requirements of the fiber serving as a bulletproof special material. Experimental results show that the monofilament titer of the coarse monofilament ultrahigh molecular weight polyethylene fiber obtained by the preparation method provided by the invention is greater than 3D, the strength is more than 36cN/dtex, and the modulus is more than 1300 cN/dtex.
The invention also provides application of the coarse monofilament ultra-high molecular weight polyethylene fiber in the technical scheme as a special bulletproof material. The thick monofilament ultra-high molecular weight polyethylene fiber provided by the invention can be used as a bulletproof special fiber; the special bulletproof fiber has the following 2 characteristics according to the practical application:
(1) the monofilament cannot be too thin so as to be beneficial to filament spreading, and the lower specific surface area can reduce the gluing amount and the monofilament titer > 3D;
(2) the strength is more than or equal to 35cN/dtex, the modulus is more than or equal to 1200cN/dtex, and the composite material has better anti-elasticity performance. Therefore, the coarse monofilament ultra-high molecular weight polyethylene fiber provided by the invention has the 2 characteristics, and can be applied as a special bulletproof fiber.
The invention provides a preparation method of coarse monofilament ultra-high molecular weight polyethylene fibers, which comprises the following steps: a) mixing solvent oil and ultrahigh molecular weight polyethylene powder to obtain spinning stock solution; the swelling ratio of the spinning solution is 1.1-1.8; b) spinning, nozzle drafting and quick cooling are carried out on the spinning stock solution obtained in the step a) in sequence to obtain a gelatinized pre-oriented tow; the drafting multiple of the spray head is 5-30 times; c) carrying out hot drawing on the gelatinized pre-oriented tows obtained in the step b) to obtain coarse monofilament ultra-high molecular weight polyethylene fibers; the multiple of the hot drawing is 25 to 46.25 times. Compared with the prior art, the preparation method provided by the invention has the advantages that by controlling the swelling ratio of the spinning solution and matching with the subsequent process conditions of firstly amplifying the drafting multiple and then reducing the drafting multiple, the mechanical property of the finished fiber is obviously improved on the basis of ensuring that the product meets the requirement of coarse monofilaments; the obtained thick monofilament ultra-high molecular weight polyethylene fiber has very high strength and modulus, and meets the performance requirements of the fiber serving as a bulletproof special material. Experimental results show that the monofilament fineness of the coarse monofilament ultrahigh molecular weight polyethylene fiber obtained by the preparation method is larger than 3D, the strength is more than 36cN/dtex, and the modulus is more than 1300 cN/dtex.
In addition, the preparation method provided by the invention has high efficiency and good stability, and is suitable for large-scale production.
To further illustrate the present invention, the following examples are provided for illustration. The ultra-high molecular weight polyethylene powder used in the following examples of the invention had an IV value of 28dl/g, a molecular weight of 750 ten thousand g/mol, a particle size of 75-150 μm, a ratio of > 78%, Mw/Mn<5 bulk density BD of 0.45g/cm 3 。
Example 1
(1) Adding 88kg of white oil into the swelling kettle, stirring, uniformly adding 12kg of ultra-high molecular weight polyethylene powder and 60g of antioxidant of CYANOX2777, stirring at 50rpm, heating to 105 ℃, closing heating, and keeping the temperature for 50min to obtain a spinning stock solution;
the dope was sampled and measured to have a swelling ratio of 1.38 and a viscosity of 1619 Pa.s.
(2) Inputting the spinning stock solution obtained in the step (1) into a double-screw extruder for shearing, uniformly mixing and extruding to obtain a first spinning solution; the screw speed of the twin-screw extruder was 220rpm, and the melt temperature was 305 ℃.
(3) Extruding the first spinning solution obtained in the step (2) through a spinning box and a spinneret plate, and obtaining a second spinning solution before entering a cooling water bath; the diameter of the spinneret orifice on the spinneret plate is 1.2mm, the extrusion temperature is 303 ℃, and the extrusion speed is 3 m/min.
(4) Drawing the second spinning solution obtained in the step (3) by 10 times of a nozzle, and quickly cooling the second spinning solution within 0.2s to 278 ℃ to obtain gelatinized pre-oriented tows (120 tows);
the sample was taken to determine the dry coil weight of the gelled pre-oriented yarn to be 10416D.
(5) Placing the gelatinized pre-oriented tows obtained in the step (4) in a filament holding barrel for standing for 36 hours after the filaments are wound, and then carrying out dry rolling to obtain 16438D; then, pre-drawing the gelled pre-oriented tows after standing treatment by 3.4 times, extracting by using a hydrocarbon cleaning agent (the drawing multiple in the extraction process is 1.15 times), and respectively performing primary drying at 50 ℃ and secondary drying at 55 ℃ (the drawing multiple in the drying process is 1.21 times) to obtain dry gel yarns;
sampling and measuring the oil content of the dry gel silk to be 1.1 per mill.
(6) Carrying out three-stage positive drafting (the first-stage drafting temperature is 125 ℃, the drafting multiple is 4.6 times, the second-stage drafting temperature is 135 ℃, the drafting multiple is 1.57 times, the third-stage drafting temperature is 145 ℃, the drafting multiple is 1.35 times) and one-stage negative drafting (the drafting temperature is 100 ℃, the drafting multiple is 0.89 times) on the xerogel silk obtained in the step (5) to obtain coarse monofilament ultra-high molecular weight polyethylene fibers;
the total hot draft (the preliminary draft multiple x the draft multiple in the extraction process x the draft multiple in the drying process x the three-stage positive draft multiple x the one-stage negative draft multiple) was calculated to be 41.1 times, and the total draft (the nozzle draft multiple x the total hot draft multiple) was calculated to be 411 times.
Through detection, the data of various properties of the coarse monofilament ultrahigh molecular weight polyethylene fiber provided by the embodiment 1 of the invention are shown in table 1.
Example 2
(1) Adding 88kg of white oil into the swelling kettle, stirring, uniformly adding 12kg of ultra-high molecular weight polyethylene powder and 60g of antioxidant with the CYANOX2777 model, stirring at the speed of 60rpm, heating to 105 ℃, closing heating, and keeping the temperature for 50min to obtain spinning stock solution;
the sample was taken to determine the swelling ratio of the dope to be 1.36 and the viscosity to be 1693 Pa.s.
(2) Inputting the spinning solution obtained in the step (1) into a double-screw extruder for shearing, uniformly mixing and extruding to obtain a first spinning solution; the screw speed of the twin-screw extruder was 220rpm, and the melt temperature was 305 ℃.
(3) Extruding the first spinning solution obtained in the step (2) through a spinning box and a spinneret plate, and obtaining a second spinning solution before entering a cooling water bath; the diameter of the spinneret hole on the spinneret plate is 1.2mm, the extrusion temperature is 302 ℃, and the extrusion speed is 3 m/min.
(4) Drawing the second spinning solution obtained in the step (3) by 9 times through a nozzle, and quickly cooling at 277 ℃ within 0.2s to obtain gelatinized pre-oriented tows (120 tows);
the sample was taken and the dry coil weight of the gelled pre-oriented yarn was measured to be 11512D.
(5) Placing the gelatinized pre-oriented tows obtained in the step (4) in a filament holding barrel for standing for 36 hours, and then carrying out dry rolling to 17036D; then, pre-drawing the gelled pre-oriented tows after standing treatment by 3.5 times, extracting by using a hydrocarbon cleaning agent (the drawing multiple in the extraction process is 1.15 times), and then respectively carrying out primary drying at 50 ℃ and secondary drying at 55 ℃ (the drawing multiple in the drying process is 1.21 times) to obtain dry gel yarns;
sampling and measuring the oil content of the dry gel silk to be 0.8 per mill.
(6) Carrying out three-stage positive drafting (the first-stage drafting temperature is 125 ℃, the drafting multiple is 4.6 times, the second-stage drafting temperature is 135 ℃, the drafting multiple is 1.57 times, the third-stage drafting temperature is 145 ℃, the drafting multiple is 1.35 times) and one-stage negative drafting (the drafting temperature is 100 ℃, the drafting multiple is 0.9 times) on the xerogel silk obtained in the step (5) to obtain coarse monofilament ultra-high molecular weight polyethylene fibers;
the total hot draft (the pre-draft multiple x the draft multiple in the extraction process x the draft multiple in the drying process x the three-stage positive draft multiple x the one-stage negative draft multiple) was calculated to be 42.7 times, and the total draft multiple (the nozzle draft multiple x the total hot draft multiple) was calculated to be 384.3 times.
Through detection, various performance data of the thick monofilament ultrahigh molecular weight polyethylene fiber provided by the embodiment 2 of the invention are shown in table 1.
Example 3
The preparation method provided in example 2 was used to prepare coarse monofilament ultra high molecular weight polyethylene fibers, with the following differences: the dope had a swelling ratio of 1.33 and a viscosity of 1599 Pa.s.
Through detection, the data of various properties of the coarse monofilament ultrahigh molecular weight polyethylene fiber provided by the embodiment 3 of the invention are shown in table 1.
Example 4
The preparation method provided in example 1 was used to prepare coarse monofilament ultra high molecular weight polyethylene fibers, with the following differences: carrying out nozzle drafting on the obtained second spinning solution by 12 times; the multiple of the pre-drafting is 3.2 times, and the multiple of the negative drafting is 0.9 time; that is, the total draft (the draft multiple of the preliminary draft, the draft multiple of the extraction process, the draft multiple of the drying process, the three-stage positive draft multiple, and the one-stage negative draft multiple) is 39.1 times, and the total draft multiple (the draft multiple of the nozzle, the total draft multiple of the hot draft) is 469.2 times.
Through detection, the performance data of the thick monofilament ultrahigh molecular weight polyethylene fiber provided by the embodiment 4 of the invention are shown in table 1.
Comparative example 1
The preparation method provided in example 2 was used to prepare coarse monofilament ultra high molecular weight polyethylene fibers, with the following differences: the dope had a swelling ratio of 1.06 and a viscosity of 1217 Pa.s.
The data of various properties of the coarse monofilament ultra-high molecular weight polyethylene fiber provided in comparative example 1 are shown in table 1.
Comparative example 2
The preparation method provided in example 2 was used to prepare coarse monofilament ultra high molecular weight polyethylene fibers, with the following differences: the dope had a swelling ratio of 1.88 and a viscosity of 2520 Pa.s.
The data of the properties of the thick monofilament ultra-high molecular weight polyethylene fiber provided in comparative example 2 are shown in table 1.
Comparative example 3
The preparation method provided in example 2 was used to prepare coarse monofilament ultra high molecular weight polyethylene fibers, with the following differences: 5 times of nozzle drafting is carried out on the obtained second spinning solution; and the multiple of the pre-drafting is 4.9 times; that is, the total draft (the pre-draft multiple x the draft multiple in the extraction process x the draft multiple in the drying process x the three-stage positive draft multiple x the one-stage negative draft multiple) is 59.8 times, and the total draft multiple (the draft multiple of the nozzle x the total multiple of the hot draft) is 299 times.
The data of the properties of the thick monofilament ultra-high molecular weight polyethylene fiber provided in comparative example 3 are shown in table 1.
Comparative example 4
The preparation method provided in example 2 was used to prepare coarse monofilament ultra high molecular weight polyethylene fibers, with the following differences: carrying out nozzle drafting on the obtained second spinning solution by 6 times; the pre-drafting multiple is 4.3 times, the second-stage drafting multiple is 1.61 times, and the third-stage drafting multiple is 1.34 times; that is, the total draft (draft multiple of pre-draft x draft multiple of extraction process x draft multiple of drying process x draft multiple of three-stage positive draft multiple x one-stage negative draft multiple) was 53.4 times, and the total draft multiple (draft multiple of nozzle x total draft multiple of hot draft) was 320.4 times.
The data of the properties of the thick monofilament ultra-high molecular weight polyethylene fiber provided in comparative example 4 are shown in table 1.
TABLE 1 Performance data of the coarse monofilament ultra-high molecular weight polyethylene fibers provided in examples 1 to 4 and comparative examples 1 to 4
As can be seen from Table 1, the coarse monofilament ultrahigh molecular weight polyethylene fibers provided in embodiments 1 to 4 of the present invention have a crystallinity of more than 83%, a molecular weight of not less than 305 ten thousand g/mol, a monofilament fineness of more than 3D, a strength of more than 36cN/dtex, and a modulus of more than 1300 cN/dtex; the thick monofilament ultra-high molecular weight polyethylene fibers provided by the embodiments 1-4 of the invention can be used as TM35 bulletproof special fibers. Meanwhile, the preparation method provided by the invention has high efficiency and good stability, the filament number of the single filament is controlled to be about 3.3D, and the number of broken ends of the dry gel filament is less than 3 per 18km (3.2kg) in the drafting process.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. A preparation method of thick monofilament ultra-high molecular weight polyethylene fiber comprises the following steps:
a) mixing solvent oil and ultrahigh molecular weight polyethylene powder to obtain spinning stock solution; the swelling ratio of the spinning solution is 1.1-1.8;
b) spinning, nozzle drafting and quick cooling are carried out on the spinning stock solution obtained in the step a) in sequence to obtain a gelatinized pre-oriented tow; the drafting multiple of the spray head is 5-30 times;
c) carrying out hot drawing on the gelatinized pre-oriented tows obtained in the step b) to obtain coarse monofilament ultra-high molecular weight polyethylene fibers; the hot drawing process specifically comprises the following steps:
c1) standing the gelatinized pre-oriented tows obtained in the step b), and sequentially performing pre-drafting, extraction and drying to obtain dry gel yarns; the pre-drafting multiple is 3.1-6.1 times;
c2) sequentially carrying out positive drafting and negative drafting on the xerogel yarn obtained in the step c1) to obtain a thick monofilament ultra-high molecular weight polyethylene fiber; the positive draft comprises three levels of draft; the temperature of the first stage of drafting is 121-130 ℃, and the multiple is 3.5-5 times; the temperature of the second-stage drafting is 131-140 ℃, and the multiple is 1.2-1.8 times; the temperature of the third stage of drafting is 141-150 ℃, and the multiple is 1.3-1.4 times; the temperature of the negative drafting is 95-105 ℃, and the multiple is 0.89-0.91;
the hot drawing multiple is 25-46.25 times.
2. The method according to claim 1, wherein the ultra-high molecular weight polyethylene powder in step a) has an intrinsic viscosity of 19 to 35dl/g, a molecular weight of 400 to 900 ten thousand g/mol, a particle size of 75 to 100 μm, and a bulk density of 0.4g/cm 3 ~0.5g/cm 3 。
3. The method according to claim 1, wherein the mixing in step a) is performed by stirring; the stirring speed is 20-80 rpm, the temperature is 100-120 ℃, and the time is 30-120 min.
4. The preparation method according to claim 1, wherein the spinning process in step b) is specifically:
b1) shearing, uniformly mixing and extruding the spinning solution obtained in the step a) in a double-screw extruder to obtain a first spinning solution; the screw rotating speed of the double-screw extruder is 200-300 rpm, and the melting temperature is 280-330 ℃;
b2) extruding the first spinning solution obtained in the step b1) through a spinneret plate to obtain a second spinning solution; the aperture of the spinneret orifice on the spinneret plate is 0.8 mm-2 mm.
5. The method of claim 1, wherein the rapid cooling in step b) is performed for a time of 0.1s to 0.3s and a temperature difference of 255 ℃ to 305 ℃.
6. A coarse monofilament ultra-high molecular weight polyethylene fiber, characterized by being prepared by the preparation method of any one of claims 1 to 5.
7. Use of the coarse monofilament ultra-high molecular weight polyethylene fiber of claim 6 as a material specifically for ballistic applications.
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| CN102433597A (en) * | 2011-10-11 | 2012-05-02 | 北京同益中特种纤维技术开发有限公司 | Gelatinized pre-oriented yarn and preparation method thereof and ultra high molecular weight polyethylene fiber and preparation method thereof |
| CN104313709A (en) * | 2014-10-21 | 2015-01-28 | 北京同益中特种纤维技术开发有限公司 | Ultrahigh molecular weight polyethylene fiber and preparation method thereof |
| CN107858763A (en) * | 2016-09-21 | 2018-03-30 | 九力绳缆有限公司 | The preparation method of superhigh molecular weight polyethylene fibers with super heavy denier yarn and its superhigh molecular weight polyethylene fibers of preparation |
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| CN102433597A (en) * | 2011-10-11 | 2012-05-02 | 北京同益中特种纤维技术开发有限公司 | Gelatinized pre-oriented yarn and preparation method thereof and ultra high molecular weight polyethylene fiber and preparation method thereof |
| CN104313709A (en) * | 2014-10-21 | 2015-01-28 | 北京同益中特种纤维技术开发有限公司 | Ultrahigh molecular weight polyethylene fiber and preparation method thereof |
| CN107858763A (en) * | 2016-09-21 | 2018-03-30 | 九力绳缆有限公司 | The preparation method of superhigh molecular weight polyethylene fibers with super heavy denier yarn and its superhigh molecular weight polyethylene fibers of preparation |
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