CN112941654A - Ultra-high molecular weight polyethylene fiber and preparation method and application thereof - Google Patents
Ultra-high molecular weight polyethylene fiber and preparation method and application thereof Download PDFInfo
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- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 title claims abstract description 93
- 239000000835 fiber Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 36
- 238000009987 spinning Methods 0.000 claims abstract description 68
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- 239000002131 composite material Substances 0.000 claims description 9
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- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
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- -1 polyethylene Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
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Images
Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
-
- D—TEXTILES; PAPER
- 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
- D01D1/00—Treatment of filament-forming or like material
- D01D1/06—Feeding liquid to the spinning head
- D01D1/065—Addition and mixing of substances to the spinning solution or to the melt; Homogenising
-
- D—TEXTILES; PAPER
- 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
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F41—WEAPONS
- F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
- F41H1/00—Personal protection gear
- F41H1/02—Armoured or projectile- or missile-resistant garments; Composite protection fabrics
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F41—WEAPONS
- F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
- F41H5/00—Armour; Armour plates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
The invention relates to an ultra-high molecular weight polyethylene fiber and a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) uniformly mixing the ultrahigh molecular weight polyethylene resin powder, an auxiliary agent and a solvent, and then performing multi-stage high-shear emulsification at the temperature of 95-105 ℃, wherein the emulsification time is 15-40 minutes, so as to obtain a spinning stock solution; 2) and (3) feeding the spinning stock solution into a double-screw extruder in a saturated feeding mode for dissolving and spinning, and performing aftertreatment to obtain the ultra-high molecular weight polyethylene fiber, wherein the prepared ultra-high molecular weight polyethylene fiber is used in the bulletproof product. Compared with the prior art, the method adopts modes of premixing, multistage high-shear emulsification, saturated feeding and the like, on one hand, the uniformity of the spinning solution is controlled, on the other hand, the infiltration of the solvent is improved and the swelling is promoted by adjusting the emulsification time and temperature, so that the stability and the improvement of the performance of the finished product are ensured.
Description
Technical Field
The invention belongs to the technical field of preparation of ultra-high molecular weight polyethylene fibers, and relates to an ultra-high molecular weight polyethylene fiber and a preparation method and application thereof.
Background
The ultra-high molecular weight polyethylene fiber is a fiber with the highest specific strength in the fiber materials which are industrialized at present, has excellent performances of high strength, high modulus, wear resistance, chemical corrosion resistance and the like, is widely applied to the fields of national defense and military, maritime work mooring ropes, individual protection and the like, particularly has continuously increased demand in military security products, and the corresponding technical requirements also rise year by year. For individual bulletproof products, the requirements of lightness, thinness and softness are high, so that higher performance requirements are provided for raw materials such as fibers for manufacturing bulletproof clothes, the performance is high, the fluctuation range is small, the probability of lowest value bullet breakdown is high due to large performance fluctuation, and weight reduction and thinning are difficult for reserving allowance.
Therefore, manufacturers continuously seek more complete production process of ultra-high molecular weight polyethylene fiber to pursue the stability and improvement of performance.
For example, chinese patent CN101691673A discloses a process for preparing ultra-high molecular weight polyethylene fiber, which comprises injecting ultra-high molecular weight polyethylene powder and solvent into a disentanglement kettle, forming a uniform emulsion-like mixed solution under the protection of nitrogen, and then feeding the mixed solution into a screw extruder at normal temperature under stirring through a storage tank for spinning. Although the method is simple, the purpose of molecular chain unwrapping can not be achieved at normal temperature, so that the improvement of the performance of the finished product is extremely limited.
The Chinese invention patent CN111118615A discloses a method for processing an ultra-high molecular weight polyethylene fiber spinning solution, which comprises the steps of injecting ultra-high molecular weight polyethylene powder, a solvent, an auxiliary agent and the like into a high-pressure stirring kettle, starting emulsification and stirring, and keeping the pressure in a high-pressure chamber at 1.5-5MPa, more preferably 3MPa, the temperature at 110-128 ℃, more preferably 125 ℃; then the mixed solution after high pressure treatment is injected into a single screw extruder, and finally enters a double screw extruder for spinning. The emulsifying device in the method is positioned in the high-pressure chamber, the rotating speed is 2000-5000r/min, preferably 3500r/min, and the emulsifying time is 2-5 h. This method has several problems: firstly, an autoclave with about 3MPa is a potential safety hazard for long-term production; secondly, the emulsifying time is too long, so that the production efficiency is influenced; and thirdly, at 125 ℃, the ultrahigh molecular weight polyethylene powder in the high-pressure cavity is in a swelling state and is agglomerated due to surface adhesion, so that the phase separation is accelerated, and uniform and stable conveying to a subsequent single screw cannot be guaranteed.
The Chinese invention patent CN109943900A discloses a method for pretreating an ultrahigh molecular weight polyethylene spinning system, which comprises the following steps: in a vacuum chamber, the surface adsorbed water of the ultra-high molecular weight polyethylene powder is removed, then a solvent with a certain temperature is injected for stirring and mixing, the soaking of the solvent on the resin is completed by heat preservation and pressure maintaining, and then the gel spinning is carried out to prepare the fiber. The pressure of the vacuum chamber is 0.001-0.06Mpa, the temperature is 50-90 ℃, the heat preservation and pressure maintaining time is 2-16h, and the stirring speed is 20-200 r/min. The method pretreats the resin, is beneficial to subsequently preparing uniform spinning solution, but has overlong heat preservation and pressure maintaining time and influences the production efficiency.
In addition, some manufacturers adopt raw material resin with higher molecular weight to improve the performance of finished products, and some manufacturers even reach seven or eight million, which undoubtedly increases the processing difficulty, is not beneficial to the improvement of production efficiency and the cost control, and especially the uniformity of fibers is difficult to guarantee, the performance fluctuation is large, and the requirements of weight reduction and thinning of final bulletproof products cannot be met.
Disclosure of Invention
The invention aims to provide an ultra-high molecular weight polyethylene fiber, a preparation method and application thereof, which have good performance and small deviation and are particularly suitable for bulletproof products.
The purpose of the invention can be realized by the following technical scheme:
a method for preparing ultra-high molecular weight polyethylene fibers comprises the following steps:
1) uniformly mixing the ultrahigh molecular weight polyethylene resin powder, an auxiliary agent and a solvent, and then performing multi-stage high-shear emulsification at the temperature of 95-105 ℃, wherein the emulsification time is 15-40 minutes, so as to obtain a spinning stock solution;
2) and (3) feeding the spinning solution into a double-screw extruder in a saturated feeding mode for dissolving and spinning, and performing post-treatment to obtain the ultra-high molecular weight polyethylene fiber.
The invention adopts modes of premixing, multistage high-shear emulsification, saturated feeding and the like, on one hand, the uniformity of the spinning stock solution is controlled, on the other hand, the infiltration of the solvent is improved by adjusting the emulsification time and temperature, and the swelling is promoted, so that the uniformity of the spinning stock solution is controlled. Thus, not only is the range of variation in properties reduced, but the average of the overall properties of the fiber is also improved.
Further, in the step 1), the molecular weight of the ultra-high molecular weight polyethylene resin powder is 400-600 ten thousand,
3 to 7, the proportion of the ultra-high molecular weight polyethylene resin powder particles having a particle diameter of 120-220 μm is 50% or more (preferably 70% or more).
Preferably, the molecular weight of the ultra-high molecular weight polyethylene resin powder is 400 to 500 ten thousand. The higher the molecular weight, the more beneficial the improvement of the properties of the finished fiber as long as the spinning solution is uniform, but correspondingly, the greater the difficulty of preparing a uniform spinning solution.
Preferably, the ultra-high molecular weight polyethylene resin powderMolecular weight distribution Range
Is 3-5. The distribution of the molecular weight of the raw materials seriously influences the fineness distribution of finished fibers, the fineness distribution is narrow, the performance fluctuation is correspondingly small, and the standard deviation of the V50 value of the final bulletproof product is small.
Further, in step 1), the auxiliary agent comprises one or more of an antioxidant, a flow promoter, a heat stabilizer, a colorant or a functional powder, and the solvent comprises one or more of halogenated hydrocarbon, mineral oil, decalin, tetralin, naphthalene, xylene, toluene, dodecane, undecane, decane, nonane, octene, chlorobenzene, petroleum ether, low molecular weight polyethylene wax or the like.
Further, in the step 1), the mass ratio of the ultra-high molecular weight polyethylene resin powder to the auxiliary agent is 1000 (1-50), preferably 1000 (2-10); the mass ratio of the ultrahigh molecular weight polyethylene resin powder to the solvent is 1 (7-50), preferably 1 (9-19).
Further, in the step 1), mixing in a stirring manner, wherein in the mixing process, the temperature is 28-35 ℃, the stirring speed is 20-200r/min, and the stirring time is 10-30 min; in the multi-stage high-shear emulsification process, the shearing precision is gradually improved, and the diameters of particles passing through are sequentially reduced to be finally lower than 15 μm, preferably lower than 5 μm. Through multi-stage high-shear emulsification and continuous interface updating, on one hand, the adhesion and agglomeration of part of ultra-high molecular weight polyethylene resin due to surface melting are reduced, on the other hand, the solvent and powder are more fully contacted, the wetting of the solvent is more facilitated, and a good basis is provided for preparing uniform spinning solution.
Further, in step 2), the post-treatment process comprises one or more of extraction, drying and multi-stage hot drawing. For volatile solvents, the extraction step can be omitted.
The device comprises a premixing kettle, a spinning stock solution preparation kettle, a high-shear emulsifying machine and a double-screw extruder which are sequentially communicated, wherein a circulating pipe communicated with the spinning stock solution preparation kettle is arranged on a pipeline between the high-shear emulsifying machine and the double-screw extruder, and an overflow pipe is arranged between the spinning stock solution preparation kettle and a liquid inlet of the double-screw extruder.
When the device is applied, the ultra-high molecular weight polyethylene resin powder, the auxiliary agent and the solvent are fully stirred in a premixing kettle, are conveyed and injected into a spinning stock solution preparation kettle through a flow pump after being uniformly mixed, are matched with a high-shear emulsifying machine for carrying out repeated circulating shearing to complete the preparation of the spinning stock solution, and then are sent into a double-screw extruder for dissolving and spinning.
The multiple-cycle shearing process specifically comprises the following steps: and starting a stirrer of the spinning stock solution preparation kettle and an external high-shear emulsifying machine, keeping the temperature in the spinning stock solution preparation kettle constant, performing multiple circulating shearing by utilizing a pipeline and a circulating pipe between the high-shear emulsifying machine and the double-screw extruder, returning one path of the mixture into the spinning stock solution preparation kettle for continuous stirring and circulating emulsifying shearing, and conveying the other path of the mixture into the double-screw extruder through a flow pump.
Judging and characterizing the emulsification effect: collecting a plurality of mixed liquor in the spinning stock solution preparation kettle from a sampling port, placing the mixed liquor in a 500mL glass measuring cylinder, and observing the sedimentation condition and the layering time of resin, wherein the shorter the layering time is, the easier the phase separation is, and the poorer the emulsification effect is; otherwise, the emulsification effect is better.
The feeding of the double-screw extruder is saturated feeding, the liquid level is constant, and the part exceeding the liquid level flows back into the spinning stock solution preparation kettle through the overflow pipe to control the pressure fluctuation in the spinning process, so that the output stability is achieved.
Preferably, the stirring form in the premixing kettle comprises one or more of an anchor type, a blade type or a ribbon type, so as to avoid sedimentation, adherence and fouling in the dispersing process of the ultra-high molecular weight polyethylene resin; the stirring speed is 20-200r/min, and the stirring time is 10-30 min. The temperature in the premixing kettle is 28-35 ℃, and the temperature is controlled to be +/-0.5 ℃. The temperature is too low, the kinematic viscosity of the solvent is high, and the resin powder is not easy to disperse uniformly; the temperature is too high, the kinematic viscosity of the solvent is low, and the sedimentation of the resin powder is accelerated, so that the solid contents of the upper layer and the lower layer are inconsistent. Meanwhile, the temperature is also the preheating for the subsequent emulsification preparation of the mixed liquid.
Preferably, the spinning solution preparation kettle is a jacket kettle, and the heating medium can be liquid or gas; the stirring form is axial flow type, propulsion type, centrifugal type or other forms of paddle stirring, the mixed liquid is driven to be longitudinally divided and dispersed in the horizontal plane, and multi-direction three-dimensional mixing in the kettle is ensured. The stirring paddles can be used in one or more groups to adapt the liquid level, and the stirring speed is 100-300 r/min.
Preferably, the volume of the mixed solution in the spinning solution preparation kettle is 1000-3000L, and the length of the emulsification time is adjusted by controlling the liquid storage amount, preferably 15-40 minutes. The hourly flow of the high-shear emulsifying machine is 3-8 times of the volume of the mixed liquid in the spinning stock solution preparation kettle, so that multiple circulating emulsification is ensured, and the aim of continuously updating an interface is fulfilled; the stirring speed is 1000-3000 r/min, so as to achieve the emulsification effect.
Preferably, the temperature in the spinning solution preparation kettle is 95-105 ℃, and the temperature is controlled to be +/-0.5 ℃. The swelling temperature of the ultra-high molecular weight polyethylene is related to concentration, molecular weight, solvent and the like, and in the system, the swelling temperature is above 120 ℃, so the temperature in the kettle is controlled to be slightly lower than the swelling temperature, and the further penetration and diffusion of the solvent are prevented from being influenced by the adhesion of the resin surface.
Preferably, the double-screw extruder is a co-rotating meshed double screw, the length-diameter ratio is 68-120, and the screw is provided with a conveying section, a mixing section, a melting section, a homogenizing section and other functional zones.
The ultrahigh molecular weight polyethylene fiber is prepared by the method.
Use of ultra high molecular weight polyethylene fibers in ballistic resistant articles.
Furthermore, the ultra-high molecular weight polyethylene fiber is sequentially warped, spread, dipped, dried and rolled to prepare ultra-high molecular weight polyethylene single-layer UD cloth, then the ultra-high molecular weight polyethylene single-layer UD cloth is compounded at 0 degree/90 degrees to obtain fiber composite cloth, and the fiber composite cloth is prepared into soft bulletproof clothes or hard bulletproof armor.
The invention adopts the 400-plus-600-ten-thousand-molecule-weight-level ultrahigh molecular weight polyethylene resin powder, and obtains high-strength high-modulus fiber and uniform and stable performance through the optimization of a spinning process, thereby ensuring that the subsequent bulletproof product is light and thin. The invention adopts multi-stage shearing emulsification and continuous interface updating to pretreat the spinning solution, greatly improves the process of solvent infiltration, accelerates swelling, and shortens the time of thermal hysteresis in the dissolution process of the ultra-high molecular weight polyethylene. Meanwhile, the spinning temperature is reduced, and the high-temperature oxidative degradation of the ultra-high molecular weight polyethylene is reduced.
Compared with the prior art, the invention has the following characteristics:
1) the temperature of the stock solution pretreatment is selected below the swelling temperature, and the further permeation of the subsequent solvent is influenced by the swelling of the surface layer of the resin, so that a softer mode is adopted, and the soaking process is improved.
2) The independent multistage shearing mode outside the kettle is selected for high-shear emulsification, the particle size distribution is effectively reduced, the dispersion is more uniform, the emulsification efficiency is higher, the emulsification time is controllable, multiple times of circulating shearing is realized, the liquid drops are fine and smooth, the stock solution is uniform, the spinning pressure change is small, and multiple process requirements of dispersion, emulsification, homogenization, mixing and the like are realized simultaneously.
3) The prepared fiber has small dispersion and stable performance, and the final bulletproof product made of the UD cloth has light weight and thin thickness on the premise of ensuring the same protection level.
4) The spinning process flow is short, the operation is convenient, the production efficiency is improved, and the production cost is reduced.
Drawings
FIG. 1 is a schematic view of the structure of an apparatus in example 1;
the notation in the figure is:
1-premixing kettle, 2-spinning stock solution preparation kettle, 3-high shear emulsifying machine, 4-double screw extruder, 5-circulating pipe and 6-overflow pipe.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Example 1:
the device shown in figure 1 comprises a premixing kettle 1, a spinning stock solution preparation kettle 2, a high-shear emulsifying machine 3 and a double-screw extruder 4 which are communicated in sequence, wherein a circulating pipe 5 communicated with the spinning stock solution preparation kettle 2 is arranged on a pipeline between the high-shear emulsifying machine 3 and the double-screw extruder 4, and an overflow pipe 6 is arranged between the spinning stock solution preparation kettle 2 and a liquid inlet of the double-screw extruder 4.
The preparation method of the ultra-high molecular weight polyethylene fiber is based on the device, and the preparation process comprises the following steps:
molecular weight is 400 ten thousand, molecular weight distribution range
5, the particle size distribution range of 120-. And uniformly mixing, injecting into a spinning stock solution preparation kettle 2, keeping the temperature in the spinning stock solution preparation kettle 2 at 98 ℃, stirring at the rotating speed of 300 revolutions per minute, and simultaneously starting a high-shear emulsifying machine 3 outside the kettle at the rotating speed of 3000 revolutions per minute, and performing high-shear emulsification for 40 minutes. The mixed solution is dispersed uniformly, and is sent into a double-screw extruder 4 for dissolving and spinning, and then the ultra-high molecular weight polyethylene fiber is prepared by extraction, drying and multi-stage hot drawing, and the fiber performance is measured according to GB/T19975-2005. The fiber is warped, spread, dipped, dried and rolled to obtain ultra-high molecular weight polyethylene single-layer UD cloth, then the ultra-high molecular weight polyethylene single-layer UD cloth is compounded at 0 degree/90 degree to obtain fiber composite cloth, the fiber composite cloth is cut and stacked into a plurality of layers to obtain soft bulletproof clothes, and secondary bulletproof performance is measured according to GA141-2010 police bullet-proof clothes standard, 7.62mm handgun bullets (lead cores) in 1951, and the bullet speed is 445 +/-10 m/s. Or pressing by a press to obtain the hard bulletproofThe armor is characterized in that four-level bulletproof performance is measured according to GA141-2010 police bullet-proof vest standard, 7.62mm type B pistol ammunition (steel core) in 1951, and the bullet speed is 515 +/-10 m/s.
Example 2:
the difference from example 1 is that: the molecular weight of the ultra-high molecular weight polyethylene resin powder is 500 ten thousand, and the mass ratio of the ultra-high molecular weight polyethylene resin powder to the solvent is 1: 11.
Example 3:
the difference from example 1 is that: the solvent injected into the premixing kettle 1 is constant temperature mineral oil with the temperature of 28 ℃, the stirring speed is 20 revolutions per minute, and the stirring time is 10 minutes.
Example 4:
the difference from example 1 is that: the solvent injected into the premixing kettle 1 is decahydronaphthalene with the constant temperature of 35 ℃. And (3) feeding the mixture into a double-screw extruder 4 for dissolving and spinning, and then directly drying and carrying out multi-stage hot drawing to obtain the ultra-high molecular weight polyethylene fiber.
Example 5:
the molecular weight is 500 ten thousand, the molecular weight distribution range
3, the weight ratio of the ultrahigh molecular weight polyethylene resin powder with the particle size distribution range of 120-.
Example 6:
the difference from example 1 is that: the spinning solution preparation kettle 2 is kept at the constant temperature of 105 ℃ and emulsified for 15 minutes by high shear.
Example 7:
the difference from example 1 is that: the stirring speed in the spinning solution preparation kettle 2 is 100 revolutions per minute, and the high-shear emulsifying machine 3 is 1000 revolutions per minute.
Comparative example 1:
the difference from example 1 is that: after the raw materials are uniformly mixed and injected into the spinning stock solution preparation kettle 2, the first-stage shearing emulsification is added in the spinning stock solution preparation kettle 2 except for stirring, the rotating speed is 3000 r/min, but a high-shearing emulsifying machine 3 outside the kettle is not started.
Comparative example 2:
the difference from example 1 is that: the molecular weight of the ultra-high molecular weight polyethylene resin powder is 700 ten thousand, and the mass ratio of the ultra-high molecular weight polyethylene resin powder to the solvent is 1: 15. After the mixture is evenly mixed and injected into a spinning stock solution preparation kettle 2, the first-stage shearing emulsification is added in the spinning stock solution preparation kettle 2 except for stirring, the rotating speed is 3000 r/min, but a high-shearing emulsifying machine 3 outside the kettle is not started.
The results of the performance test of the ultra-high molecular weight polyethylene fibers prepared in the above examples and comparative examples are shown in table 1 below.
TABLE 1
According to the test results, the bulletproof product prepared by the method has obvious advantages in weight and thickness on the premise of the same protection level. Comparative example 1 is a typical embodiment in the industry, and high shear in-tank emulsification is generally the choice, but generally has large performance fluctuations. Comparative example 2 is also a means conventionally adopted in the industry, and improves the performance by improving the molecular weight of the raw materials, but has the defects of high spinning difficulty, only reduction of solid content, increase of production cost and difficulty in ensuring the uniformity of the fibers. The invention selects multi-stage high-speed shearing, improves the precision step by step and ensures the uniformity of the mixed liquid. Moreover, in the multi-stage shearing process, the interface is continuously updated, so that the resin is more fully contacted with the solvent, and the wetting is more facilitated.
Example 8:
a method for preparing ultra-high molecular weight polyethylene fibers comprises the following steps:
1) uniformly mixing the ultrahigh molecular weight polyethylene resin powder, an auxiliary agent and a solvent, and then performing multistage high-shear emulsification at 95 ℃ for 40 minutes to obtain a spinning stock solution;
2) and (3) feeding the spinning stock solution into a double-screw extruder in a saturated feeding mode for dissolving and spinning, and performing post-treatment to obtain the ultra-high molecular weight polyethylene fiber.
In the step 1), the molecular weight of the ultra-high molecular weight polyethylene resin powder is 400 ten thousand,
7, the proportion of the ultra-high molecular weight polyethylene resin powder particles having a particle diameter of between 120-220 μm was 50%.
The auxiliary agent comprises one or more of an antioxidant, a flow promoter, a heat stabilizer, a colorant or a functional powder, and the solvent comprises one or more of halogenated hydrocarbon, mineral oil, decahydronaphthalene, tetrahydronaphthalene, naphthalene, xylene, toluene, dodecane, undecane, decane, nonane, octene, chlorobenzene, petroleum ether or low molecular weight polyethylene wax and the like. The mass ratio of the ultra-high molecular weight polyethylene resin powder to the auxiliary agent is 1000:50, and the mass ratio of the ultra-high molecular weight polyethylene resin powder to the solvent is 1: 7.
Mixing in a stirring mode, wherein the temperature is 35 ℃, the stirring speed is 20 revolutions per minute, and the stirring time is 30 minutes in the mixing process; in the multi-stage high-shear emulsification process, the shearing precision is gradually improved, and the diameters of passing particles are sequentially reduced and finally are lower than 15 micrometers.
In step 2), the post-treatment process comprises one or more of extraction, drying and multi-stage hot drawing.
Ultra-high molecular weight polyethylene fibers are used in ballistic resistant articles. When the ultra-high molecular weight polyethylene composite fabric is applied, the ultra-high molecular weight polyethylene fibers are sequentially warped, spread, impregnated, dried and rolled to obtain ultra-high molecular weight polyethylene single-layer UD fabric, then the ultra-high molecular weight polyethylene single-layer UD fabric is compounded at 0 degree/90 degrees to obtain fiber composite fabric, and the fiber composite fabric is further prepared into soft bulletproof clothes or hard bulletproof armor.
Example 9:
a method for preparing ultra-high molecular weight polyethylene fibers comprises the following steps:
1) uniformly mixing the ultrahigh molecular weight polyethylene resin powder, an auxiliary agent and a solvent, and then performing multistage high-shear emulsification at 105 ℃ for 15 minutes to obtain a spinning stock solution;
2) and (3) feeding the spinning stock solution into a double-screw extruder in a saturated feeding mode for dissolving and spinning, and performing post-treatment to obtain the ultra-high molecular weight polyethylene fiber.
In the step 1), the molecular weight of the ultra-high molecular weight polyethylene resin powder is 600 ten thousand,
3, the proportion of the ultra-high molecular weight polyethylene resin powder particles having a particle diameter of between 120-220 μm was 80%.
The mass ratio of the ultra-high molecular weight polyethylene resin powder to the auxiliary agent is 1000:1, and the mass ratio of the ultra-high molecular weight polyethylene resin powder to the solvent is 1: 50.
Mixing in a stirring mode, wherein in the mixing process, the temperature is 28 ℃, the stirring speed is 200 revolutions per minute, and the stirring time is 10 minutes; in the multi-stage high-shear emulsification process, the shearing precision is gradually improved, and the diameters of passing particles are sequentially reduced and finally are lower than 15 micrometers.
The rest is the same as example 8.
Example 10:
a method for preparing ultra-high molecular weight polyethylene fibers comprises the following steps:
1) uniformly mixing the ultrahigh molecular weight polyethylene resin powder, an auxiliary agent and a solvent, and then performing multi-stage high-shear emulsification at 100 ℃ for 25 minutes to obtain a spinning stock solution;
2) and (3) feeding the spinning stock solution into a double-screw extruder in a saturated feeding mode for dissolving and spinning, and performing post-treatment to obtain the ultra-high molecular weight polyethylene fiber.
In the step 1), the molecular weight of the ultra-high molecular weight polyethylene resin powder is 500 ten thousand,
5, the proportion of the ultrahigh molecular weight polyethylene resin powder particles having a particle diameter of between 120-220 μm was 70%.
The mass ratio of the ultra-high molecular weight polyethylene resin powder to the auxiliary agent is 1000:25, and the mass ratio of the ultra-high molecular weight polyethylene resin powder to the solvent is 1: 30.
Mixing in a stirring mode, wherein the temperature is 31 ℃, the stirring speed is 120 revolutions per minute, and the stirring time is 20 minutes in the mixing process; in the multi-stage high-shear emulsification process, the shearing precision is gradually improved, and the diameters of passing particles are sequentially reduced and finally are lower than 15 micrometers.
The rest is the same as example 8.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A method for preparing ultra-high molecular weight polyethylene fibers is characterized by comprising the following steps:
1) uniformly mixing the ultrahigh molecular weight polyethylene resin powder, an auxiliary agent and a solvent, and then performing multi-stage high-shear emulsification at the temperature of 95-105 ℃, wherein the emulsification time is 15-40 minutes, so as to obtain a spinning stock solution;
2) and (3) feeding the spinning solution into a double-screw extruder in a saturated feeding mode for dissolving and spinning, and performing post-treatment to obtain the ultra-high molecular weight polyethylene fiber.
2. The method of claim 1, wherein in step 1), the molecular weight of the ultra-high molecular weight polyethylene resin powder is 400 to 600 ten thousand,
3-7, the proportion of the ultra-high molecular weight polyethylene resin powder particles with the particle diameter of 120-220 mu m is more than or equal to 50 percent.
3. The method of claim 1, wherein the auxiliary agent comprises one or more of an antioxidant, a flow promoter, a thermal stabilizer, a colorant or a functional powder, and the solvent comprises one or more of a halogenated hydrocarbon, mineral oil, decalin, tetralin, naphthalene, xylene, toluene, dodecane, undecane, decane, nonane, octene, chlorobenzene, petroleum ether, or low molecular weight polyethylene wax.
4. The method for preparing ultra-high molecular weight polyethylene fiber according to claim 1, wherein in step 1), the mass ratio of the ultra-high molecular weight polyethylene resin powder to the auxiliary agent is 1000 (1-50), and the mass ratio of the ultra-high molecular weight polyethylene resin powder to the solvent is 1 (7-50).
5. The method for preparing ultra-high molecular weight polyethylene fiber according to claim 1, wherein in step 1), the mixing is performed by stirring, and during the mixing, the temperature is 28-35 ℃, the stirring speed is 20-200r/min, and the stirring time is 10-30 min; in the multi-stage high-shear emulsification process, the shearing precision is gradually improved, and the diameters of passing particles are sequentially reduced and finally are lower than 15 micrometers.
6. The method of claim 1, wherein the post-treatment process in step 2) comprises one or more of extraction, drying, and multi-stage hot drawing.
7. An apparatus for carrying out the method of preparing ultra-high molecular weight polyethylene fiber according to any one of claims 1 to 6, wherein the apparatus comprises a premixing kettle (1), a spinning solution preparing kettle (2), a high shear emulsifying machine (3) and a twin-screw extruder (4) which are communicated in sequence, a circulating pipe (5) communicated with the spinning solution preparing kettle (2) is arranged on a pipeline between the high shear emulsifying machine (3) and the twin-screw extruder (4), and an overflow pipe (6) is arranged between the spinning solution preparing kettle (2) and a liquid inlet of the twin-screw extruder (4).
8. Ultra-high molecular weight polyethylene fiber, characterized in that it is produced by the process according to any one of claims 1 to 6.
9. Use of ultra high molecular weight polyethylene fibres according to claim 8, wherein the ultra high molecular weight polyethylene fibres are used in ballistic resistant articles.
10. The use of the ultra-high molecular weight polyethylene fiber according to claim 9, wherein the ultra-high molecular weight polyethylene fiber is sequentially subjected to warping, spreading, gum dipping, drying and rolling to obtain ultra-high molecular weight polyethylene single-layer UD cloth, then the ultra-high molecular weight polyethylene single-layer UD cloth is subjected to 0 °/90 ° compounding to obtain fiber composite cloth, and the fiber composite cloth is further prepared into soft body armor or hard body armor.
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