CN115961374A - Thermotropic liquid crystal polymer fiber, non-woven fabric, and preparation method and application thereof - Google Patents
Thermotropic liquid crystal polymer fiber, non-woven fabric, and preparation method and application thereof Download PDFInfo
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- CN115961374A CN115961374A CN202211684321.9A CN202211684321A CN115961374A CN 115961374 A CN115961374 A CN 115961374A CN 202211684321 A CN202211684321 A CN 202211684321A CN 115961374 A CN115961374 A CN 115961374A
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- 239000000835 fiber Substances 0.000 title claims abstract description 81
- 239000004974 Thermotropic liquid crystal Substances 0.000 title claims abstract description 48
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- 238000002360 preparation method Methods 0.000 title abstract description 6
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims abstract description 15
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000009987 spinning Methods 0.000 claims abstract description 14
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 24
- 239000004744 fabric Substances 0.000 claims description 23
- 229910000856 hastalloy Inorganic materials 0.000 claims description 18
- 238000002844 melting Methods 0.000 claims description 17
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- 238000010583 slow cooling Methods 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- BIJAWQUBRNHZGE-UHFFFAOYSA-N n-pyridin-4-ylacetamide Chemical compound CC(=O)NC1=CC=NC=C1 BIJAWQUBRNHZGE-UHFFFAOYSA-N 0.000 claims description 6
- 238000006068 polycondensation reaction Methods 0.000 claims description 6
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- 238000007731 hot pressing Methods 0.000 claims description 4
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- 238000003825 pressing Methods 0.000 claims description 4
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- 238000005096 rolling process Methods 0.000 claims description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
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- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
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- 229920005594 polymer fiber Polymers 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000003292 glue Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002759 woven fabric Substances 0.000 description 5
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 4
- 229920006231 aramid fiber Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- OTIDWUALRXXVIM-UHFFFAOYSA-N n-ethylpyridin-4-amine Chemical compound CCNC1=CC=NC=C1 OTIDWUALRXXVIM-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
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- 239000002270 dispersing agent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
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- 238000009941 weaving Methods 0.000 description 2
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 1
- PVMNPAUTCMBOMO-UHFFFAOYSA-N 4-chloropyridine Chemical compound ClC1=CC=NC=C1 PVMNPAUTCMBOMO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
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- 150000001412 amines Chemical class 0.000 description 1
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- 229920001971 elastomer Polymers 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
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- 235000011056 potassium acetate Nutrition 0.000 description 1
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- 238000010992 reflux Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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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- Artificial Filaments (AREA)
Abstract
The invention belongs to the technical field of high polymer fibers, and particularly relates to thermotropic liquid crystal polymer fibers, a piece of non-woven fabric, and a preparation method and application thereof. The thermotropic liquid crystal polymer fiber is prepared by melt spinning of a liquid crystal polymer, wherein the liquid crystal polymer is prepared by polymerizing the following monomers: relative to 100 mole parts of p-hydroxybenzoic acid, the 6-hydroxy-2-naphthoic acid is 40 to 55 mole parts, the 4,4' -cyclododecanediphenol is 3 to 10 mole parts, and the terephthalic acid is 3 to 10 mole parts. The liquid crystal polymer which can be used for stable spinning is obtained by regulating and controlling the monomer with specific content, the strength retention rate of the liquid crystal polymer fiber prepared from the liquid crystal polymer is more than 95% at 120 ℃, the moisture regain does not exceed 0.024%, and the apparent quality is good. The non-woven fabric made of the fiber is used for light or hard bulletproof clothes, and has better bulletproof effect through a target hitting test and a water absorption test.
Description
Technical Field
The invention belongs to the technical field of high polymer fibers, and particularly relates to thermotropic liquid crystal polymer fibers, a piece of non-woven fabric, and a preparation method and application thereof.
Background
The body armor is used as an important component of individual protective equipment, and plays an important role in reducing the casualties of combat personnel of troops, improving the survival capability of individual soldiers and enhancing the combat effectiveness. The original bulletproof vest material is mainly a hard bulletproof material made of special steel, aluminum alloy and other metals, has certain bulletproof performance, but has larger weight and inconvenient wearing, and limits the mobility of a human body to a great extent. In order to improve the wearing comfort of the body armor, lightweight bulletproof materials are produced.
The light bulletproof material which is widely applied at present comprises aramid fiber and ultra-high molecular weight polyethylene fiber. The aramid fiber has low density, high temperature resistance, fire resistance, chemical resistance and extremely high mechanical property and fatigue resistance, but is easy to absorb moisture, the moisture regain is as high as more than 5% under normal conditions, when soldiers wade in the field, the body load is greatly increased due to the fact that the bulletproof clothes absorb water, the combat effectiveness is influenced, and meanwhile, the bulletproof property of the bulletproof clothes can be reduced due to the fact that the water absorbs water; in addition, the strength of the aramid fiber is obviously attenuated by ultraviolet radiation in the sun, and the use performance of the aramid fiber is influenced. The ultra-high molecular weight polyethylene fiber has the characteristics of high modulus, high strength, impact resistance, cutting resistance, corrosion resistance, low density ratio to water, low friction coefficient and the like, but the surface of the ultra-high molecular weight polyethylene fiber does not have any active functional group, the friction coefficient is low, the interface bonding is difficult, and the composite bonding difficulty is large. Meanwhile, the ultra-high molecular weight polyethylene fiber has a low melting point and poor heat resistance (the strength retention rate is about 70% at 80 ℃), and is flammable and remarkably reduced in strength when exposed to a high-temperature environment. Thermotropic Liquid Crystal Polymer (TLCP) fiber is a high-performance special fiber obtained by melt spinning, and is expected to be popularized and applied in the bulletproof field due to the excellent performances of high strength and modulus, high temperature resistance, cutting resistance, creep resistance, radiation resistance, wear resistance, chemical resistance, low moisture absorption, good flame retardance and the like.
US09261333B2 describes a potential application of liquid crystal polymer fibers in laminated textiles as a bulletproof material, but no specific embodiment is given, and in addition, the disclosed laminated textiles are woven by warp yarns and weft yarns to form woven fabrics, and in the woven fabrics, the fibers are easily damaged in the weaving process, so that the strength of the woven fabrics is reduced.
The liquid crystal polymer fibers and products thereof on the market have different performances, and the application of the liquid crystal polymer fibers in the bulletproof field is severely restricted, so that the development of high-performance liquid crystal polymer fibers becomes a key for extending the liquid crystal polymer fibers to the bulletproof field.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide thermotropic liquid crystal polymer fibers which have high strength and high modulus, extremely low water absorption rate and strength retention rate of more than 95% at high temperature, and the thermotropic liquid crystal polymer fibers are made into weftless cloth by a specific process to be used as a bulletproof garment material and have higher protection level.
The above object of the present invention can be achieved by the following technical solutions: a thermotropic liquid crystalline polymer fiber made from melt spinning a liquid crystalline polymer polymerized from the following monomers: p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4 '-cyclododecanediphenol and terephthalic acid, wherein the 6-hydroxy-2-naphthoic acid is 40 to 55 mol parts, the 4,4' -cyclododecanediphenol is 3 to 10 mol parts and the terephthalic acid is 3 to 10 mol parts based on 100 mol parts of the p-hydroxybenzoic acid.
For the present invention, too high or too low a molar amount of parahydroxybenzoic acid causes a significant increase in the melting point, resulting in the polymer curing in the reaction vessel and failing to obtain the desired molecular weight. Compared with 100 mole parts of p-hydroxybenzoic acid, if the mole part of 6-hydroxy-2-naphthoic acid is lower than 40, the high temperature resistance is reduced and is higher than 55, the polymerization viscosity is obviously increased, and the polymer is difficult to be smoothly discharged from the reaction kettle; the 4,4' -cyclododecanebisahenol contains cyclododecane, the cyclododecane is a saturated group, has strong inertia, is not easy to combine with water molecules, and can further improve the water absorption performance of the polymer, and meanwhile, the heat resistance stability of the polymer is reduced due to excessive content of the cyclododecane due to the angular tension and non-bonding interaction, so that the molar content is more suitably controlled within the range of 3-10; if the molar fraction of terephthalic acid is less than 3 or more than 10, the melting point rises significantly and the polymer solidifies in the reaction vessel to fail to obtain the desired molecular weight.
Preferably, the thermotropic liquid crystalline polymer has a melt viscosity of 30 to 60pa.s. For spinning-grade liquid crystal polymers, the viscosity is lower than 30, the strength meeting the requirements is difficult to obtain, and the viscosity is higher than 60, the requirements for equipment are higher, special equipment needs to be added to match with the equipment, and the manufacturing cost is increased.
Preferably, the thermotropic liquid crystal polymer has a weight average molecular weight of 8 to 14 ten thousand. The liquid crystal polymer has a molecular weight of more than 8 ten thousand, has proper viscosity at the spinning temperature, and is convenient for spinning. The strength and modulus of the fiber increase with the increase in molecular weight, but the molecular weight is too high, the melt viscosity increases, the fluidity deteriorates, and even the liquid crystal polymer does not have fluidity and cannot be spun, so that the molecular weight of the liquid crystal polymer is preferably not more than 14 ten thousand for ensuring smooth spinning.
Preferably, the single filament fineness of the thermotropic liquid crystal polymer fiber is not more than 5D. The body armor made of fine denier fiber can further reduce the weight and improve the maneuverability of human body.
Preferably, the preparation of the thermotropic liquid crystalline polymer fiber comprises the following steps:
1. putting p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4' -cyclododecanediphenol, terephthalic acid, an acetylation reagent acetic anhydride and a catalyst 4-acetaminopyridine into a Hastelloy reaction kettle, keeping the temperature at 135-150 ℃ for 2-10 h, heating to 300-320 ℃ at the speed of 0.5-1.0 ℃/min, keeping the temperature for 2-4 h, filling nitrogen into the Hastelloy reaction kettle, discharging the mixture through a Hastelloy polymerization kettle, crushing and drying to obtain a prepolymer; carrying out solid phase polycondensation on the prepolymer in a rotary kiln at 220-320 ℃ for 12-48 h under the protection of nitrogen to obtain a thermotropic liquid crystal polymer;
2. drying the thermotropic liquid crystal polymer, melting and plasticizing the thermotropic liquid crystal polymer in a nitrogen atmosphere, then melting and spraying the thermotropic liquid crystal polymer from a spinneret plate, slowly cooling, circularly blowing, drafting and shaping, dividing filaments and winding to prepare and obtain thermotropic liquid crystal polymer nascent fibers;
3. and (3) carrying out heat treatment on the thermotropic liquid crystal polymer nascent fiber for 12-24h at the liquid crystal polymer melting point Tm-50-Tm-5 ℃ in the nitrogen atmosphere to obtain the thermotropic liquid crystal polymer fiber.
Further preferably, the amount of the added acetic anhydride is 1.0 to 2.0 times of the total mole number of all the monomer hydroxyl groups.
Further preferably, the 4-ethylaminopyridine is added in an amount of 200 to 400ppm based on the total weight of all monomers.
Further preferably, the slow cooling temperature is 270-320 ℃, and the circular blowing temperature is 250-300 ℃.
More preferably, the aperture of the spinneret is 0.08 to 0.18mm, and the drawing speed is 500 to 1200m/min.
Another object of the present invention is to provide a laid fabric, which is prepared by the following steps: the thermotropic liquid crystal polymer fiber is sequentially warped, spread, dipped in glue, dried and rolled to prepare thermotropic liquid crystal polymer single-layer UD cloth, and then the single-layer UD cloth is subjected to hot-pressing compounding at 0 degree/90 degrees to obtain fiber composite cloth, namely the weftless cloth.
The non-woven fabric is manufactured by a special unidirectional composite process, the fibers are arranged in a unidirectional mode, damage to the fibers and weft skew defects in the weaving process of woven fabric warp yarns and weft yarns are avoided, and the non-woven fabric has better dimensional stability. In addition, compared with woven fabric, the non-woven fabric has more cross joints, after the shot or the fragment hits the fabric, the generated strain wave is divided into longitudinal wave and transverse wave, the cross joints of the longitudinal wave can transfer stress to the auxiliary fiber, and the displacement generated by the transverse wave can make the edge fiber bear the conducted stress through the cross joints. Ballistic tests show that 40-50% of the energy is absorbed by the fibers. Therefore, the more the fabric has cross-over points, the more energy is absorbed and the better the ballistic performance.
Preferably, the gum solution for gum dipping comprises an adhesive and a curing agent in a mass ratio of 100 (0.1-3).
More preferably, the adhesive can be a water-soluble acrylate adhesive, a polyurethane adhesive or an elastomer adhesive; the curing agent may be an amine-based curing agent, an acid anhydride-based curing agent, a catalyst-based curing agent, a low molecular weight polyamide curing agent, or the like, for example, aqueous isocyanate, aziridine, carbodiimide, epoxy, or amino resin.
Preferably, the glue solution can also contain auxiliary agents such as a defoaming agent and a dispersing agent, and the content of the auxiliary agents is not more than 8% of the total mass of the glue solution.
Preferably, the hot pressing is carried out by pressing the plurality of UD fabrics at 60-120 ℃ and 1.5-3.0 MPa for 5-15 min.
It is a further object of the present invention to provide a use of the above-mentioned laid fabric for body armor.
Compared with the prior art, the invention has the technical effects that:
(1) The liquid crystal polymer material with moderate viscosity and molecular weight and capable of being used for stable spinning can be obtained by regulating and controlling the monomer with specific content for polymerization.
(2) The strength retention rate of the liquid crystal polymer fiber prepared by the invention at a high temperature of 120 ℃ is more than 95%, the moisture regain is not more than 0.024%, the surface of the finished product fiber is smooth and continuous, and the phenomena of yarn breakage and fuzzing are avoided.
(3) The bulletproof performance of the lightweight or hard bulletproof clothes made of the non-woven fabric is obviously improved through a target shooting test, and the bulletproof performance is still good after being soaked in water.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
A thermotropic liquid crystalline polymer fiber is prepared by melt spinning a liquid crystalline polymer, wherein the liquid crystalline polymer is prepared by polymerizing the following monomers: p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4 '-cyclododecanediphenol, and terephthalic acid, wherein 6-hydroxy-2-naphthoic acid is 40 to 55 parts by mole, 4' -cyclododecanediphenol is 3 to 10 parts by mole, and terephthalic acid is 3 to 10 parts by mole, based on 100 parts by mole of p-hydroxybenzoic acid;
preferably, the thermotropic liquid crystal polymer has a melt viscosity of 30 to 60Pa.s and a weight-average molecular weight of 8 to 14 ten thousand;
the thermotropic liquid crystal polymer fiber is prepared by the following method:
1. putting p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4' -cyclododecanediphenol, terephthalic acid, an acetylation reagent acetic anhydride and a catalyst 4-acetaminopyridine into a Hastelloy reaction kettle, keeping the temperature at 135-150 ℃ for 2-10 h, then heating to 300-320 ℃ at the speed of 0.5-1.0 ℃/min, keeping the temperature for 2-4 h, then filling nitrogen into the Hastelloy reaction kettle, discharging through the Hastelloy polymerization kettle, crushing and drying to obtain a prepolymer; carrying out solid-phase polycondensation on the prepolymer in a rotary kiln for 12-48 h at 220-320 ℃ under the protection of nitrogen to obtain a thermotropic liquid crystal polymer;
2. drying the thermotropic liquid crystal polymer, melting and plasticizing the thermotropic liquid crystal polymer in a nitrogen atmosphere, then performing melt ejection from a spinning nozzle, performing slow cooling circular blowing, drafting and shaping, dividing filaments and winding to prepare and obtain thermotropic liquid crystal polymer nascent fibers;
3. and (3) carrying out heat treatment on the thermotropic liquid crystal polymer nascent fiber for 12-24h at the liquid crystal polymer melting point Tm-50-Tm-5 ℃ in the nitrogen atmosphere to obtain the thermotropic liquid crystal polymer fiber.
More preferably, the amount of the acetic anhydride added is 1.0 to 2.0 times the total mole number of all the hydroxyl groups in the monomer.
More preferably, the amount of the 4-ethylaminopyridine added is 200 to 400ppm based on the total weight of all monomers.
Further preferably, the slow cooling temperature is 270-320 ℃, and the circular blowing temperature is 250-300 ℃.
More preferably, the aperture of the spinneret is 0.08 to 0.18mm, and the drawing speed is 500 to 1200m/min.
It is specifically noted that the catalyst of the present invention is prepared by the following method:
adding 1kg of ammonia water solution into a 2.5L three-neck flask, cooling to 0 ℃, then adding 150g of 4-chloropyridine, heating and refluxing for 1h, cooling, adding 50g of toluene, extracting for 2 times, combining extract liquor, adding 100g of anhydrous magnesium sulfate, drying for 24h, filtering, carrying out rotary evaporation to obtain a crude product, adding the crude product into 0.5kg of xylene, and recrystallizing to obtain 70g of near-colorless flaky crystals 4-ethylaminopyridine. Compared with the existing metal salt catalyst, the catalyst prepared by the method has higher catalytic efficiency and fewer reaction byproducts, and is beneficial to improving the production efficiency and improving the product performance.
Example 1
Putting 100 mole parts of p-hydroxybenzoic acid, 50 mole parts of 6-hydroxy-2-naphthoic acid, 5 mole parts of 4,4' -cyclododecanediphenol, 5 mole parts of terephthalic acid, acetic anhydride which is 1.5 times of the total mole number of all monomer hydroxyl groups and 4-acetamidopyridine which is 200ppm of the total weight of all monomers into a Hastelloy alloy reaction kettle, keeping the temperature at 140 ℃ for 6h, heating to 310 ℃ at the speed of 0.8 ℃/min, keeping the temperature for 3h, then filling nitrogen into the Hastelloy reaction kettle, discharging the nitrogen through the Hastelloy polymerization kettle, crushing and drying to obtain a prepolymer; carrying out solid phase polycondensation on the prepolymer in a rotary kiln at 290 ℃ under the protection of nitrogen for 24 hours to obtain a liquid crystal polymer;
drying the liquid crystal polymer, after melting and plasticizing in a nitrogen atmosphere, melting and spraying out the liquid crystal polymer at the spraying rate of 85g/min from a spinneret with the aperture of 0.12mm and the number of holes of 160, slowly cooling at 300 ℃, then circularly blowing at 280 ℃, drafting and shaping at the drafting speed of 500m/min, and winding in a filament separating manner to prepare the thermotropic liquid crystal polymer nascent fiber with the single-filament number of 5D and the total filament number of 800D;
and (3) carrying out heat treatment on the thermotropic liquid crystal polymer nascent fiber at the temperature of 270 ℃ for 24h in the nitrogen atmosphere to obtain the thermotropic liquid crystal polymer fiber.
Examples 2 to 4 and comparative examples 1 to 7 differ from example 1 only in the formulation used for the polymerization, which is specified in Table 1 and otherwise identical to example 1.
Example 5
This example uses the same formulation as example 1, except that:
putting p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4' -cyclododecanediphenol, terephthalic acid, acetic anhydride accounting for 1.0 time of the total mole number of all monomer hydroxyl groups and 4-acetamidopyridine accounting for 300ppm of the total weight of all monomer groups into a Hastelloy reaction kettle, keeping the temperature at 135 ℃ for 10 hours, then heating to 300 ℃ at the speed of 0.5 ℃/min, keeping the temperature for 4 hours, then filling nitrogen into the Hastelloy reaction kettle, discharging through the Hastelloy polymerization kettle, crushing and drying to obtain a prepolymer; carrying out solid-phase polycondensation on the prepolymer in a rotary kiln at 220 ℃ for 12h under the protection of nitrogen to obtain a thermotropic liquid crystal polymer;
drying the liquid crystal polymer, melting and plasticizing the liquid crystal polymer in a nitrogen atmosphere, then performing melt ejection from a spinneret with the aperture of 0.12mm and the number of holes of 160 at the ejection rate of 170g/min, performing slow cooling at 270 ℃, performing ring blowing at 250 ℃, performing drawing and shaping at the drawing speed of 1000m/min, and performing split winding to prepare the thermotropic liquid crystal polymer nascent fiber with the filament number of 5D and the total filament number of 800D;
and (3) carrying out heat treatment on the thermotropic liquid crystal polymer nascent fiber at the temperature of 280 ℃ for 20h in the nitrogen atmosphere to obtain the thermotropic liquid crystal polymer fiber.
Example 6
This example uses the same formulation as example 1, except that: putting p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4' -cyclododecanediphenol, terephthalic acid, acetic anhydride accounting for 2.0 times of the total mole number of all monomer hydroxyl groups and 4-acetamidopyridine accounting for 400ppm of the total weight of all monomer groups into a Hastelloy reaction kettle, keeping the temperature at 150 ℃ for 2h, then heating to 320 ℃ at the speed of 1.0 ℃/min, keeping the temperature for 2h, then filling nitrogen into the Hastelloy reaction kettle, discharging through the Hastelloy polymerization kettle, crushing and drying to obtain a prepolymer; carrying out solid-phase polycondensation on the prepolymer in a rotary kiln at 320 ℃ for 48h under the protection of nitrogen to obtain a thermotropic liquid crystal polymer;
drying the liquid crystal polymer, melting and plasticizing the liquid crystal polymer in a nitrogen atmosphere, then performing melt ejection from a spinneret with the aperture of 0.12mm and the number of holes of 160 at an ejection rate of 205g/min, performing slow cooling at 320 ℃, performing circular blowing at 300 ℃, performing drawing and shaping at a drawing speed of 1200m/min, and performing split winding to prepare the thermotropic liquid crystal polymer nascent fiber with the filament number of 5D and the total filament number of 800D;
and (3) carrying out heat treatment on the thermotropic liquid crystal polymer nascent fiber for 12h at the temperature of 295 ℃ in a nitrogen atmosphere to obtain the thermotropic liquid crystal polymer fiber.
Comparative example 8
This comparative example differs from example 3 only in that the catalyst used was potassium acetate, a metal salt catalyst commonly used in the prior art.
The properties of the liquid crystalline polymers, fibers of the present invention were tested in the following manner.
1. Liquid crystal polymer testing
(1) Melting point (Tm): melting point measurements were carried out using a differential scanning calorimeter/DSC-500C according to ISO11357-1/-3 standard.
(2) Melt viscosity: heating the liquid crystalline polymer to a temperature of 25 ℃ + -5 ℃ above the melting point for 1000s -1 Melt viscosity was measured at shear rate using a rheometer according to GB/T25278-2010.
(3) Weight average molecular weight: the liquid crystal polymer was dissolved in a mixed solvent of pentafluorophenol/chloroform =35/65 (weight ratio) at a concentration of 0.04 to 0.08 wt/vol%, and the supernatant was measured with a GPC measuring apparatus to obtain a weight average molecular weight (Mw) in terms of polystyrene.
(4) Spinning property: the results were evaluated based on the actual spinning effect, and "+" indicates good spinning properties, "+" indicates general spinning properties, and "-" indicates poor spinning properties.
2. Liquid crystal polymer fiber testing
(1) Tensile strength and tensile modulus: the test is carried out by adopting a microcomputer control electronic universal tester/GBW-1T according to the GB/T19975-2005 standard.
(2) Water absorption: the test was carried out according to GB/T6284-2006 standard.
(3) Strength retention ratio: the drafting strength of the fiber is tested by a universal tester at normal temperature and recorded as T1, the fiber is treated at 120 ℃ for 2h, the drafting strength is tested by the universal tester and recorded as T2, and T2/T1 is the strength retention rate.
(4) Appearance quality: and (5) observing by naked eyes to check whether the surface of the fiber is flat, smooth and continuous.
TABLE 1
TABLE 2
TABLE 3
The thermotropic liquid crystal polymer fibers in examples 1 to 6 and comparative examples 1 to 8 are made into a non-woven fabric and then applied to body armor, and the method specifically comprises the following steps:
(1) preparing glue solution:
mixing the adhesive and the curing agent according to the mass ratio of 100 (0.1-3), and adding a defoaming agent and a dispersing agent which are not more than 8% of the weight of the glue solution for uniform mixing; the main body equipment adopts a winding machine for manufacturing the weftless fabric, and the prepared glue solution is placed in a glue box of the winding machine to complete the glue solution preparation;
(2) warping, spreading and gum dipping: warping liquid crystal polymer fibers by a warping machine, enabling fiber bundles to enter a fiber spreading module to enable each fiber bundle to achieve uniform filament spreading, enabling the liquid crystal polymer fibers after filament spreading to penetrate through a glue box and to be wound on a winding machine in parallel, setting the speed of a roller of the winding machine according to the linear density of the liquid crystal polymer fibers, and ensuring that the fibers are arranged in parallel without gaps;
(3) heating, drying and rolling: heating and drying the fibers subjected to gum dipping at 60-120 ℃, and rolling to form UD cloth;
(4) hot-pressing and superposing: and taking down the arranged UD cloth, cutting the UD cloth into 400mm multiplied by 400mm, pressing the UD cloth for 5 to 15min at the temperature of between 60 and 120 ℃ and under the pressure of between 1.5 and 3.0MPa according to the 0 degree/90 degree direction to obtain a multi-layer overlapped soft bulletproof cloth, and measuring the secondary bulletproof performance according to the GA141-2010 police bulletproof cloth standard, namely a 7.62mm pistol bullet (lead core) in 1951 and the bullet speed of 445 +/-10 m/s, wherein the test result is shown in a table 4. Or compounding with ceramic plates such as silicon carbide and the like to obtain the hard bulletproof garment, and testing the four-grade bulletproof performance according to the GA141-2010 police bulletproof garment standard, a 7.62mm pistol (steel core) in 1951 and the bullet speed of 515 +/-10 m/s, wherein the test results are shown in Table 4.
TABLE 4
The test of the resistance to water immersion in table 4 above was carried out as follows: and horizontally immersing the body armor into water with the depth of 0.5m at normal temperature, standing for 30min, taking out the suspended dropping water for 5min, starting a first launch test within 10, finishing a shooting test within 30, and recording data.
Standard deviation μ = (V) 50 -V min ) /3 (wherein V) 50 Is ballistic limit velocity, V min Minimum penetration velocity).
In conclusion, the liquid crystal polymer has good spinning property, the fiber obtained by spinning has excellent strength, modulus, low water absorption and high-temperature strength retention rate, the non-woven fabric made of the fiber has excellent apparent quality and performance, and the non-woven fabric has better protection effect when being used for bullet-proof clothes.
In particular, those skilled in the art can prepare fibers having specifications of 400D, 1200D, 1500D, 1600D by adjusting process parameters such as the discharge amount, the spinneret hole diameter, the drawing speed, etc., according to actual needs, but the invention is not limited thereto.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above examples, and it is obvious to those skilled in the art that the present invention is within the protection scope of the present invention as long as the present invention does not depart from the spirit and scope of the present invention.
Claims (10)
1. A thermotropic liquid crystal polymer fiber is prepared by melt spinning a liquid crystal polymer, and is characterized in that the liquid crystal polymer is polymerized by the following monomers: p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4 '-cyclododecanediphenol and terephthalic acid, wherein the 6-hydroxy-2-naphthoic acid is 40 to 55 mol parts, the 4,4' -cyclododecanediphenol is 3 to 10 mol parts and the terephthalic acid is 3 to 10 mol parts based on 100 mol parts of the p-hydroxybenzoic acid.
2. The thermotropic liquid crystalline polymer fiber of claim 1, wherein the thermotropic liquid crystalline polymer has a melt viscosity of 30 to 60pa-s.
3. The thermotropic liquid crystalline polymer fiber of claim 1, wherein the thermotropic liquid crystalline polymer has a weight average molecular weight of 8 to 14 ten thousand.
4. The thermotropic liquid crystalline polymer of claim 1, having a single fiber denier of no more than 5D.
5. The thermotropic liquid crystalline polymer fiber of claim 1, prepared by a method comprising the steps of:
1. putting p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4' -cyclododecanediphenol, terephthalic acid, an acetylation reagent acetic anhydride and a catalyst 4-acetaminopyridine into a Hastelloy reaction kettle, keeping the temperature at 135-150 ℃ for 2-10 h, then heating to 300-320 ℃ at the speed of 0.5-1.0 ℃/min, keeping the temperature for 2-4 h, then filling nitrogen into the Hastelloy reaction kettle, discharging through the Hastelloy polymerization kettle, crushing and drying to obtain a prepolymer; carrying out solid phase polycondensation on the prepolymer in a rotary kiln at 220-320 ℃ for 12-48 h under the protection of nitrogen to obtain a thermotropic liquid crystal polymer;
2. drying the thermotropic liquid crystal polymer, melting and plasticizing the thermotropic liquid crystal polymer in a nitrogen atmosphere, then performing melt ejection from a spinning nozzle, performing slow cooling circular blowing, drafting and shaping, dividing filaments and winding to prepare and obtain thermotropic liquid crystal polymer nascent fibers;
3. and (3) carrying out heat treatment on the thermotropic liquid crystal polymer nascent fiber for 12-24h at the liquid crystal polymer melting point Tm-50-Tm-5 ℃ in the nitrogen atmosphere to obtain the thermotropic liquid crystal polymer fiber.
6. The thermotropic liquid crystalline polymer fiber of claim 5, wherein the slow cooling temperature is 270 to 320 ℃ and the circular blowing temperature is 250 to 300 ℃.
7. The thermotropic liquid crystalline polymer fiber of claim 5, wherein the spinneret has a hole diameter of 0.08 to 0.18mm and a drawing speed of 500 to 1200m/min.
8. A non-woven fabric is characterized in that the thermotropic liquid crystal polymer fiber in any one of claims 1 to 7 is sequentially subjected to warping, spreading, gum dipping, drying and rolling to obtain thermotropic liquid crystal polymer single-layer UD fabric, and then the single-layer UD fabric is subjected to hot-pressing compounding at 0 degrees/90 degrees to obtain fiber composite fabric, namely the non-woven fabric.
9. The laid fabric as claimed in claim 8, wherein the heat pressing is carried out by pressing the plurality of UD fabrics at 60-120 ℃ and 1.5-3.0 MPa for 5-15 min.
10. Use of the laid fabric of claim 8 in soft or hard body armor.
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