CN108505137B - Thermotropic liquid crystal polyarylester fiber and preparation method thereof - Google Patents
Thermotropic liquid crystal polyarylester fiber and preparation method thereof Download PDFInfo
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
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Abstract
The invention discloses a thermotropic liquid crystal polyarylate fiber and a preparation method thereof. The preparation method comprises the following steps: plasticizing the thermotropic liquid crystal polyarylate slices at 300-370 ℃ by a single-screw extruder, exhausting, and sequentially metering by a metering pump, spinning by a spinning assembly, drafting and collecting to obtain nascent polyarylate fibers; and carrying out solid phase polymerization on the nascent polyarylate fiber at 240-330 ℃ for 2-20h under a nitrogen flow containing organic acid anhydride to obtain the thermotropic liquid crystal polyarylate fiber. The breaking strength of the prepared thermotropic liquid crystal polyarylate fiber is 4.6-6.5 GPa. The preparation method of the high-strength thermotropic liquid crystal polyarylate fiber has the advantages of simple operation, easily controlled process conditions, convenient continuous production, wide application prospect and important economic value.
Description
Technical Field
The invention relates to a high-performance thermotropic liquid crystal polymer fiber and a preparation method thereof, belonging to the technical field of high-performance chemical fibers.
Background
The Liquid Crystal Polymer (LCP) is a novel material developed in the 60 s of the 20 th century, and a molecular chain contains rigid rod-shaped or dish-shaped groups, and can form a liquid crystal phase in a solution or molten state, so that the material is endowed with certain unique properties. Under the induction of external force, molecules of the LCP are highly oriented, so that the LCP has excellent mechanical, photoelectric and thermal stability. Liquid crystal polymer LCP can be classified into thermotropic liquid crystal polymer and lyotropic liquid crystal polymer according to the condition of liquid crystal formation. The thermotropic liquid crystalline polymer is mainly represented by thermotropic liquid crystalline polyarylate. The lyotropic liquid crystalline polymer is typically represented by aromatic polyamide obtained by polycondensation of aromatic diacid and aromatic diamine. In the 50 s to 70 s, DuPont, USA, invested a lot of manpower and financial resources to research the development of polymer liquid crystal, and in 1972, developed ultrahigh strength and high modulus glass fiber with better strength
Fiber and is applied to industrialization. Thermotropic liquid crystal polymer is a polymer which presents liquid crystal state in a molten state, and compared with the lyotropic liquid crystal polymer which presents liquid crystal state in a solution, the thermotropic liquid crystal polymer has simple processing mode and is environment-friendly. The thermotropic liquid crystal polymer can be melt spun, injected and formed into a film, does not generally relate to the use and the recovery of a solvent in the processing process, and is the liquid crystal polymer with the largest commercial brand in the current industrialized production. E.g. of Saranis
Of Amoxico oil Co Ltd
Of the firm Ishmann Kodak
Isotropic liquid crystalline polymers have dominated the LCP market worldwide. In addition, since most thermotropic liquid crystal polymer TLCP products are polyarylate liquid crystals, the thermotropic liquid crystal polymer TLCP is also commonly referred to as polyarylate, and to some extent, the thermotropic liquid crystal polymer TLCP is also equivalent to polyarylate.
The polyarylate is a polymer formed by connecting aromatic rings through ester bonds, the molecular structure of the polyarylate is different from that of the traditional random coil or cross-linked network structure, and the polyarylate is formed by linking long rigid rod-shaped molecular units. Liquid crystals are formed during the heating process. When the liquid crystal material is cooled from a liquid crystal state to a solid state, the highly oriented arrangement of the molecular chains is retained, a specific highly oriented structure is formed, and the properties are made anisotropic. The thermotropic liquid crystal polyarylate has a series of advantages of high strength and high modulus, flame resistance, low water absorption, good dimensional stability and the like, and is widely applied to the fields of automobiles, electronics, war industry, protection and the like. The monomers used for synthesizing the aromatic polyester liquid crystal are numerous and can be divided into 3 types according to the properties of the functional groups of the monomers: one end of the aromatic ring is hydroxyl (H) and the other end is carboxylic acid group (A) is AH type, such as p-hydroxybenzoic acid (HBA), 2-hydroxy-6-naphthoic acid (HNA), etc.; aromatic rings containing 2 carboxylic acid groups and of the AA type, such as terephthalic acid (TPA), isophthalic acid, diphenic acid, 2, 6-naphthalenedicarboxylic acid; containing 2 hydroxyl groups on the aromatic ring, of the HH type, such as Hydroquinone (HQ), Biphenol (BP), 2, 6-naphthalenediol, etc.
When the thermotropic liquid crystalline polymer is extruded through the spinneret under high shear stress, the molecules thereof are highly oriented, and the oriented structure is almost completely maintained during cooling solidification due to the long relaxation time, and thus, a high-performance thermotropic liquid crystalline polyarylate fiber can be obtained by melt spinning. But due to polymerization raw materials, formula design, polymerization equipment and spinningThe practical realization of industrialization of equipment, heat treatment equipment, etc. under various restrictions was developed by the cooperation of the American Seranian corporation and the Japanese Coly corporation in 1990
The fiber, the Colrison Bar factory starts to produce
A fibrous product. In 4 months 2005, the company, clony, purchased high performance fiber services from advanced materials of selanis (CAMI) in south carolina, usa. This co-purchase makes the cola group the only world
The source of the fiber. And subsequently, glary further expands the business and product sales on a global scale. With the rapid increase of market demand in 2007, the production device of the city of western stripes in Yuan county of love is expanded by the Coly corporation, and the capacity is increased from 600 tons to 1000 tons.
The breaking strength of the polyarylate fiber is about 3GPa generally, and is slightly higher than that of aramid fiber (2.8 GPa).
The fiber can reach 3.3GPa (polyarylate fiber, national defense industry press, 2017, page 135; CN 1252462A; US 5945216). The fiber breaking strength of the polyarylate fiber can be greatly improved by heat treatment of the as-spun fiber by dupont, but the strength thereof is also about 3 GPa. A novel liquid crystal polyarylester (CN201410612674.7) with the strength as high as 4.0-4.5 GPa is prepared by the co-polymerization of p-hydroxybenzoic acid and 2- (4-hydroxyphenyl) -5-carboxyl benzimidazole by Heilongjiang Polyxiang scientific and technological development Limited company. In recent years, with the expansion of the field of application of polyarylate fibers and the advancement of aerospace technology, further demands have been made on the strength of polyarylate fibers. The invention provides a high-performance thermotropic liquid crystal polyarylate fiber with the fiber breaking strength of more than 4.6GPa and a preparation method thereof through systematic innovative research.
Disclosure of Invention
The invention aims to solve the problems that: provides a high-performance thermotropic liquid crystal polyarylate fiber with the fiber breaking strength of more than 4.6GPa and a preparation method thereof.
In order to solve the above problems, the present invention provides a method for preparing thermotropic liquid crystalline polyarylate fiber, comprising the steps of:
step 1): plasticizing the thermotropic liquid crystal polyarylate slices at 300-370 ℃ by a single-screw extruder, exhausting, and sequentially metering by a metering pump, spinning by a spinning assembly, drafting and collecting to obtain nascent polyarylate fibers;
step 2): and carrying out solid phase polymerization on the nascent polyarylate fiber at 240-330 ℃ for 2-20h under a nitrogen flow containing organic acid anhydride to obtain the thermotropic liquid crystal polyarylate fiber.
Preferably, the thermotropic liquid crystalline polyarylate in the step 1) is a copolyester of p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid.
Preferably, the concentration of the organic acid anhydride in the step 2) in the nitrogen flow is 0.1-10 mu mol/L.
Preferably, the organic acid anhydride in step 2) is acetic anhydride.
In the solid phase polymerization process of the nascent fiber, the solid phase polymerization temperature is determined by the melting point of thermotropic liquid crystal polyarylate. The polymerization speed is slow in consideration of the fact that the temperature is too low; the solid phase polymerization temperature is generally set to be about 10-50 ℃ below the melting point of the polyarylate, whereas the melting point of the high-performance polyarylate is generally between 280-350 ℃, and the plasticizing temperature is generally set to be 230-340 ℃. Preferably between 240 ℃ and 330 ℃. In the present invention, since the polymerization rate is high in the presence of an acid anhydride, a high molecular weight polyarylate fiber can be obtained in 1 to 30 hours, preferably 2 to 20 hours.
The invention provides a thermotropic liquid crystal polyarylate fiber prepared by the preparation method of the thermotropic liquid crystal polyarylate fiber, which is characterized in that the breaking strength of the fiber is 4.6-6.5 GPa, and preferably the breaking strength is 5.0-6.5 GPa.
Preferably, a 1g/L polyarylate fiber solution is prepared by using a mixture of pentafluorophenol and hexafluoroisopropanol as a solvent, wherein the volume part of the mixture is equal to the volume part of the mixture, and the inherent viscosity IV of the solution at 25 ℃ is 10-50 dL/g.
More preferably, the inherent viscosity IV is 30 to 50 dL/g. The inherent viscosity is measured by the following method: thermotropic liquid crystalline polyarylate fibers were dissolved in a pentafluorophenol/hexafluoroisopropanol mixed solvent (equal parts of pentafluorophenol and hexafluoroisopropanol) to prepare a solution of 0.1g polyarylate/100 ml mixed solvent, which was then measured and calculated at 25 ℃ using an Ubbelohde viscometer.
The thermotropic liquid crystal polyarylate fiber has excellent extensibility, and the elongation at break is generally more than 4.0%, preferably between 4.5 and 6.0%. Now for other known thermotropic liquid crystalline polyarylate fibers, the high elongation at break of the present invention is also derived from the high molecular weight. The high strength results from the high molecular weight of the fibers, which results from the solid phase polymerization of the as-spun fibers.
The linear density of the thermotropic liquid crystalline polyarylate fiber of the present invention has a large influence on the fiber strength, and generally the linear density increases and the fiber strength tends to decrease. In order to ensure the high strength of the fiber, the linear density of the thermotropic liquid crystal polyarylate fiber is generally between 3.00 dtex and 6.00 dtex; preferably between 3.00 and 4.00 dtex.
The single-screw extrusion temperature in the preparation method is determined by the properties of thermotropic liquid crystal polyarylate, the plasticizing temperature is generally set to be about 20 ℃ above the melting point of polyarylate, the melting point of high-performance polyarylate is generally between 280 ℃ and 350 ℃, and the plasticizing temperature is generally set to be 300-370 ℃. On the one hand, the fluidity is considered, and on the other hand, the thermal degradation is reduced as much as possible, and the temperature is preferably between 310 and 350 ℃.
The invention has no special requirement on the spinning speed of the primary silk, and the winding speed is generally set between 200 and 2000 m/min in consideration of the production efficiency. The aspect ratio of the orifices in the spinneret in the present invention is generally in the range of 1 to 15, preferably 4 to 10.
The present invention utilizes solid phase polymerization to increase the molecular weight of polyarylate fibers. The solid-phase polymerization is a polymerization reaction of solid oligomer at a temperature higher than the glass transition temperature and lower than the melting point of the polymer, and the method can effectively improve the molecular weight of the polyester polymer. The mechanism of solid-phase polymerization is: in the low molecular weight polyester prepolymer (fiber, slice, powder, etc.), functional group end group, small molecular monomer, catalyst, etc. are enriched in amorphous region by crystallization, so that the reaction balance moves to positive direction; the small molecular by-products in the reaction system are taken away by means of reduced pressure or inert gas, so that the molecular chain continues to grow, and the product with higher molecular weight is obtained. The solid-phase polymerization of polyester depends on two aspects of chemical reaction and physical diffusion, and small molecule products are diffused from the interior of particles to the surfaces of the particles through reversible chemical reaction and then diffused from the surfaces of the particles into the surrounding reduced pressure atmosphere or inert gas atmosphere. The reaction rate of the whole polymerization reaction is determined by the slowest step described above according to the low rate determination principle. The polymerization time, polymerization temperature, catalyst, pressure or inert gas flow, prepolymer crystallinity, prepolymer geometry, etc., will all affect the progress of the solid phase polymerization reaction.
In the solid-phase polymerization process of the nascent fiber, organic acid anhydride is used for promoting the polymerization speed and improving the polymerization degree so as to obtain the high molecular weight polyarylate. The present invention is not particularly limited with respect to the kind of the acid anhydride. In view of volatility and diffusion rate in polyarylate fibers, low carbon number fatty acid anhydrides are generally preferred, anhydrides of organic acids having C2-C6 are preferred, and acetic anhydride, propionic anhydride, and butyric anhydride are most preferred. The content of the organic acid anhydride in the nitrogen flow is generally between 0.01 and 100. mu. mol/L, preferably between 0.1 and 10. mu. mol/L.
The polyarylate of the present invention is not particularly limited in kind, and may be any copolymer of monomers selected from the group consisting of p-hydroxybenzoic acid (HBA), 2-hydroxy-6-naphthoic acid (HNA), terephthalic acid (TPA), isophthalic acid, biphenyldicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, Hydroquinone (HQ), Biphenyldiol (BP), 2, 6-naphthalenediol, and the like. Preferred are copolymerized polyarylates copolymerized from p-hydroxybenzoic acid (HBA), 2-hydroxy-6-naphthoic acid (HNA), and copolymerized polyarylates copolymerized from p-hydroxybenzoic acid (HBA), Biphenol (BP), phthalic acid. Most preferred are copolymerized polyarylates obtained by copolymerizing p-hydroxybenzoic acid (HBA) and 2-hydroxy-6-naphthoic acid (HNA).
The preparation method of the high-strength thermotropic liquid crystal polyarylate fiber is simple to operate, the process conditions are easy to control, continuous production is facilitated, the drawing strength of the finally obtained thermotropic liquid crystal polyarylate fiber can reach 4.6-6.5 GPa, and the preparation method has wide application prospect and important economic value.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below.
The polyarylates employed in examples 1 to 9 are
A950 (copolymer of HBA and HNA), Sumitomo chemical SUMIKASUPER LCP E6000 (copolymer of HBA, BP and phthalic acid).
IV is the inherent viscosity in examples 1-9; the unit dL/g is deciliter per gram.
And IV determination: 0.2g of a polymer sample was dissolved in 200ml of a mixed solvent of pentafluorophenol and hexafluoroisopropanol in equal volume parts to prepare a solution, which was measured at 25 ℃ using an Ubbelohde viscometer.
Example 1
A950 was vacuum dried at 120 ℃ to a water content of less than 12ppm and then melt spun. The heating temperatures of the screws for melt spinning are respectively as follows: the feeding zone is 260 ℃, the melting zone is 320 ℃, the compression zone is 315 ℃, the box body temperature is 315 ℃, the winding speed is 800m/min, and the nascent fiber is obtained after spinning forming. The as-spun fibers were then solid phase polymerized: placing the nascent fiber in a solid-phase polymerization box, replacing nitrogen for 3 times, adjusting the flow of the nitrogen to be 10L/min, and heating to 260 ℃ at the heating rate of 1 ℃/min; at this time, acetic anhydride was introduced into a nitrogen stream by a syringe pump at an injection rate of 1. mu.L/min; solid-phase polymerization under the conditions for 10 hours; the high-strength thermotropic liquid crystal polyarylate fiber is obtained, the breaking strength of the fiber is 4.8GPa, the elongation is 4.8 percent, and the IV is 15 dL/g.
Example 2
A950 was vacuum dried at 120 ℃ to a water content of less than 12ppm and then melt spun. The heating temperatures of the screws for melt spinning are respectively as follows: the feeding zone is 260 ℃, the melting zone is 320 ℃, the compression zone is 315 ℃, the box body temperature is 315 ℃, the winding speed is 800m/min, and the nascent fiber is obtained after spinning forming. The as-spun fibers were then solid phase polymerized: placing the nascent fiber in a solid-phase polymerization box, replacing nitrogen for 3 times, adjusting the flow of the nitrogen to be 10L/min, and heating to 260 ℃ at the heating rate of 1 ℃/min; at this time, acetic anhydride was introduced into a nitrogen stream by a syringe pump at an injection rate of 10. mu.L/min; solid-phase polymerization under the conditions for 20 hours; the high-strength thermotropic liquid crystal polyarylate fiber is obtained, the breaking strength of the fiber is 6.3GPa, the elongation is 4.7 percent, and the IV is 41 dL/g.
Example 3
A950 was vacuum dried at 120 ℃ to a water content of less than 12ppm and then melt spun. The heating temperatures of the screws for melt spinning are respectively as follows: the feeding zone is 260 ℃, the melting zone is 320 ℃, the compression zone is 315 ℃, the box body temperature is 315 ℃, the winding speed is 800m/min, and the nascent fiber is obtained after spinning forming. The as-spun fibers were then solid phase polymerized: placing the nascent fiber in a solid phase polymerization box, replacing nitrogen for 3 times, adjusting the flow of the nitrogen to be 10L/min, and heating to 240 ℃ at the heating speed of 1 ℃/min; at this time, acetic anhydride was introduced into a nitrogen stream by a syringe pump at an injection rate of 10. mu.L/min; solid-phase polymerization under the conditions for 20 hours; the high-strength thermotropic liquid crystal polyarylate fiber is obtained, the breaking strength of the fiber is 4.9GPa, the elongation is 5.3 percent, and the IV is 18 dL/g.
Example 4
A950 was vacuum dried at 120 ℃ to a water content of less than 12ppm and then melt spun. The heating temperatures of the screws for melt spinning are respectively as follows: the feeding zone is 260 ℃, the melting zone is 320 ℃, the compression zone is 315 ℃, the box body temperature is 315 ℃, the winding speed is 800m/min, and the nascent fiber is obtained after spinning forming. The as-spun fibers were then solid phase polymerized: placing the nascent fiber in a solid-phase polymerization box, replacing nitrogen for 3 times, adjusting the flow of the nitrogen to be 10L/min, and heating to 270 ℃ at the heating speed of 1 ℃/min; at this time, acetic anhydride was introduced into a nitrogen stream by a syringe pump at an injection rate of 80. mu.L/min; solid-phase polymerization was carried out under these conditions for 6 hours; the high-strength thermotropic liquid crystal polyarylate fiber is obtained, the breaking strength of the fiber is 5.5GPa, the elongation is 5.4 percent, and the IV is 25 dL/g.
Example 5
A950 was vacuum dried at 120 ℃ to a water content of less than 12ppm and then melt spun. The heating temperatures of the screws for melt spinning are respectively as follows: the feeding zone is 260 ℃, the melting zone is 320 ℃, the compression zone is 315 ℃, the box body temperature is 315 ℃, the winding speed is 800m/min, and the nascent fiber is obtained after spinning forming. The as-spun fibers were then solid phase polymerized: placing the nascent fiber in a solid-phase polymerization box, replacing nitrogen for 3 times, adjusting the flow of the nitrogen to be 10L/min, and heating to 260 ℃ at the heating rate of 1 ℃/min; at this time, propionic anhydride was introduced into a nitrogen stream by an injection pump at an injection rate of 10. mu.L/min; solid-phase polymerization under the conditions for 20 hours; the high-strength thermotropic liquid crystal polyarylate fiber is obtained, the breaking strength of the fiber is 5.9GPa, the elongation is 4.5 percent, and the IV is 38 dL/g.
Example 6
A950 was vacuum dried at 120 ℃ to a water content of less than 12ppm and then melt spun. The heating temperatures of the screws for melt spinning are respectively as follows: the feeding zone is 260 ℃, the melting zone is 320 ℃, the compression zone is 315 ℃, the box body temperature is 315 ℃, the winding speed is 800m/min, and the nascent fiber is obtained after spinning forming. The as-spun fibers were then solid phase polymerized: placing the nascent fiber in a solid-phase polymerization box, replacing nitrogen for 3 times, adjusting the flow of the nitrogen to be 10L/min, and heating to 260 ℃ at the heating rate of 1 ℃/min; at this time, butyric anhydride was introduced into a nitrogen stream by an injection pump at an injection rate of 10. mu.L/min; solid-phase polymerization under the conditions for 20 hours; the high-strength thermotropic liquid crystal polyarylate fiber is obtained, the breaking strength of the fiber is 5.6GPa, the elongation is 4.2 percent, and the IV is 36 dL/g.
Example 7
E6000 was vacuum dried at 120 ℃ to a water content of less than 12ppm and then melt spun. The heating temperatures of the screws for melt spinning are respectively as follows: the feeding zone is 330 ℃, the melting zone is 350 ℃, the compression zone is 350 ℃, the box body temperature is 350 ℃, the winding speed is 800m/min, and the nascent fiber is obtained after spinning forming. The as-spun fibers were then solid phase polymerized: placing the nascent fiber in a solid-phase polymerization box, replacing nitrogen for 3 times, adjusting the flow of the nitrogen to be 10L/min, and heating to 320 ℃ at the heating speed of 1 ℃/min; at this time, acetic anhydride was introduced into a nitrogen stream by a syringe pump at an injection rate of 10. mu.L/min; solid-phase polymerization under the conditions for 15 hours; the high-strength thermotropic liquid crystal polyarylate fiber is obtained, the breaking strength of the fiber is 6.4GPa, the elongation is 5.5 percent, and the IV is 38 dL/g.
Example 8
A950 was vacuum dried at 120 ℃ to a water content of less than 12ppm and then melt spun. The heating temperatures of the screws for melt spinning are respectively as follows: the feeding zone is 260 ℃, the melting zone is 320 ℃, the compression zone is 315 ℃, the box body temperature is 315 ℃, the winding speed is 800m/min, and the nascent fiber is obtained after spinning forming. The as-spun fibers were then solid phase polymerized: placing the nascent fiber in a solid-phase polymerization box, replacing nitrogen for 3 times, adjusting the flow of the nitrogen to be 10L/min, and heating to 260 ℃ at the heating rate of 1 ℃/min; at this time, acetic anhydride was introduced into a nitrogen stream by a syringe pump at an injection rate of 0.5. mu.L/min; solid-phase polymerization under the conditions for 10 hours; the high-strength thermotropic liquid crystal polyarylate fiber is obtained, the breaking strength of the fiber is 4.6GPa, the elongation is 4.6 percent, and the IV is 12 dL/g.
Example 9
A950 was vacuum dried at 120 ℃ to a water content of less than 12ppm and then melt spun. The heating temperatures of the screws for melt spinning are respectively as follows: the feeding zone is 260 ℃, the melting zone is 320 ℃, the compression zone is 315 ℃, the box body temperature is 315 ℃, the winding speed is 800m/min, and the nascent fiber is obtained after spinning forming. The as-spun fibers were then solid phase polymerized: placing the nascent fiber in a solid-phase polymerization box, replacing nitrogen for 3 times, adjusting the flow of the nitrogen to be 10L/min, and heating to 270 ℃ at the heating speed of 1 ℃/min; at this time, acetic anhydride was introduced into a nitrogen stream by a syringe pump at an injection rate of 250. mu.L/min; solid-phase polymerization was carried out under these conditions for 6 hours; the high-strength thermotropic liquid crystal polyarylate fiber is obtained, the breaking strength of the fiber is 5.3GPa, the elongation is 5.1 percent, and the IV is 23 dL/g.
Comparative example 1
A950 was vacuum dried at 120 ℃ to a water content of less than 12ppm and then melt spun. The heating temperatures of the screws for melt spinning are respectively as follows: the feeding zone is 260 ℃, the melting zone is 320 ℃, the compression zone is 315 ℃, the box body temperature is 315 ℃, the winding speed is 800m/min, and the nascent fiber is obtained after spinning forming. The as-spun fibers were then solid phase polymerized: placing the nascent fiber in a solid-phase polymerization box, replacing nitrogen for 3 times, adjusting the flow of the nitrogen to be 10L/min, and heating to 260 ℃ at the heating rate of 1 ℃/min; solid-phase polymerization was carried out for 20 hours without introducing an organic acid anhydride; the high-strength thermotropic liquid crystal polyarylate fiber is obtained, and the fiber breaking strength is 3.3GPa, the elongation is 3.2 percent, and the IV is 9.5 dL/g.
Comparative example 2
E6000 was vacuum dried at 120 ℃ to a water content of less than 12ppm and then melt spun. The heating temperatures of the screws for melt spinning are respectively as follows: the feeding zone is 330 ℃, the melting zone is 350 ℃, the compression zone is 350 ℃, the box body temperature is 350 ℃, the winding speed is 800m/min, and the nascent fiber is obtained after spinning forming. The as-spun fibers were then solid phase polymerized: placing the nascent fiber in a solid-phase polymerization box, replacing nitrogen for 3 times, adjusting the flow of the nitrogen to be 10L/min, and heating to 320 ℃ at the heating speed of 1 ℃/min; solid-phase polymerization was carried out for 15 hours without introducing an organic acid anhydride; the high-strength thermotropic liquid crystal polyarylate fiber is obtained, the breaking strength of the fiber is 3.5GPa, the elongation is 3.5 percent, and the IV is 8 dL/g.
Claims (9)
1. A method for preparing thermotropic liquid crystal polyarylate fiber is characterized by comprising the following steps:
step 1): plasticizing the thermotropic liquid crystal polyarylate slices at 300-370 ℃ by a single-screw extruder, exhausting, and sequentially metering by a metering pump, spinning by a spinning assembly, drafting and collecting to obtain nascent polyarylate fibers;
step 2): under the flow of nitrogen containing organic acid anhydride, carrying out solid phase polymerization on the nascent polyarylate fiber at 240-330 ℃ for 2-20h to obtain thermotropic liquid crystal polyarylate fiber;
the organic acid anhydride in the step 2) is acetic anhydride.
2. The method of preparing the thermotropic liquid-crystalline polyarylate fiber of claim 1, wherein the thermotropic liquid-crystalline polyarylate in the step 1) is a copolyester of p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid.
3. The method for preparing the thermotropic liquid crystalline polyarylate fiber of claim 1, wherein the concentration of the organic acid anhydride in the nitrogen stream in the step 2) is 0.1 to 10 μmol/L.
4. A thermotropic liquid crystalline polyarylate fiber prepared by the method for preparing a thermotropic liquid crystalline polyarylate fiber according to any one of claims 1 to 3, wherein the fiber has a breaking strength of 4.6 to 6.5 GPa.
5. The thermotropic liquid crystalline polyarylate fiber of claim 4, wherein a polyarylate fiber solution having a concentration of 1g/L is prepared using a mixture of pentafluorophenol and hexafluoroisopropanol as a solvent in equal volume parts, and has an inherent viscosity IV of 10 to 50dL/g at 25 ℃.
6. The thermotropic liquid crystalline polyarylate fiber of claim 5, wherein the inherent viscosity IV is from 30 to 50 dL/g.
7. The thermotropic liquid crystalline polyarylate fiber of claim 4, wherein the elongation at break of the fiber is 4.5 to 6.0%.
8. The thermotropic liquid crystalline polyarylate fiber of claim 4, wherein the fiber has a linear density of 3.00 to 6.00 dtex.
9. The thermotropic liquid crystalline polyarylate fiber of claim 7, wherein the fiber has a linear density of 3.00 to 4.00dtex and a breaking strength of 5.0 to 6.5 GPa.
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| CN111186112B (en) * | 2018-11-14 | 2021-11-12 | 宁波聚嘉新材料科技有限公司 | Preparation method of novel thermotropic liquid crystal high-performance polyarylate film |
| CN109930270B (en) * | 2019-03-08 | 2020-06-12 | 东华大学 | Production method of blended yarn containing flame-retardant polyester fibers and polyarylate fibers |
| CN111072936A (en) * | 2019-12-23 | 2020-04-28 | 上海普利特化工新材料有限公司 | Wholly aromatic liquid crystal polyester resin and application thereof |
| CN113103710B (en) * | 2021-04-02 | 2022-01-07 | 宁波聚嘉新材料科技有限公司 | LCP composite film suitable for high frequency and high speed and preparation method thereof |
| CN113698642A (en) * | 2021-09-29 | 2021-11-26 | 宁夏清研高分子新材料有限公司 | High-strength liquid crystal polymer film and preparation method thereof |
| CN117661139B (en) * | 2024-02-02 | 2024-05-07 | 烟台泰和新材高分子新材料研究院有限公司 | Preparation method of liquid crystal polyester fiber |
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Application publication date: 20180907 Assignee: ZHEJIANG HAILIDE NEW MATERIAL Co.,Ltd. Assignor: DONGHUA University Contract record no.: X2022310000178 Denomination of invention: A thermotropic liquid crystalline polyarylester fiber and its preparation method Granted publication date: 20200811 License type: Exclusive License Record date: 20221219 |