WO2018045932A1 - Composition moulée de polyester à cristaux liquides et son application - Google Patents

Composition moulée de polyester à cristaux liquides et son application Download PDF

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WO2018045932A1
WO2018045932A1 PCT/CN2017/100371 CN2017100371W WO2018045932A1 WO 2018045932 A1 WO2018045932 A1 WO 2018045932A1 CN 2017100371 W CN2017100371 W CN 2017100371W WO 2018045932 A1 WO2018045932 A1 WO 2018045932A1
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magnesium
liquid crystal
crystal polyester
ppm
molding composition
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PCT/CN2017/100371
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English (en)
Chinese (zh)
Inventor
孙华伟
肖中鹏
周广亮
王鹏
谢湘
许柏荣
罗德彬
宋彩飞
姜苏俊
曹民
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金发科技股份有限公司
上海金发科技发展有限公司
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Publication of WO2018045932A1 publication Critical patent/WO2018045932A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C09K19/3804—Polymers with mesogenic groups in the main chain
    • C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/12—Applications used for fibers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the invention relates to the field of special engineering plastics, and in particular to a liquid crystal polyester molding composition and application thereof.
  • Thermotropic Liquid Crystalline Polyester (TLCP) is a high performance special engineering plastic with excellent mechanical properties, good hot processing fluidity, creep resistance and high dimensional stability, high and low temperature resistance, chemical resistance and resistance. Aging, self-reinforcing self-flame retardant and electrical insulation properties, currently widely used in electronic and electrical parts and other fields, especially as a field of exhaust blade device parts with high requirements for use in the environment, such as high temperature, heavy dust, air Computers, televisions, air conditioners, communication products, optoelectronic products, consumer electronics, automotive electronics, switches, medical equipment, heaters, air conditioners, inverters, teller machines, car refrigerators, welding machines operating in harsh environments such as humidity Induction cookers, audio equipment, environmental protection equipment, refrigeration equipment, etc. will generate a lot of hot equipment.
  • TLCP Thermotropic Liquid Crystalline Polyester
  • the exhaust fan device on the market generally uses polypropylene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, nylon and polybutylene terephthalate, but Thermoplastic polypropylene, styrene-acrylonitrile, is unsatisfactory in terms of mechanical properties, heat resistance, warpage resistance, etc., while nylon has poor dimensional stability due to high water absorption, and acrylonitrile-butadiene-styrene copolymerization The high temperature resistance of polybutylene terephthalate is inferior, so the above materials are no longer suitable for the requirements of the exhaust blade device of the special environment.
  • Liquid crystal polyester molding compositions with high fluidity, ultra high strength and high rigidity, excellent fatigue resistance, creep resistance, high and low temperature resistance, warpage resistance, and aging resistance are the best choices.
  • the tensile strength generally exceeds 100 MPa
  • the flexural strength is greater than 100 MPa
  • the flexural modulus exceeds 10000 MPa
  • the dimensional warpage deformation is less than 0.02%
  • the high temperature resistance can exceed 180 ° C
  • the low temperature resistance can reach minus 30 ° C
  • the self-flame retardant property is FV0 grade.
  • the prepared exhaust device blades can be accurately controlled to a thickness of 0.1 mm, which ensures the stability of the blades during high-speed rotation at different temperatures and the excellent performance of light weight and energy saving.
  • Patent CN204299902U and CN204125918U mention that the liquid crystal polymer as a fan application material has the advantage of thin wall and light weight, but as a new practical patent, it does not optimize its performance shortcomings. Since the liquid crystal polyester has anisotropic characteristics and has a single orientation in the processing flow direction, it has completely different properties in the flow direction and the vertical flow direction, and in particular, the thermal expansion property of the workpiece has a large difference in the vertical and horizontal directions. Therefore, during use under high temperature conditions, the blade shape changes during long-term use due to the difference in thermal expansion coefficient, affecting the exhaust effect and the use stability, etc., although the deformation amount is relative to other materials. Extremely small, but still affects the stability of the use of precision exhaust blade parts.
  • the inventors have surprisingly found through extensive experiments that in the liquid crystal polyester molding composition, the content of fluorine in the liquid crystal polyester molding composition is increased by adding an appropriate amount of a fluorine-containing compound or a fluorine-containing polymer and a magnesium-containing compound.
  • control in The content of the magnesium element is controlled in the range of 50-2000 ppm and the content of the magnesium element is controlled to be 0.1-500 ppm, so that the obtained liquid crystal polyester molding composition has excellent high-rigidity properties and can significantly reduce the difference in longitudinal and transverse thermal expansion coefficients thereof.
  • the stability of use of the high temperature exhaust vane device prepared therefrom is greatly improved.
  • liquid crystal polyester molding composition which has excellent high rigidity and can significantly reduce the difference in longitudinal and transverse thermal expansion coefficients, and is particularly suitable for exhausting air. For blade installations.
  • a liquid crystal polyester molding composition comprising, by weight, the following components:
  • thermoplastic polymers 0-30 parts
  • the fluorine element has a weight content of 50 ppm to 2000 ppm and a magnesium element weight content of 0.1 ppm to 500 ppm based on the total weight of the liquid crystal polyester molding composition.
  • the weight content of the fluorine element is determined by the ICP method, and the specific method is: the ICP test is tested by a German SPECTRO CIROS CC atomic emission spectrometer, and the standard curve is tested with different concentrations of the halogen standard solution, with sodium carbonate and sodium hydrogencarbonate. The aqueous solution is used as the eluent. After the ICP detector is tested, the fluorine content is calculated. The sample is pretreated by oxygen bomb combustion method, that is, 0.1-1.0g sample is accurately weighed into quartz crucible or nickel crucible, and 20ml absorption is weighed.
  • the liquid is added along the inner wall of the oxygen bomb, covered with an oxygen bomb cover and rotated on the support; the oxygen bomb containing the sample is placed under an oxygenator to be oxygenated until the pressure gauge above the oxygenator is stabilized at 1.5 MPa, using an oxygen bomb Dedicated venting cap venting; repeat the oxygen deflation for more than three times, completely replace the air in the oxygen bomb and then rush the oxygen; put the oxygen bomb into the ignition device, add water to just submerge the oxygen bomb cover, check whether After the air leaks, the ignition device is ignited; after the ignition is completed, it is fully cooled and then taken out.
  • the oxygen bomb is gently shaken several times to fully absorb the gas generated by the combustion, then let it stand and let off the oxygen; Rinsed with ultrapure water and oxygen bomb crucibles stent inner wall, a plastic volumetric flask of 50ml or 100ml, filtered on a membrane filter of 0.22 ⁇ m nylon test machine.
  • the method for testing the weight content of the magnesium element is as follows: drying the liquid crystal polyester composition at 120 ° C for 4 hours, taking 1 g of the sample to be treated, adding nitric acid and hydrogen peroxide, heating for 2 hours, continuously adding nitric acid and hydrogen peroxide; and digesting the sample After completion, the sample was removed and the weight content of magnesium in the sample was analyzed by Agilent's Model 720ES fully automated inductively coupled plasma atomic emission spectrometer. During the research, it was found that the content of fluorine element in the liquid crystal polyester molding composition was controlled to 50-2000 ppm by adding an appropriate amount of a fluorine-containing compound or a fluorine-containing polymer and a magnesium-containing compound to the liquid crystal polyester molding composition.
  • the high-rigidity performance can simultaneously improve the self-forming ability of the liquid crystal resin, and the liquid crystal polyester molding composition without fluorine element and magnesium element compared to,
  • the liquid crystal resin has a significant increase in self-forming fibers, which may be due to the strong electronegativity of the fluorine atom and the ability to bind to the ester groups in the molecular chain, which induces the ordered arrangement of the rod-like liquid crystal molecular chains, which is favorable for the orientation of the liquid crystal polyester.
  • the fluorine element is derived from one or more of a fluorine-containing compound or a fluorine-containing polymer; the fluorine-containing compound is a copolymer of tetrafluoroethylene and ethylene, and copolymerization of tetrafluoroethylene and perfluoroalkyl vinyl ether.
  • the fluoropolymer is polytetrafluoroethylene, polyvinylidene fluoride, fluorinated ethylene propylene, polytetrafluoroethylene-ethylene copolymer, One or more of perfluoroalkoxy resin, ethylene chlorotrifluoroethylene, polyvinyl fluoride, and polychlorotrifluoroethylene.
  • the magnesium element is derived from a magnesium-containing compound selected from the group consisting of magnesium oxide, magnesium fluoride, magnesium chloride, magnesium iodide, magnesium nitride, magnesium hydroxide, magnesium nitrate, magnesium acetate, magnesium sulfate, magnesium phosphate, Magnesium carbonate, magnesium hydrogencarbonate, magnesium silicate, magnesium methoxide, magnesium ethoxide, magnesium t-butoxide, magnesium molybdate, magnesium citrate, magnesium oxalate, magnesium lactate, magnesium trisilicate, magnesium pyrophosphate, magnesium stearate, Magnesium perchlorate, magnesium porphyrin, magnesium tetraborate, magnesium borohydride, magnesium acrylate, potassium magnesium chloride, magnesium bis(cyclopentadienyl), magnesium bis(ethylcyclopentadienyl), bis(n-propyl) Cyclopentadienyl)magnesium, bis(pentamethylcyclopentadienyl
  • the fluorine-containing compound or the fluorine-containing polymer and the magnesium-containing compound are added in an amount of from 50 ppm to 2000 ppm in the liquid crystal polyester molding composition, and the content of the magnesium element is preferably from 0.1 to 500 ppm.
  • the content of fluorine is less than 50ppm and the content of magnesium is less than 0.1ppm, the self-forming disordered fiber capacity of the part is reduced, the difference between the longitudinal and transverse thermal expansion coefficients of the workpiece is increased and the rigidity is decreased; when the fluorine content is higher than 2000ppm, magnesium
  • the element content is more than 500 ppm, the flowability of the liquid crystal polyester molding composition is lowered.
  • the fluorine element has a weight content of from 300 ppm to 1500 ppm, preferably from 500 ppm to 1000 ppm, based on the total weight of the liquid crystal polyester molding composition, and the magnesium element has a weight content of from 0.5 ppm to 300 ppm, preferably from 1 ppm to 100 ppm.
  • the liquid crystal polyester of the present invention is a thermotropic liquid crystal polyester which exhibits melt anisotropy in a molten state.
  • the thermotropic liquid crystal polyester is a wholly aromatic liquid crystal polyester or a semi-aromatic liquid crystal polyester, preferably a wholly aromatic liquid crystal polyester.
  • the liquid crystal polyester may select a main chain type liquid crystal polyester whose liquid crystal element is located in a molecular main chain according to a position of a liquid crystal cell, and the liquid crystal element may be connected to a side chain type of a main chain in a side group or a side chain form.
  • the liquid crystal polyester and the liquid crystal polyester having a liquid crystal cell on the main chain and the side chain.
  • the liquid crystal polyester includes liquid crystal polyester, liquid crystal polycarbonate, liquid crystal polyurethane, liquid crystal polyester amide, liquid crystal polyester imide;
  • the liquid crystal polyester may be selected from a type I resin having a heat distortion temperature higher than 300 ° C according to a heat distortion temperature, a type II liquid crystal resin having a heat distortion temperature between 240 and 280 ° C, and a heat distortion temperature not higher than 210 ° C.
  • Type III liquid crystal resin a type I resin having a heat distortion temperature higher than 300 ° C according to a heat distortion temperature, a type II liquid crystal resin having a heat distortion temperature between 240 and 280 ° C, and a heat distortion temperature not higher than 210 ° C.
  • the liquid crystal polyester is any two or more of p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, biphenyldiol, hydroquinone, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid.
  • the monomer is combined and polymerized.
  • the liquid crystal polyester has a melting point of 150-400 ° C, preferably 260-380 ° C; the melting point is tested by using DSC 200 F3 manufactured by NETZSCH Co., Ltd., and the temperature is raised from room temperature at 20 ° C/min. At the rate of temperature, the temperature is raised to the highest temperature of the melting point +30 ° C. After staying at this temperature for 3 min, the temperature is lowered to room temperature at a rate of 20 ° C / min. The test sample is allowed to stand at room temperature for 3 min and then heated again at a heating rate of 20 ° C / min. To the highest temperature of the melting point + 30 ° C, the second melting curve of the polymer is obtained, and the melting peak is selected as the melting point.
  • the other thermoplastic polymer is a polymer which can be melt-extruded with a base material by using a liquid crystal polyester as a base material, and has a polymer which improves the overall performance of the liquid crystal polyester molding composition, and can be selected as a general-purpose plastic such as poly.
  • the reinforcing filler has a fibrous shape with an average length of 0.01 to 20 mm, preferably 0.1 mm to 6 mm; an aspect ratio of 5:1 to 2000:1, preferably 30:1 to 600:1;
  • the content is 10-50 parts, more preferably 15-40 parts;
  • the reinforcing filler is an inorganic reinforcing filler or an organic reinforcing filler, including but not limited to glass fiber, carbon fiber, asbestos fiber, potassium titanate fiber
  • One or more of metal-clad glass fiber, ceramic fiber, wollastonite fiber, basalt fiber, metal carbide fiber, metal-cured fiber, insomnia fiber, alumina fiber, silicon carbide fiber, asbestos fiber or boron fiber are glass fibers;
  • the organic fillers include, but are not limited to, liquid crystal polyester fibers and/or carbon fibers.
  • the reinforcing filler has a non-fibrous shape and an average particle diameter of 0.001 ⁇ m to 50 ⁇ m, including but not limited to potassium titanate whiskers, zinc oxide whiskers, aluminum borate whiskers, talc, carbon black, gypsum, asbestos.
  • zeolite zeolite, sericite, kaolin, montmorillonite, clay, hectorite, synthetic mica, aluminosilicate, silica, titania, alumina, zinc oxide,
  • zirconia iron oxide, calcium carbonate, dolomite, aluminum sulfate, barium sulfate, calcium carbonate, mica, quartz powder, calcium hydroxide, aluminum hydroxide, glass beads, ceramic beads, boron nitride or silicon carbide Several.
  • the liquid crystal polyester molding composition of the embodiment of the present invention further includes 0 to 10 parts by weight of other auxiliary agents, within the range not impairing the effects of the present invention, the other auxiliary
  • the agent is selected from one or more of an antioxidant, a heat stabilizer, a UV absorber, a lubricant, a compatibilizer, a mold release agent, a colorant, a plasticizer, and an antistatic agent.
  • the antioxidant includes a hindered phenol antioxidant, a phosphite antioxidant, and the like;
  • the thermal stability includes a fatty acid-based heat stabilizer, a salt-based heat stabilizer, an organotin-based heat stabilizer, and the like;
  • the ultraviolet absorbers are salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, triazines, and the like;
  • the compatibilizing agent is one or more of a polypropylene grafted maleic anhydride, a polyethylene grafted maleic anhydride, an ethylene-octene copolymer grafted maleic anhydride, and a silane coupling agent;
  • the lubricant is one or more of calcium stearate, zinc stearate, silicone oil and other silicon-containing compounds having lubricating effects;
  • the release agent includes metal stearate, alkyl stearate, pentaerythritol stearate, paraffin, montan wax, and the like;
  • the coloring agent includes various pigments, dyes
  • the plasticizer includes a phthalate
  • the antistatic agent includes an alkyl sulfate type anionic antistatic agent, a quaternary ammonium salt type cationic antistatic agent, a nonionic antistatic agent such as polyoxyethylene sorbitan monostearate, and a beet. Alkaline amphoteric antistatic agent.
  • the method of blending a filler, an additive, or the like in the liquid crystal polyester molding composition of the embodiment of the present invention is not particularly limited, and a dry blending, a solution mixing method, or a polymerization of a liquid crystalline polyester may be used.
  • melt kneading or the like is preferred, and melt kneading is preferred.
  • kneading machine A uniaxial or biaxial extruder, a rubber roller machine or the like, in which a twin screw extruder is preferably used.
  • the temperature of the melt-kneading is not less than the melting point of the liquid crystal polyester, and the melting point is +50 ° C or lower.
  • a method of kneading a liquid crystal polyester, a reinforcing agent, or an additive from a post-loading machine may be used; or a liquid crystal polyester and other additives may be introduced from a post-loading machine, and the side may be fed.
  • a method of mixing a filler with a filler to carry out kneading can also prepare a liquid crystal polymer composition masterbatch containing a liquid crystal polymer and other additives at a high concentration, and then kneading the master batch with a liquid crystal polyester and a filling aid. Any method such as a method of obtaining a predetermined concentration.
  • a method for preparing a liquid crystal polyester molding composition according to the present invention comprises the following steps:
  • the liquid crystal polyester molding composition of the embodiment of the present invention is injection-molded, and is known as a known melt-molded article such as compression molding, compression molding, extrusion molding, blow molding, press molding, or the like.
  • the molded article described herein may be various molded articles such as injection molded articles, extrusion molded articles, press molded articles, sheets, tubes, unstretched films, uniaxially stretched films, and biaxially stretched films, and may be undrawn.
  • Various kinds of filaments such as stretched silk and super drawn yarn.
  • the effects of the present invention can be remarkably obtained, and therefore it is preferable.
  • the molded article formed by the liquid crystalline polymer molding composition obtained by the present invention can be applied to various blades, gears, various housings, connectors, sockets, resistors, relay housings, relay bases, relays.
  • Electrical and electronic components represented by bobbins, coil shafts, capacitors, variable capacitor housings, transformers, plugs, printed wiring boards, small motors, head mounts, power modules, housings, semiconductors, liquid crystal display components, computer-related components, etc.
  • Equipment precision machinery related components; exhaust valves and other valves, fuel related, exhaust system, various types of suction system, inlet nozzle snorkel, intake manifold, fuel pump, engine cooling water connector , vaporizer body, vaporizer separator, exhaust gas sensor, motor insulator for air conditioner, electric window insulator, etc., heater heater flow control valve, radiator motor brush holder, water pump impeller, turbine blade, window washer Nozzle, air conditioning panel switch substrate, fuel-related solenoid valve coil, fuse connector, horn terminal, electrical component insulation board, stepping motor rotor, lamp ring, lamp holder, light reflector, lamp housing, brake piston, Automobiles, vehicle-related components, etc., such as solenoid line shafts, engine oil filters, and ignition housings, have special applications in blades of electronic and electrical equipment exhaust devices such as printed wiring boards and small thin-walled electronic devices, particularly with heating. In the field of blade parts for ventilation and exhaust, such as in fans of electronic appliances.
  • the invention has the following beneficial effects:
  • the content of fluorine element in the liquid crystal polyester molding composition is controlled within a range of 50 ppm to 2000 ppm by adding an appropriate amount of a fluorine-containing compound or a fluorine-containing polymer and a magnesium-containing compound.
  • the content of magnesium element is controlled to be 0.1-500 ppm, which can effectively improve the self-forming ability of liquid crystal polyester, and the fluorine element induces self-forming fiber arrangement.
  • the disordered property solves the problem that the longitudinal and lateral thermal expansion of the workpiece is large due to the single orientation of the fiber, and the synergistic combination of the two elements of magnesium and fluorine makes the obtained liquid crystal polyester molding composition excellent.
  • the difference in longitudinal and transverse thermal expansion properties can be significantly reduced, whereby the liquid crystal polyester molding composition is used as the material of the exhausting vane device, and the prepared article has the advantages of thin wall and light weight, and can significantly improve the row.
  • the raw materials used in the present invention are as follows: all are commercially available raw materials.
  • Liquid crystal polyester (LCP1), a wholly aromatic liquid crystal polyester having a melting point of 350 ° C;
  • Liquid crystal polyester (LCP2), fully aromatic liquid crystal polyester, melting point of 385 ° C;
  • Reinforcing filler glass fiber, grade CS03JAPX-1, average fiber diameter 10 microns, length to diameter ratio 300, average fiber length 3000 microns;
  • Lubricant calcium stearate
  • Fluorine-containing compound or fluoropolymer Fluorine-containing compound or fluoropolymer:
  • PTFE Polytetrafluoroethylene
  • thermoplastic polymers are also thermoplastic polymers.
  • PC Polycarbonate
  • the weight content of fluorine element is determined by ICP method: it is tested by German SPECTRO CIROS CC atomic emission spectrometer; the standard curve is tested with different concentrations of halogen standard solution, and the aqueous solution of sodium carbonate and sodium bicarbonate is used as the eluent.
  • the F element content was calculated after the ICP detector was tested.
  • the sample preparation method is as follows: the sample is pretreated by oxygen bomb combustion method, that is, accurately weigh 0.1-1.0 g sample into quartz crucible or nickel crucible, weigh 20 ml of absorption liquid along the inner wall of the oxygen bomb, and cover with oxygen bomb cover.
  • the weight content of magnesium element is tested by drying the liquid crystal polyester composition at 120 ° C for 4 hours, taking 1 g of the sample to be treated, adding nitric acid and hydrogen peroxide, heating for 2 hours, continuously adding nitric acid and hydrogen peroxide; After the digestion was completed, the sample after the dissolution was canceled, and the weight content of magnesium in the sample was analyzed by a fully automated inductively coupled plasma atomic emission spectrometer of Agilent Model 720ES.
  • Example 1-21 and Comparative Example 1-2 Preparation of Liquid Crystalline Polyester Molding Composition
  • weight content of the fluorine element and the magnesium element in the liquid crystal polyester molding composition is the actual addition amount of the fluorine-containing compound or the fluorine-containing polymer or the magnesium-containing compound in the preparation process of the liquid crystal polyester molding composition. Make adjustments and measurements.
  • the fluorine element in the liquid crystal polyester molding composition is obtained by adding a fluorine-containing compound or a fluorine-containing polymer and a magnesium-containing compound to the liquid crystal polyester molding composition.
  • the content of the content of the magnesium element is controlled to be in the range of 50 to 2000 ppm and the content of the magnesium element is controlled to be 0.1 to 500 ppm, so that the obtained liquid crystal polyester molding composition has excellent mechanical properties, and the lower linear thermal expansion coefficient thereof is further obtained.
  • the improvement of the longitudinal and transverse thermal expansion coefficients is also significantly reduced, and the difference between the longitudinal and transverse thermal expansion coefficients is also significantly reduced, which solves the problem of the stability of the use of the high-temperature exhaust vane device.
  • the liquid crystal polyester molding The content of fluorine element in the composition is less than 50 ppm, and the content of magnesium element is less than 0.1 ppm.
  • the content of fluorine element in the liquid crystal polyester molding composition is higher than 2000 ppm, and when the content of magnesium element is higher than 500 ppm, The difference between the longitudinal and transverse thermal expansion coefficients is obvious, and the stability of use when applied to the high temperature exhaust vane device is poor.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition moulée de polyester à cristaux liquides et son application. La composition comprend les composants suivants : 30 à 100 parties de polyester à cristaux liquides, 0 à 30 parties d'autres polymères thermoplastiques et 0 à 70 parties de charge renforçante. Sur la base du poids total de la composition moulée de polyester à cristaux liquides, la teneur en poids de fluor varie de 50 à 2 000 ppm, et la teneur en poids de magnésium varie de 0,1 à 500 ppm. Selon la présente invention, la teneur en fluor de la composition moulée de polyester à cristaux liquides est maintenue dans la plage de 50 à 2 000 ppm, et la teneur en magnésium est maintenue dans la plage de 0,1 à 500 ppm, ce qui permet d'améliorer efficacement la capacité autologue des fibres du polyester à cristaux liquides. De plus, l'agencement de fibres autologues induites de fluor a la caractéristique de présenter un désordre directionnel. La combinaison synergique des deux éléments peut réduire de manière significative la différence en termes de dilatation thermique dans le sens vertical et horizontal tout en permettant à la composition moulée de polyester à cristaux liquides de présenter une remarquable rigidité. Par conséquent, les pièces préparées à partir de la composition moulée de polyester à cristaux liquides utilisée en tant que matériau pour aube d'échappement présentent une paroi mince, sont légères et peu bruyantes, peuvent améliorer de manière significative la stabilité d'utilisation de l'aube d'échappement, prolonger sa durée de vie en environnement difficile et ne sont susceptibles ni de s'user, ni de vieillir ni de se déformer.
PCT/CN2017/100371 2016-09-07 2017-09-04 Composition moulée de polyester à cristaux liquides et son application WO2018045932A1 (fr)

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CN116178905A (zh) * 2022-12-19 2023-05-30 珠海万通特种工程塑料有限公司 一种液晶聚酯组合物及其制备方法和应用

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