WO2018045932A1 - Liquid crystal polyester molded composition and application thereof - Google Patents

Liquid crystal polyester molded composition and application thereof Download PDF

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Publication number
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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Prior art keywords
magnesium
liquid crystal
crystal polyester
ppm
molding composition
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PCT/CN2017/100371
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French (fr)
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
Original Assignee
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/en

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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.

Abstract

Disclosed are a liquid crystal polyester molded composition and application thereof. The composition comprises the following components: 30-100 parts of liquid crystal polyester, 0-30 parts of other thermoplastic polymers, and 0-70 parts of reinforcing filler. On the basis of the total weight of the liquid crystal polyester molded composition, the weight content of fluorine is 50-2,000 ppm, and the weight content of magnesium is 0.1-500 ppm. According to the present invention, the content of fluorine in the liquid crystal polyester molded composition is controlled within the range of 50-2,000 ppm, and the content of magnesium is controlled within the range of 0.1-500 ppm, thereby effectively improving the autologous fiber ability of the liquid crystal polyester. Moreover, induced autologous fiber arrangement of fluorine has the directional disorder characteristic. Synergistic combination of the two elements can significantly reduce the difference of thermal expansion in vertical and horizontal directions while enabling the liquid crystal polyester molded composition to have excellent rigidity. Therefore, workpieces prepared from the liquid crystal polyester molded composition as the material of an exhaust blade are thin in wall, light in weight and low in noise, can significantly improve usage stability of the exhaust blade, prolong the service life in severe environment, and are not liable to wear, age or deform.

Description

一种液晶聚酯模塑组合物及其应用Liquid crystal polyester molding composition and application thereof 技术领域Technical field
本发明涉及特种工程塑料领域，具体涉及一种液晶聚酯模塑组合物及其应用。The invention relates to the field of special engineering plastics, and in particular to a liquid crystal polyester molding composition and application thereof.
背景技术Background technique
热致性液晶聚酯(TLCP)作为一种高性能特种工程塑料，具有优良的机械性能，良好的热加工流动性，耐蠕变和高尺寸稳定性，耐高低温性能，耐化学腐蚀，耐老化性，自增强自阻燃及电绝缘性能，目前在电子电器零部件等领域应用广泛，特别可作为一些使用环境要求较高的排风叶片装置制件领域，如在高温，灰尘重，空气潮湿等较为恶劣环境下运行的电脑，电视，空调，通讯产品、光电产品、消费电子产品、汽车电子设备、交换器，医疗设备，加热器，冷气机、变频器、柜员机、汽车冷柜、焊接机、电磁炉、音响设备、环保设备、制冷设备等工作会产生大量的热的设备。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.
目前，市场上排风叶片装置一般采用的是聚丙烯，苯乙烯-丙烯腈共聚物，丙烯腈-丁二烯-苯乙烯共聚物，尼龙以及聚对苯二甲酸丁二醇酯等材料，但热塑性聚丙烯，苯乙烯-丙烯腈，在力学性能，耐热性能，防翘曲变形等性能要求上差强人意，而尼龙又由于吸水率高导致尺寸稳定性差，丙烯腈-丁二烯-苯乙烯共聚物，聚对苯二甲酸丁二醇酯的耐高温性能较差，因此上述材料已经不能胜任特种环境的排风叶片装置的要求。At present, 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.
具有高流动性，超高强度和高刚性，优异的耐疲劳，抗蠕变性能，耐高低温性能，防翘曲变形性，耐老化等优点的液晶聚酯模塑组合物是最佳选择，其拉伸强度一般超过100MPa，弯曲强度大于100MPa，弯曲模量超过10000MPa，尺寸翘曲变形低于0.02％，耐高温可超过180℃，耐低温可至零下30℃，自阻燃性能为FV0级，制备的排风装置叶片可精确控制在0.1mm厚，确保了叶片在不同温度下高速旋转过程中的稳定性及其质轻节能的优良性能。专利CN204299902U，CN204125918U中提到了液晶高分子作为风扇的应用材料具有薄壁质轻的优势，但作为新型实用专利并未对其性能缺点进行优化。由于液晶聚酯具有各向异性特性，在加工流动方向具有单取向的特点，因此在流动方向和垂直流动方向具有完全不一样的性能，特别是制件的热膨胀性在纵横向具有较大区别，从而导致在高温条件下使用过程中，由于热膨胀系数的差异导致的叶片在长期使用过程中，叶片的形状发生改变，影响排风效果和使用稳定性等，虽然此变形量相对于其他材料而言极其微小，但对精密排风叶片制件的使用稳定性仍然会造成影响。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, and 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.
本发明人经过大量实验惊讶地发现，在液晶聚酯模塑组合物中，通过添加适量的含氟化合物或含氟聚合物以及含镁化合物，将液晶聚酯模塑组合物中氟元素的含量控制在 50-2000ppm范围内并将镁元素的含量控制在0.1-500ppm，可以使制得的液晶聚酯模塑组合物具有优良的高刚性能的同时，能明显降低其纵向和横向热膨胀系数的差异，极大的提高了由其制备得到的高温排风叶片装置的使用稳定性。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.
发明内容Summary of the invention
为了克服现有技术的缺点与不足，本发明的目的在于提供一种具有优良的高刚性能，且能明显降低纵向和横向热膨胀系数的差异的液晶聚酯模塑组合物，特别适用于排风叶片装置用。In order to overcome the shortcomings and deficiencies of the prior art, it is an object of the present invention to provide a 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.
本发明是通过以下技术方案实现的：The invention is achieved by the following technical solutions:
一种液晶聚酯模塑组合物，按重量份计，包括以下组份：A liquid crystal polyester molding composition comprising, by weight, the following components:
液晶聚酯           30-100份Liquid crystal polyester 30-100 parts
其他热塑性聚合物   0-30份Other thermoplastic polymers 0-30 parts
增强填料           0-70份Reinforcing filler 0-70 parts
其中，基于液晶聚酯模塑组合物的总重量，氟元素的重量含量为50ppm-2000ppm，镁元素的重量含量为0.1ppm-500ppm。Among them, 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.
其中，所述氟元素的重量含量采用ICP方法测定，具体方法为：ICP测试采用德国SPECTRO CIROS CC型原子发射光谱仪测试，以不同浓度的卤素标准液测试标准曲线，以碳酸钠与碳酸氢钠的水溶液作为淋洗液，经ICP检测器测试后计算得到氟元素含量；样品的前处理采用氧弹燃烧法，即准确称取0.1-1.0g样品放入石英坩埚或镍坩埚内，称取20ml吸收液沿氧弹内壁加入，盖上氧弹盖并旋转放在支架上；将装好样品的氧弹放置在充氧器下充氧直至充氧器上面的压力表稳定在1.5Mpa，用氧弹专用的放气帽放气；如此重复充氧放气三次以上，将氧弹中的空气彻底置换后再冲上氧气；将氧弹放到点火装置中，加水至刚好淹没氧弹盖，检查是否漏气后盖上点火装置点火；点火完毕后待充分冷却后拿出，将氧弹轻轻摇晃数次使燃烧产生的气体充分吸收后静置并放掉氧气；打开氧弹，用超纯水冲洗支架坩埚和氧弹内壁，用50ml或100ml的塑料容量瓶进行定容，用0.22μm的尼龙过滤膜过滤后上机测试。Wherein, 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 0.22μm nylon test machine.
所述镁元素的重量含量的测试方法为：将液晶聚酯组合物在120℃干燥4小时，取1g待处理样品，加入硝酸和双氧水，加热2小时，期间不断加入硝酸和双氧水；样品的消解完成后，取消解后的试样，采用Agilent公司型号为720ES的全自动电感耦合等离子体原子发射光谱仪分析样品中镁元素的重量含量。本发明在研究过程中发现，在液晶聚酯模塑组合物加入适量的含氟化合物或含氟聚合物以及含镁化合物，将液晶聚酯模塑组合物中氟元素的含量控制在50-2000ppm范围内并将镁元素的含量控制在0.1-500ppm，在带来高刚性能的同时，能够有效提高液晶树脂的自成纤维能力，与不含氟元素和镁元素的液晶聚酯模塑组合物相比， 液晶树脂自成纤维明显增多，这可能是由于氟原子的强电负性，与分子链中酯基的结合能力较大，诱导了棒状液晶分子链的有序排列，有利于液晶聚酯的取向排列成纤维而至，并且这种取向排列成的纤维具有排列无序特性，沿垂直和剪切流动方向的自成纤维能力均增大，在带来高刚性能的同时，有效解决了由于液晶聚酯单取向特性导致的制件纵横向热膨胀差异较大的问题。由于排列无序的自成纤维的增多，因此在液晶聚酯中添加适量的氟元素和镁元素，两种元素的协效组合带来了优良的高刚性能的同时，降低了纵横向热膨胀性的差异，特别适用于制备薄壁，质轻的叶片和面状结构制件。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. Within the range and controlling the content of magnesium element in the range of 0.1-500 ppm, 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. Arranged into fibers, and the fibers arranged in such an orientation have disordered characteristics, and the self-forming ability in the vertical and shear flow directions is increased, and the high-rigidity performance is effectively solved due to the liquid crystal. The problem of large difference in longitudinal and lateral thermal expansion of the workpiece caused by the single orientation property of the polyester. Due to the increase in the disordered self-forming fibers, an appropriate amount of fluorine and magnesium are added to the liquid crystal polyester, and the synergistic combination of the two elements brings excellent high-rigidity properties while reducing the longitudinal and transverse thermal expansion. The difference is particularly suitable for the preparation of thin-walled, lightweight blades and planar structural parts.
所述氟元素来源于含氟化合物或含氟聚合物中的一种或几种；所述含氟化合物为四氟乙烯与乙烯的共聚物、四氟乙烯与全氟烷基乙烯基醚的共聚物或四氟乙烯与六氟丙烯共聚物中的一种或几种；所述含氟聚合物为聚四氟乙烯、聚偏氟乙烯、氟化乙丙烯、聚四氟乙烯-乙烯共聚物、全氟烷氧基树脂、乙烯三氟氯乙烯、聚氟乙烯、聚三氟氯乙烯的一种或几种。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. Or one or more of a copolymer of tetrafluoroethylene and hexafluoropropylene; the fluoropolymer is polytetrafluoroethylene, polyvinylidene fluoride, fluorinated ethylene propylene, polytetrafluoroethylene-ethylene copolymer, One or more of perfluoroalkoxy resin, ethylene chlorotrifluoroethylene, polyvinyl fluoride, and polychlorotrifluoroethylene.
所述镁元素来源于含镁化合物，所述含镁化合物选自氧化镁、氟化镁、氯化镁、碘化镁、氮化镁、氢氧化镁、硝酸镁、醋酸镁、硫酸镁、磷酸镁、碳酸镁、碳酸氢镁、硅酸镁、甲醇镁、乙醇镁、叔丁醇镁、钼酸镁、柠檬酸镁、草酸镁、乳酸镁、三硅酸镁、焦磷酸镁、硬脂酸镁、高氯酸镁、镁卟啉、四硼酸镁、硼氢化镁、丙烯酸镁、氯化钾镁、双(环戊二烯)镁、双(乙基环戊二烯)镁、双(正丙基环戊二烯基)镁、双(五甲基环戊二烯)镁、2-乙基己酸镁、2-乙基丁酸镁、乙酰丙酮镁、双(二异丙氨基)镁、肌醇六磷酸钙镁、丙戊酸镁、二丁基镁、甲基碘化镁、氯化苯基镁、甘油磷酸镁、2-乙基丁酸镁、L-谷氨酸盐镁氢溴酸、3-噻吩基碘化镁、双(二异丙胺基)镁、双(三氟甲基磺酰)亚胺镁、间四苯基卟吩镁单水合物、双(2,4-戊二酸)镁、双(五甲基环戊二烯)镁、双(2,2,6,6,-四甲基-3,5-庚二酮酸)镁、溴化苯基镁、异丙基氯化镁、3,5-双(三氟甲基)苯基溴化镁、3-联苯溴化镁、4-氟苄基氯化镁、***溴化镁、2,3-二甲基苯基溴化镁、2-甲基-1-萘基溴化镁、3,4,5-三甲氧基苯基溴化镁或3,5-二甲基-4-甲氧基苯基溴化镁中的一种或几种。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)magnesium, magnesium 2-ethylhexanoate, magnesium 2-ethylbutyrate, magnesium acetylacetonate, magnesium bis(diisopropylamino), muscle Calcium magnesium hexaphosphate, magnesium valproate, dibutyl magnesium, magnesium methyl iodide, phenyl magnesium chloride, magnesium glycerate phosphate, magnesium 2-ethylbutyrate, magnesium chlorobromide , 3-thienyl magnesium iodide, bis(diisopropylamino)magnesium, bis(trifluoromethylsulfonyl)imide magnesium, m-tetraphenylporphine magnesium monohydrate, bis(2,4-pentane) Acid magnesium, bis(pentamethylcyclopentadienyl) magnesium, double (2,2,6,6 ,-tetramethyl-3,5-heptanedionate magnesium, phenylmagnesium bromide, isopropylmagnesium chloride, 3,5-bis(trifluoromethyl)phenylmagnesium bromide, 3-biphenyl bromide Magnesium, 4-fluorobenzylmagnesium chloride, diethyl ether bromide, 2,3-dimethylphenylmagnesium bromide, 2-methyl-1-naphthylmagnesium bromide, 3,4,5-trimethoxy One or more of phenyl magnesium bromide or 3,5-dimethyl-4-methoxyphenyl magnesium bromide.
所述的含氟化合物或含氟聚合物和含镁化合物的添加量以液晶聚酯模塑组合物中的氟元素含量在50ppm-2000ppm范围内，镁元素的含量控制在0.1-500ppm为宜，当氟元素含量低于50ppm，镁元素含量低于0.1ppm时，制件的自成无序纤维能力降低，制件纵横向热膨胀系数差异变大且刚性降低；当氟元素含量高于2000ppm，镁元素含量高于500ppm时，液晶聚酯模塑组合物加工流动性能降低。优选的，基于液晶聚酯模塑组合物的总重量，氟元素的重量含量为300ppm-1500ppm，优选为500ppm-1000ppm，镁元素的重量含量为0.5ppm-300ppm，优选为1ppm-100ppm。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. When 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 When the element content is more than 500 ppm, the flowability of the liquid crystal polyester molding composition is lowered. Preferably, 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.
本发明所述的液晶聚酯为热致性液晶聚酯，在熔融状态下表现出熔体各向异性的聚合物。 所述的热致性液晶聚酯为全芳香型液晶聚酯或半芳香型液晶聚酯，优选为全芳香型液晶聚酯。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.
所述的液晶聚酯根据液晶基元所在位置，可选择液晶基元位于分子主链中的主链型液晶聚酯，液晶基元以侧基或侧链形式连接于主链上的侧链型液晶聚酯和主链和侧链上都有液晶基元的液晶聚酯。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.
所述的液晶聚酯包括液晶聚酯、液晶聚碳酸酯、液晶聚氨酯、液晶聚酯酰胺、液晶聚酯酰亚胺；The liquid crystal polyester includes liquid crystal polyester, liquid crystal polycarbonate, liquid crystal polyurethane, liquid crystal polyester amide, liquid crystal polyester imide;
所述的液晶聚酯根据热变形温度高低，可选择热变形温度高于300℃的I型树脂，热变形温度在240-280℃之间的Ⅱ型液晶树脂和热变形温度不高于210℃的Ⅲ型液晶树脂。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.
所述的液晶聚酯是由对羟基苯甲酸，6-羟基-2-萘甲酸，联苯二酚，对苯二酚，对苯二甲酸，间苯二甲酸，萘二甲酸的任意两种以上单体组合聚合而成。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.
所述的液晶聚酯的熔点是150-400℃，优选为260-380℃；所述熔点的测试方法为：通过采用NETZSCH公司制DSC 200 F3测得，从室温起以20℃/min的升温速率条件下升温到熔点+30℃的最高温度，在此温度下停留3min后再以20℃/min的速率降温至室温，测试样品在室温下停留3min后再次以20℃/min的升温速率升温到熔点+30℃的最高温度，得到聚合物的第二次熔融曲线，选取熔融峰值即为熔点。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.
所述的其他热塑性聚合物为能以液晶聚酯为基体材料的，可与基体材料共熔融挤出的，具有改善液晶聚酯模塑组合物综合性能的聚合物，可选择为通用塑料如聚丙烯，聚乙烯，聚氯乙烯，苯乙烯，苯乙烯-丙烯腈共聚物等；工程塑料如聚碳酸酯，聚氨酯，聚对苯二甲酸乙二醇酯，聚对苯二甲酸丙二醇酯，聚对苯二甲酸丁二醇酯，聚苯硫醚等，特种工程塑料如聚醚砜，聚甲醛，聚酰胺，聚醚醚酮等。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. Propylene, polyethylene, polyvinyl chloride, styrene, styrene-acrylonitrile copolymer, etc.; engineering plastics such as polycarbonate, polyurethane, polyethylene terephthalate, polytrimethylene terephthalate, polypair Butylene phthalate, polyphenylene sulfide, etc., special engineering plastics such as polyethersulfone, polyoxymethylene, polyamide, polyetheretherketone, etc.
所述增强填料的形状为纤维状，平均长度为0.01～20mm，优选为0.1mm～6mm；长径比为5:1～2000:1，优选为30:1～600：1；所述增强填料的含量为10-50份，更优选为15-40份；所述增强填料为无机增强填料或有机增强填料，所述无机增强填料包括但不仅限于玻璃纤维、碳纤维、石棉纤维、钛酸钾纤维、金属包层的玻璃纤维、陶瓷纤维、硅灰石纤维、玄武岩纤维、金属碳化物纤维、金属固化纤维、失眠纤维、氧化铝纤维、碳化硅纤维、石棉纤维或硼纤维的一种或几种，优选为玻璃纤维；所述有机填料包括但不仅限于液晶聚酯纤维和/或碳纤维。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 Preferred are glass fibers; the organic fillers include, but are not limited to, liquid crystal polyester fibers and/or carbon fibers.
所述增强填料的形状为非纤维状，其平均粒径为0.001μm-50μm，包括但不仅限于钛酸钾晶须、氧化锌晶须、硼酸铝晶须、滑石粉、炭黑、石膏、石棉、沸石、绢云母、高岭土、蒙脱土、粘土、锂蒙脱土、合成云母、硅铝酸盐、二氧化硅、氧化钛、氧化铝、氧化锌、 氧化锆、氧化铁、碳酸钙、白云石、硫酸铝、硫酸钡、碳酸钙、云母、石英粉、氢氧化钙、氢氧化铝、玻璃珠、陶瓷珠、氮化硼或碳化硅的一种或几种。The reinforcing filler has a non-fibrous shape and an average particle diameter of 0.001 μm to 50 μm, including but not limited to potassium titanate whiskers, zinc oxide whiskers, aluminum borate whiskers, talc, carbon black, gypsum, asbestos. , zeolite, sericite, kaolin, montmorillonite, clay, hectorite, synthetic mica, aluminosilicate, silica, titania, alumina, zinc oxide, One type of 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.
本发明的实施方式的液晶聚酯模塑组合物中，在不损坏本发明的效果的范围内，所述液晶聚酯模塑组合物还包括0-10重量份其它助剂，所述其它助剂选自抗氧化剂、热稳定剂、紫外线吸收剂、润滑剂、相容剂、脱模剂、着色剂、增塑剂、抗静电剂中的一种或几种。In the liquid crystal polyester molding composition of the embodiment of the present invention, the liquid crystal polyester molding composition 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.
所述的抗氧剂包括受阻酚类抗氧剂、亚磷酸酯类抗氧剂等；The antioxidant includes a hindered phenol antioxidant, a phosphite antioxidant, and the like;
所述的热稳定包括脂肪酸类热稳定剂、盐基类热稳定剂、有机锡类热稳定剂等；The thermal stability includes a fatty acid-based heat stabilizer, a salt-based heat stabilizer, an organotin-based heat stabilizer, and the like;
所述的紫外线吸收剂为水杨酸酯类、苯酮类、苯并***类、取代丙烯腈类、三嗪类和其他类等；The ultraviolet absorbers are salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, triazines, and the like;
所述的相容剂为聚丙烯接枝马来酸酐，聚乙烯接枝马来酸酐，乙烯-辛烯共聚物接枝马来酸酐，硅烷偶联剂中的一种或几种；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;
所述的润滑剂为硬脂酸钙，硬脂酸锌，硅油以及其他具有润滑效果的含硅化合物中的一种或几种；The lubricant is one or more of calcium stearate, zinc stearate, silicone oil and other silicon-containing compounds having lubricating effects;
所述的脱模剂包括硬脂酸金属盐类，硬脂酸烷基酯类，硬脂酸季戊四醇酯类，石蜡，褐煤蜡等等；The release agent includes metal stearate, alkyl stearate, pentaerythritol stearate, paraffin, montan wax, and the like;
所述的着色剂包括各种颜料，染料；The coloring agent includes various pigments, dyes;
所述的增塑剂包括邻苯二甲酸酯；The plasticizer includes a phthalate;
所述的抗静电剂包括烷基硫酸盐型阴离子系抗静电剂、季铵盐型阳离子系抗静电剂、聚氧乙烯失水山梨糖醇单硬脂酸酯等非离子系抗静电剂、甜菜碱系两性抗静电剂等。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.
作为在本发明的实施方式的液晶聚酯模塑组合物中配合填充材料、添加剂等的方法，没有特定的限定，可以使用干式掺混、溶液混合法、液晶性聚酯的聚合是添加、熔融混炼等，其中优选为熔融混炼。如捏合机。单轴或双轴挤出机、胶辊机等，其中优选使用双轴挤出机。熔融混炼的温度为液晶聚酯的熔点以上，熔点+50℃以下。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. Among them, melt kneading or the like is preferred, and melt kneading is preferred. Such as 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.
作为混炼方法，可以使用从后装进料机一并投入液晶聚酯、增强剂、添加剂来进行混炼的方法；也可以从后装进料机投入液晶聚酯和其他添加剂，从侧进料机添加填充助剂进行混炼的方法，亦可以制备高浓度包含液晶性聚合物和其他添加剂的液晶性聚合物组合物母粒，接着将母粒与液晶聚酯，填充助剂进行混炼以成为规定的浓度的方法等的任一种方法。As a kneading method, 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.
作为本发明优选的一种实施方式，本发明所述的液晶聚酯模塑组合物的制备方法，包括如下步骤：As a preferred embodiment of the present invention, a method for preparing a liquid crystal polyester molding composition according to the present invention comprises the following steps:
(1)将液晶聚酯及其他热塑性树脂分别在100-150℃的温度干燥4-6h；(1) drying the liquid crystal polyester and other thermoplastic resins at a temperature of 100-150 ° C for 4-6 h;
(2)利用高速混合机将需要添加的其它助剂混合均匀后，80℃干燥4-6h； (2) using a high-speed mixer to mix the other additives that need to be added, and then drying at 80 ° C for 4-6h;
(3)将(1)和(2)干燥后的材料与含氟化合物或含氟聚合物和含镁化合物利用高速混合机混合均匀后投入到双螺杆挤出机的主喂料口，将增强填料从挤出机的侧喂料口加入，经熔融挤出、造粒，即得。(3) The materials after drying of (1) and (2) and the fluorine-containing compound or the fluorine-containing polymer and the magnesium-containing compound are uniformly mixed by a high-speed mixer and then introduced into the main feed port of the twin-screw extruder to be enhanced. The filler is added from the side feed port of the extruder, and is obtained by melt extrusion and granulation.
本发明的实施方式的液晶聚酯模塑组合物通过进行注射成型，注射压缩成型、压缩成型、挤出成型、吹塑成型、压制成型纺丝等公知的熔融成型品。这里所述的成型品，可以为注射成型品、挤出成型品、压制成型品、片、管、未拉伸薄膜、单轴拉伸薄膜、双轴拉伸薄膜等各种膜制品、未拉伸丝、超拉伸丝等各种纤维丝等。在注射成型的情况下，可显著获得本发明的效果，因此优选。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. In the case of injection molding, the effects of the present invention can be remarkably obtained, and therefore it is preferable.
本发明所获得的液晶性聚合物模塑组合物形成的成型品可以有如下应用，以各种叶片，齿轮、各种壳体、连接器、插座、电阻器、继电器壳体、继电器底座、继电器用绕线轴、线圈轴、电容器、可变电容器壳体、变压器、插头、印刷布线板、小型电动机、磁头底座、功率模块、外壳、半导体、液晶显示器部件、计算机相关部件等为代表的电气电子部件、电视部件、熨斗、电吹风、电饭煲部件、微波炉部件、音响部件、音频、激光盘、光盘等语音设备部件、照明部件、电冰箱部件、空调部件、打字机部件、文字处理机部件等为代表的家庭、企业电气制品部件、办公室计算机相关部件、电话机相关部件、传真机相关部件、复印机相关部件、电动机部件、以点火器、打字机等为代表的机械相关部件、以显微镜、双筒望远镜、照相机、钟表等为代表的光学设备、精密机械相关部件；排气气阀等各种阀、燃料关联、排气系、吸气系的各种管、进气口喷嘴通气管、进气歧管、燃料泵、发动机冷却水接头、汽化器主体、汽化器隔离物、排气气体传感器、空调用电动机绝缘体、电动窗等车载用电动机绝缘体、取暖器暖风流量控制阀、散热器电动机用刷握、水泵叶轮、涡轮叶片、窗户洗涤器喷嘴、空调面板开关基板、燃料关联电磁阀用线圈、保险丝用连接器、喇叭端子、电装部件绝缘板、步进电动机转子、灯圈、灯座、灯光反射器、灯壳、制动活塞、螺线管线轴、发动机滤油器、点火装置壳体等汽车、车辆相关部件等，在印刷布线板，小型薄壁电子器件等电子电气设备排风装置的叶片中有特别应用，特别是具有加热、通风和排气用的叶片制件领域，如在电子电器的风扇中的应用。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. Representatives of TV components, irons, hair dryers, rice cooker parts, microwave oven parts, audio parts, audio, laser discs, optical discs, etc., lighting parts, refrigerator parts, air conditioning parts, typewriter parts, word processor parts, etc. Household, corporate electrical parts, office computer related parts, telephone related parts, fax machine related parts, copier related parts, motor parts, mechanical related parts represented by igniters, typewriters, etc., with microscope, binoculars, camera Optics represented by watches, clocks, 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.
本发明与现有技术相比，具有如下有益效果：Compared with the prior art, the invention has the following beneficial effects:
本发明在液晶聚酯模塑组合物中，通过添加适量的含氟化合物或含氟聚合物和含镁化合物，将液晶聚酯模塑组合物中氟元素的含量控制在50ppm-2000ppm范围内并将镁元素的含量控制在0.1-500ppm，能有效提高液晶聚酯自成纤维能力，且氟元素诱导自成纤维排列具有方 向无序特性，解决了由于纤维的单取向导致的制件纵横向热膨胀差异大的问题，镁元素和氟元素两种元素的协效组合使制得的液晶聚酯模塑组合物具有优良的高刚性能的同时，能明显降低其纵横向热膨胀性的差异，由此液晶聚酯模塑组合物作为排风叶片装置材料，制备的制件具有薄壁，质轻的优点，能显著提高排风装置的使用稳定性，在恶劣环境中使用寿命增加，不易磨损老化变形，噪音小等特点。In the liquid crystal polyester molding composition, 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. At the same time of high-rigidity performance, 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 stability of the use of the wind device, the increase in service life in harsh environments, the difficulty of wear and aging deformation, and low noise.
具体实施方式detailed description
下面通过具体实施方式来进一步说明本发明，以下实施例为本发明较佳的实施方式，但本发明的实施方式并不受下述实施例的限制。The invention is further illustrated by the following detailed description of the preferred embodiments of the invention, but the embodiments of the invention are not limited by the following examples.
本发明中使用的原料如下：全部为市售原料。The raw materials used in the present invention are as follows: all are commercially available raw materials.
液晶聚酯(LCP1)，全芳香型液晶聚酯，熔点为350℃；Liquid crystal polyester (LCP1), a wholly aromatic liquid crystal polyester having a melting point of 350 ° C;
液晶聚酯(LCP2)，全芳香型液晶聚酯，熔点为385℃；Liquid crystal polyester (LCP2), fully aromatic liquid crystal polyester, melting point of 385 ° C;
增强填料：玻璃纤维，牌号CS03JAPX-1，平均纤维直径10微米，长径比300，平均纤维长度3000微米；Reinforcing filler: glass fiber, grade CS03JAPX-1, average fiber diameter 10 microns, length to diameter ratio 300, average fiber length 3000 microns;
润滑剂：硬脂酸钙；Lubricant: calcium stearate;
相容剂：聚乙烯接枝马来酸酐(mPE)，Compatibilizer: polyethylene grafted maleic anhydride (mPE),
含氟化合物或含氟聚合物：Fluorine-containing compound or fluoropolymer:
聚四氟乙烯(PTFE)；Polytetrafluoroethylene (PTFE);
四氟乙烯与乙烯的共聚物(ETFE)；a copolymer of tetrafluoroethylene and ethylene (ETFE);
含镁化合物：Magnesium containing compounds:
氯化镁；Magnesium chloride
甲基碘化镁；Methyl magnesium iodide;
其他热塑性聚合物：Other thermoplastic polymers:
聚碳酸酯(PC)；Polycarbonate (PC);
聚苯硫醚(PPS)。Polyphenylene sulfide (PPS).
各性能的测试标准或方法：Test criteria or methods for each performance:
(1)力学性能测试：按照标准测试方法和条件进行测试，如拉伸强度采用ISO 527标准，缺口冲击强度按照ISO 180测试，弯曲模量按照ISO 178测试；(1) Mechanical properties test: Test according to standard test methods and conditions, such as tensile strength using ISO 527 standard, notched impact strength according to ISO 180 test, and flexural modulus according to ISO 178;
(2纵横向热膨胀系数测试：采用一端进浇注塑的表面平滑2mm色板，分别沿流动方向和垂直流动裁取24*6*2mm矩形样条，在2℃/min的升温速率条件下，通过TMA测试-50℃-200℃的热膨胀系数，并将沿进浇方向的膨胀系数定义为纵向热膨胀系数，将垂直进浇方向的膨胀系数定义为横向热膨胀系数； (2 longitudinal and transverse thermal expansion coefficient test: using a smooth 2mm swatch on one end of the injection molding, respectively, cutting 24*6*2mm rectangular splines along the flow direction and vertical flow, and passing at a heating rate of 2 °C/min TMA tests the coefficient of thermal expansion from -50 °C to 200 °C, and defines the expansion coefficient along the in-feeding direction as the longitudinal thermal expansion coefficient, and the expansion coefficient in the vertical pouring direction as the transverse thermal expansion coefficient;
(3)氟元素的重量含量采用ICP方法测定：采用德国SPECTRO CIROS CC型原子发射光谱仪测试；以不同浓度的卤素标准液测试标准曲线，以碳酸钠与碳酸氢钠的水溶液作为淋洗液，经ICP检测器测试后计算得到F元素含量。其样品制备方法如下：样品的前处理采用氧弹燃烧法，即准确称取0.1-1.0g样品放入石英坩埚或镍坩埚内，称取20ml吸收液沿氧弹内壁加入，盖上氧弹盖并旋转放在支架上；将装好样品的氧弹放置在充氧器下充氧直至充氧器上面的压力表稳定在1.5Mpa，用氧弹专用的放气帽放气。如此重复充氧放气三次以上，将氧弹中的空气彻底置换后再冲上氧气；将氧弹放到点火装置中，加水至刚好淹没氧弹盖，检查是否漏气后盖上点火装置点火；点火完毕后待充分冷却后拿出，将氧弹轻轻摇晃数次使燃烧产生的气体充分吸收后静置并放掉氧气。打开氧弹，用超纯水冲洗支架坩埚和氧弹内壁，用50ml或100ml的塑料容量瓶进行定容用0.22μm的尼龙过滤膜过滤后上机测试。(3) 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. And rotate it on the bracket; place the oxygen bomb with the sample under the oxygenator to oxygenate until the pressure gauge above the oxygenator is stable at 1.5Mpa, and deflate with the special venting cap of the oxygen bomb. Repeat the oxygenation and deflation for more than three times, completely replace the air in the oxygen bomb and then flush the oxygen; put the oxygen bomb into the ignition device, add water to just submerge the oxygen bomb cover, check whether the ignition device is ignited after the air leaks. 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, and then the oxygen is allowed to stand and let go. Open the oxygen bomb, rinse the bracket and the inner wall of the oxygen bomb with ultrapure water, and use a 50ml or 100ml plastic volumetric flask for constant volume filtration with a 0.22μm nylon filter membrane.
(4)镁元素的重量含量的测试方法为：将液晶聚酯组合物在120℃干燥4小时，取1g待处理样品，加入硝酸和双氧水，加热2小时，期间不断加入硝酸和双氧水；样品的消解完成后，取消解后的试样，采用Agilent公司型号为720ES的全自动电感耦合等离子体原子发射光谱仪分析样品中镁元素的重量含量。(4) 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.
实施例1-21及对比例1-2：液晶聚酯模塑组合物的制备Example 1-21 and Comparative Example 1-2: Preparation of Liquid Crystalline Polyester Molding Composition
(1)将液晶聚酯及其他热塑性树脂分别在100-150℃的温度干燥4-6h；(1) drying the liquid crystal polyester and other thermoplastic resins at a temperature of 100-150 ° C for 4-6 h;
(2)利用高速混合机将需要添加的其它助剂混合均匀后，80℃干燥4-6h；(2) using a high-speed mixer to mix the other additives that need to be added, and then drying at 80 ° C for 4-6h;
(3)将(1)和(2)干燥后的材料与含氟化合物或含氟聚合物、含镁化合物按表1所示比例利用高速混合机混合均匀后投入到双螺杆挤出机的主喂料口，将增强填料从挤出机的侧喂料口加入，经熔融挤出、造粒，即得。对液晶聚酯模塑组合物进行性能测试，数据见表1。(3) The materials after drying (1) and (2) are mixed with a fluorine-containing compound or a fluorine-containing polymer or a magnesium-containing compound in a ratio shown in Table 1 by a high-speed mixer, and then introduced into a main part of a twin-screw extruder. At the feed port, the reinforcing filler is added from the side feed port of the extruder, and is obtained by melt extrusion and granulation. The liquid crystal polyester molding composition was tested for performance, and the data is shown in Table 1.
其中，液晶聚酯模塑组合物中的氟元素、镁元素的重量含量是在液晶聚酯模塑组合物的制备过程中通过含氟化合物或含氟聚合物、含镁化合物的实际添加量来进行调整并测得的。Wherein the 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.
表1 实施例1-21及对比例1-2的具体配比(重量份)及其测试性能结果Table 1 Specific ratios (parts by weight) of Examples 1-21 and Comparative Examples 1-2 and test performance results thereof
Figure PCTCN2017100371-appb-000001
Figure PCTCN2017100371-appb-000001
Figure PCTCN2017100371-appb-000002
Figure PCTCN2017100371-appb-000002
续表1：Continued Table 1:
Figure PCTCN2017100371-appb-000003
Figure PCTCN2017100371-appb-000003
Figure PCTCN2017100371-appb-000004
Figure PCTCN2017100371-appb-000004
从表1的实施例和对比例的比较可以看出：通过在液晶聚酯模塑组合物中添加含氟化合物或含氟聚合物和含镁化合物，将液晶聚酯模塑组合物中氟元素的含量控制在50-2000ppm范围内并将镁元素的含量控制在0.1-500ppm，可以使制得的液晶聚酯模塑组合物具有优良的力学性能，同时其较低的线性热膨胀系数得到了进一步的改善，纵向和横向热膨胀系数也明显降低，纵向和横向热膨胀系数的差异也降低明显，极好的解决了高温排风叶片装置的使用稳定性的问题，对比例1中，液晶聚酯模塑组合物中氟元素的含量低于50ppm，镁元素的含量低于0.1ppm，实施例2中，液晶聚酯模塑组合物中氟元素的含量高于2000ppm，镁元素的含量高于500ppm时，纵向和横向热膨胀系数的差异较为明显，应用于高温排风叶片装置时的使用稳定性差。 From the comparison of the examples of Table 1 and the comparative examples, it can be seen that 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. In Comparative Example 1, 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. In the embodiment 2, 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.

Claims (13)

  1. 一种液晶聚酯模塑组合物，其特征在于，按重量份计，包括以下组份：A liquid crystal polyester molding composition characterized by comprising the following components by weight:
    液晶聚酯   30-100份Liquid crystal polyester 30-100 parts
    其他热塑性聚合物  0-30份Other thermoplastic polymers 0-30 parts
    增强填料   0-70份。Reinforcing filler 0-70 parts.
  2. 根据权利要求1所述的液晶聚酯模塑组合物，其特征在于，基于液晶聚酯模塑组合物的总重量，氟元素的重量含量为50ppm-2000ppm，镁元素的重量含量为0.1ppm-500ppm。The liquid crystal polyester molding composition according to claim 1, wherein the fluorine element has a weight content of 50 ppm to 2000 ppm and a magnesium element weight content of 0.1 ppm based on the total weight of the liquid crystal polyester molding composition. 500ppm.
  3. 根据权利要求2所述的液晶聚酯模塑组合物，其特征在于，所述氟元素的重量含量采用ICP方法测定，具体方法为：ICP测试采用德国SPECTRO CIROS CC型原子发射光谱仪测试，以不同浓度的卤素标准液测试标准曲线，以碳酸钠与碳酸氢钠的水溶液作为淋洗液，经ICP检测器测试后计算得到氟元素含量；样品的前处理采用氧弹燃烧法，即准确称取0.1-1.0g样品放入石英坩埚或镍坩埚内，称取20ml吸收液沿氧弹内壁加入，盖上氧弹盖并旋转放在支架上；将装好样品的氧弹放置在充氧器下充氧直至充氧器上面的压力表稳定在1.5Mpa，用氧弹专用的放气帽放气；如此重复充氧放气三次以上，将氧弹中的空气彻底置换后再冲上氧气；将氧弹放到点火装置中，加水至刚好淹没氧弹盖，检查是否漏气后盖上点火装置点火；点火完毕后待充分冷却后拿出，将氧弹轻轻摇晃数次使燃烧产生的气体充分吸收后静置并放掉氧气；打开氧弹，用超纯水冲洗支架坩埚和氧弹内壁，用50ml或100ml的塑料容量瓶进行定容，用0.22μm的尼龙过滤膜过滤后上机测试；The liquid crystal polyester molding composition according to claim 2, wherein the weight content of the fluorine element is determined by an ICP method, and the specific method is: the ICP test is performed by a German SPECTRO CIROS CC type atomic emission spectrometer, and is different. The standard curve of the concentration of the halogen standard solution is determined by using an aqueous solution of sodium carbonate and sodium hydrogencarbonate as the eluent, and the content of fluorine is calculated by the ICP detector; the pretreatment of the sample is performed by the oxygen bomb combustion method, that is, accurately weighs 0.1. -1.0g sample is placed in quartz crucible or nickel crucible, 20ml absorption liquid is added along the inner wall of the oxygen bomb, covered with oxygen bomb cover and rotated on the bracket; the oxygen bomb with sample is placed under the oxygenator Oxygen until the pressure gauge above the oxygenator is stable at 1.5Mpa, and ventilate with the special venting cap of the oxygen bomb; repeat the oxygen deflation for more than three times, completely replace the air in the oxygen bomb and then rush the oxygen; Put the bomb into the ignition device, add water to just submerge the oxygen bomb cover, check whether the ignition device is ignited after the air leaks; after the ignition is completed, fully cool it and take it out, shake the oxygen bomb several times to make the combustion After the generated gas is fully absorbed, it is allowed to stand and the oxygen is released; the oxygen bomb is opened, the stent and the inner wall of the oxygen bomb are washed with ultrapure water, and the volume is fixed with a 50 ml or 100 ml plastic volumetric flask, and filtered with a 0.22 μm nylon filter membrane. On-machine test;
    所述镁元素的重量含量的测试方法为：将液晶聚酯组合物在120℃干燥4小时，取1g待处理样品，加入硝酸和双氧水，加热2小时，期间不断加入硝酸和双氧水；样品的消解完成后，取消解后的试样，采用Agilent公司型号为720ES的全自动电感耦合等离子体原子发射光谱仪分析样品中镁元素的重量含量。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.
  4. 根据权利要求2所述的液晶聚酯模塑组合物，其特征在于，基于液晶聚酯模塑组合物的总重量，氟元素的重量含量为300ppm-1500ppm，优选为500ppm-1000ppm，镁元素的重量含量为0.5ppm-300ppm，优选为1ppm-100ppm。The liquid crystal polyester molding composition according to claim 2, wherein the fluorine element has a weight content of from 300 ppm to 1,500 ppm, preferably from 500 ppm to 1,000 ppm, based on the total weight of the liquid crystal polyester molding composition. The weight content is from 0.5 ppm to 300 ppm, preferably from 1 ppm to 100 ppm.
  5. 根据权利要求1-4任一项所述的液晶聚酯模塑组合物，其特征在于，所述的液晶聚酯为热致性液晶聚酯，所述的热致性液晶聚酯为全芳香型液晶聚酯或半芳香型液晶聚酯，优选为全芳香型液晶聚酯。The liquid crystal polyester molding composition according to any one of claims 1 to 4, wherein the liquid crystal polyester is a thermotropic liquid crystal polyester, and the thermotropic liquid crystal polyester is wholly aromatic The liquid crystal polyester or semi-aromatic liquid crystal polyester is preferably a wholly aromatic liquid crystal polyester.
  6. 根据权利要求5所述的液晶聚酯模塑组合物，其特征在于，所述的液晶聚酯的熔点是150-400℃，优选为260-380℃，所述熔点的测试方法为：通过采用NETZSCH公司制DSC200F3测得，从室温起以20℃/min的升温速率条件下升温到熔点+30℃的最高温度，在此 温度下停留3min后再以20℃/min的速率降温至室温，测试样品在室温下停留3min后再次以20℃/min的升温速率升温到熔点+30℃的最高温度，得到液晶聚酯的第二次熔融曲线，选取熔融峰值即为熔点。The liquid crystal polyester molding composition according to claim 5, wherein the liquid crystal polyester has a melting point of 150 to 400 ° C, preferably 260 to 380 ° C, and the melting point is tested by using NETZSCH company DSC200F3 measured from room temperature at a temperature increase rate of 20 ° C / min to the highest temperature of the melting point + 30 ° C, here After staying at temperature for 3 min, the temperature was lowered to room temperature at a rate of 20 ° C / min. The test sample was allowed to stand at room temperature for 3 min and then heated again at a temperature increase rate of 20 ° C / min to the highest temperature of the melting point + 30 ° C to obtain the liquid crystal polyester. For the secondary melting curve, the melting peak is selected as the melting point.
  7. 根据权利要求1-4任一项所述的液晶聚酯模塑组合物，其特征在于，所述其他热塑性聚合物选自聚丙烯、聚乙烯、聚氯乙烯、苯乙烯、苯乙烯-丙烯腈共聚物、聚碳酸酯、聚氨酯、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丙二醇酯、聚对苯二甲酸丁二醇酯、聚醚砜、聚甲醛、聚苯硫醚、聚酰胺或聚醚醚酮中的一种或几种。The liquid crystal polyester molding composition according to any one of claims 1 to 4, wherein the other thermoplastic polymer is selected from the group consisting of polypropylene, polyethylene, polyvinyl chloride, styrene, and styrene-acrylonitrile. Copolymer, polycarbonate, polyurethane, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyether sulfone, polyoxymethylene, polyphenylene sulfide, poly One or more of an amide or polyetheretherketone.
  8. 根据权利要求1-4任一项所述的液晶聚酯模塑组合物，其特征在于，所述增强填料的形状为纤维状，平均长度为0.01～20mm，优选为0.1mm～6mm；长径比为5:1～2000:1，优选为30:1～600：1；所述增强填料的含量为10-50份，更优选为15-40份；所述增强填料为无机增强填料或有机增强填料，所述无机增强填料包括但不仅限于玻璃纤维、碳纤维、石棉纤维、钛酸钾纤维、金属包层的玻璃纤维、陶瓷纤维、硅灰石纤维、玄武岩纤维、金属碳化物纤维、金属固化纤维、失眠纤维、氧化铝纤维、碳化硅纤维、石棉纤维或硼纤维的一种或几种，优选为玻璃纤维；所述有机填料包括但不仅限于液晶聚酯纤维和/或碳纤维。The liquid crystal polyester molding composition according to any one of claims 1 to 4, wherein the reinforcing filler has a fibrous shape and an average length of 0.01 to 20 mm, preferably 0.1 mm to 6 mm; The ratio is from 5:1 to 2000:1, preferably from 30:1 to 600:1; the reinforcing filler is contained in an amount of from 10 to 50 parts, more preferably from 15 to 40 parts; the reinforcing filler is an inorganic reinforcing filler or organic Reinforcing filler, including but not limited to glass fiber, carbon fiber, asbestos fiber, potassium titanate fiber, metal clad glass fiber, ceramic fiber, wollastonite fiber, basalt fiber, metal carbide fiber, metal curing One or more of fibers, insomnia fibers, alumina fibers, silicon carbide fibers, asbestos fibers or boron fibers, preferably glass fibers; the organic fillers include, but are not limited to, liquid crystal polyester fibers and/or carbon fibers.
  9. 根据权利要求1-4任一项所述的液晶聚酯模塑组合物，其特征在于，所述增强填料的形状为非纤维状，其平均粒径为0.001μm-50μm，包括但不仅限于钛酸钾晶须、氧化锌晶须、硼酸铝晶须、滑石粉、炭黑、石膏、石棉、沸石、绢云母、高岭土、蒙脱土、粘土、锂蒙脱土、合成云母、硅铝酸盐、二氧化硅、氧化钛、氧化铝、氧化锌、氧化锆、氧化铁、碳酸钙、白云石、硫酸铝、硫酸钡、碳酸钙、云母、石英粉、氢氧化钙、氢氧化铝、玻璃珠、陶瓷珠、氮化硼或碳化硅的一种或几种。The liquid crystal polyester molding composition according to any one of claims 1 to 4, wherein the reinforcing filler has a non-fibrous shape and an average particle diameter of from 0.001 μm to 50 μm, including but not limited to titanium. Potassium acid whisker, zinc oxide whisker, aluminum borate whisker, talc, carbon black, gypsum, asbestos, 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 One or more of ceramic beads, boron nitride or silicon carbide.
  10. 根据权利要求2-4任一项所述的液晶聚酯模塑组合物，其特征在于，所述氟元素来源于含氟化合物或含氟聚合物中的一种或几种；所述含氟化合物为四氟乙烯与乙烯的共聚物、四氟乙烯与全氟烷基乙烯基醚的共聚物或四氟乙烯与六氟丙烯共聚物中的一种或几种；所述含氟聚合物为聚四氟乙烯、聚偏氟乙烯、氟化乙丙烯、聚四氟乙烯-乙烯共聚物、全氟烷氧基树脂、乙烯三氟氯乙烯、聚氟乙烯、聚三氟氯乙烯的一种或几种。The liquid crystal polyester molding composition according to any one of claims 2 to 4, wherein the fluorine element is derived from one or more of a fluorine-containing compound or a fluorine-containing polymer; The compound is a copolymer of tetrafluoroethylene and ethylene, a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether, or one or more of a copolymer of tetrafluoroethylene and hexafluoropropylene; the fluoropolymer is One type of polytetrafluoroethylene, polyvinylidene fluoride, fluorinated ethylene propylene, polytetrafluoroethylene-ethylene copolymer, perfluoroalkoxy resin, ethylene chlorotrifluoroethylene, polyvinyl fluoride, polychlorotrifluoroethylene or Several.
  11. 根据权利要求2-4任一项所述的液晶聚酯模塑组合物，其特征在于，所述镁元素来源于含镁化合物，所述含镁化合物选自氧化镁、氟化镁、氯化镁、碘化镁、氮化镁、氢氧化镁、硝酸镁、醋酸镁、硫酸镁、磷酸镁、碳酸镁、碳酸氢镁、硅酸镁、甲醇镁、乙醇镁、叔丁醇镁、钼酸镁、柠檬酸镁、草酸镁、乳酸镁、三硅酸镁、焦磷酸镁、硬脂酸镁、高氯酸镁、镁卟啉、四硼酸镁、硼氢化镁、丙烯酸镁、氯化钾镁、双(环戊二烯)镁、双(乙基环戊二烯) 镁、双(正丙基环戊二烯基)镁、双(五甲基环戊二烯)镁、2-乙基己酸镁、2-乙基丁酸酶、乙酰丙酮镁、双(二异丙氨基)镁、肌醇六磷酸钙镁、丙戊酸镁、二丁基镁、甲基碘化镁、氯化苯基镁、甘油磷酸镁、2-乙基丁酸镁、L-谷氨酸盐镁氢溴酸、3-噻吩基碘化镁、双(二异丙胺基)镁、双(三氟甲基磺酰)亚胺镁、间四苯基卟吩镁单水合物、双(2,4-戊二酸)镁、双(五甲基环戊二烯)镁、双(2,2,6,6,-四甲基-3,5-庚二酮酸)镁、溴化苯基镁、异丙基氯化镁、3,5-双(三氟甲基)苯基溴化镁、3-联苯溴化镁、4-氟苄基氯化镁、***溴化镁、2,3-二甲基苯基溴化镁、2-甲基-1-萘基溴化镁、3,4,5-三甲氧基苯基溴化镁或3,5-二甲基-4-甲氧基苯基溴化镁中的一种或几种。The liquid crystal polyester molding composition according to any one of claims 2 to 4, wherein 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, double (cyclopentadienyl) magnesium, bis(ethylcyclopentadiene) Magnesium, bis(n-propylcyclopentadienyl)magnesium, bis(pentamethylcyclopentadienyl)magnesium, magnesium 2-ethylhexanoate, 2-ethylbutyrate, magnesium acetylacetonate, bis (two Isopropylamino)magnesium, calcium magnesium phytate, magnesium valproate, dibutylmagnesium, methylmagnesium iodide, phenylmagnesium chloride, magnesium glycerophosphate, magnesium 2-ethylbutyrate, L-Valley Magnesium hydrobromide, 3-thienyl magnesium iodide, bis(diisopropylamino)magnesium, bis(trifluoromethylsulfonyl)imide magnesium, m-tetraphenylporphin magnesium monohydrate, double Magnesium (2,4-glutaric acid), magnesium bis(pentamethylcyclopentadienyl), magnesium bis(2,2,6,6,-tetramethyl-3,5-heptanedionate), bromine Phenyl magnesium, isopropylmagnesium chloride, 3,5-bis(trifluoromethyl)phenylmagnesium bromide, 3-biphenylmagnesium bromide, 4-fluorobenzylmagnesium chloride, diethyl ether bromide, 2,3 - dimethylphenylmagnesium bromide, 2-methyl-1-naphthylmagnesium bromide, 3,4,5-trimethoxyphenylmagnesium bromide or 3,5-dimethyl-4-methoxy One or more of phenyl phenyl bromide.
  12. 根据权利要求1-4任一项所述的液晶聚酯模塑组合物，其特征在于，所述液晶聚酯模塑组合物还包括0-10重量份其它助剂，所述其它助剂选自抗氧化剂、热稳定剂、紫外线吸收剂、润滑剂、相容剂、脱模剂、着色剂、增塑剂、抗静电剂中的一种或几种。The liquid crystal polyester molding composition according to any one of claims 1 to 4, wherein the liquid crystal polyester molding composition further comprises 0 to 10 parts by weight of other auxiliary agents, and the other auxiliary agents are selected. 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.
  13. 权利要求1-12任一项所述的液晶聚酯模塑组合物在排风叶片装置中应用，特别是在电子电器的风扇中的应用。 Use of the liquid crystal polyester molding composition according to any one of claims 1 to 12 in an exhausting vane device, in particular in a fan of an electronic appliance.
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