WO2017114161A1 - 一种液晶聚酯组合物 - Google Patents

一种液晶聚酯组合物 Download PDF

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WO2017114161A1
WO2017114161A1 PCT/CN2016/109984 CN2016109984W WO2017114161A1 WO 2017114161 A1 WO2017114161 A1 WO 2017114161A1 CN 2016109984 W CN2016109984 W CN 2016109984W WO 2017114161 A1 WO2017114161 A1 WO 2017114161A1
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liquid crystal
crystal polyester
polyester composition
repeating unit
mol
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PCT/CN2016/109984
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English (en)
French (fr)
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李闻达
孙华伟
肖中鹏
王鹏
罗德彬
许柏荣
易庆锋
周广亮
曹民
姜苏俊
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金发科技股份有限公司
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Publication of WO2017114161A1 publication Critical patent/WO2017114161A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/065—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids the hydroxy and carboxylic ester groups being bound to aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
    • 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
    • C08K3/34—Silicon-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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/132—Phenols containing keto groups, e.g. benzophenones
    • 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
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
    • 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
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the present invention relates to the field of polymer materials, and in particular to a liquid crystal polyester composition.
  • liquid crystal polyester As a special engineering material, liquid crystal polyester (LCP) has higher melting point and high heat stability than general-purpose resin. However, liquid crystal polyester still has thermal decomposition or external force when processed at high temperature. Thermal shearing and molecular chain scission lead to a decline in performance in all aspects. In order to improve the heat resistance stability of liquid crystal polyesters, many attempts have been made by those skilled in the art.
  • US 5,539,502 discloses a liquid crystal polymer composition having improved heat stability, the composition comprising 15 to 3000 ppm of an alkali metal or 50 to 3000 ppm of magnesium or calcium; and a liquid crystal polymer containing p-hydroxybenzoic acid, hydroquinone, and a combination Resorcinol, terephthalic acid, 2,6-naphthalene dicarboxylic acid and phthalic acid repeating units.
  • the introduction of the metal substance increases the melting point and heat distortion temperature of the composition, and the heat resistance is improved.
  • the liquid crystal polymer is contacted with the functional compound at a high temperature for a time sufficient for the melt viscosity to decrease by at least 10%.
  • CN1408816 discloses a liquid crystal polyester resin composition which is improved in thermal stability and which does not generate bubbles during soldering, which is achieved by adding 0.01 to 0.2 part by weight of a phosphite compound to 100 parts by weight of the liquid crystal polyester.
  • the patent does not mention whether its liquidity has improved.
  • the inventors have surprisingly found through a large number of experiments that the liquid crystal polyester combination obtained when the content of 4-hydroxyacetophenone added in the liquid crystal polyester composition formulation is 0.1 ppm to 500 ppm based on the total weight of the liquid crystal polyester composition.
  • the high temperature heat resistance stability of the material is unexpectedly improved, and the fluidity is also improved.
  • liquid crystal polyester composition which is remarkably improved in high temperature heat resistance stability, improved in fluidity, and which does not affect other properties.
  • a liquid crystal polyester composition having a weight content of 4-hydroxyacetophenone of from 0.1 ppm to 500 ppm based on the total weight of the liquid crystal polyester composition.
  • the weight content of 4-hydroxyacetophenone is preferably from 0.5 ppm to 300 ppm, more preferably from 1 ppm to 100 ppm, based on the total weight of the liquid crystal polyester composition.
  • the method for testing the weight content of 4-hydroxyacetophenone taking 500 mg of the liquid crystal polyester composition sample into a 25 ml volumetric flask, adding 2.5 ml of a 5 mol/L NaOH/CH 3 OH mixed solution, and adding 10 ml of the solution.
  • Water dimethyl sulfoxide maintain a nitrogen atmosphere at a temperature of 60 ° C, and shake the volumetric flask for more than 24 h.
  • water is added to dissolve the aromatic monomer salt formed by hydrolysis, and neutralized with hydrochloric acid.
  • liquid crystal polyester composition comprises, by weight, the following components:
  • the liquid crystal polyester composition has a melting point of 150 ° C - 400 ° C; the melting point is tested by a NETZSCH DSC 200 F3 differential scanning calorimeter DSC at 20 ° C / min from room temperature
  • the temperature rise condition test was carried out, and after the endothermic peak temperature T m1 was observed, it was kept at a temperature 20 ° C higher than T m1 for 5 minutes, then cooled to room temperature under a temperature drop condition of 20 ° C / minute, and then again at 20 ° C / minute.
  • the temperature rise condition was measured, and the endothermic peak temperature T m2 observed at this time was the melting point of the liquid crystal polyester composition.
  • liquid crystal polyester by mole percentage, comprises the following repeating unit:
  • the repeating unit derived from the aromatic dicarboxylic acid is from 0 mol% to 35 mol%.
  • the liquid crystal polyester by mole percentage, comprises the following repeating unit:
  • the repeating unit derived from the aromatic dicarboxylic acid is from 0 mol% to 25 mol%.
  • the repeating unit derived from the aromatic hydroxycarboxylic acid is selected from the group consisting of a repeating unit derived from 4-hydroxybenzoic acid and/or a repeating unit of 2-hydroxy-6-naphthoic acid; the derived from an aromatic diol
  • the repeating unit is selected from the group consisting of repeating units of hydroquinone and/or repeating units of 4,4′-dihydroxybiphenyl; the repeating unit derived from the aromatic dicarboxylic acid is selected from repeating units of terephthalic acid, One or more of a repeating unit of phthalic acid and a repeating unit of 2,6-naphthalenedicarboxylic acid.
  • a repeating unit derived from an aromatic hydroxycarboxylic acid, a repeating unit derived from an aromatic diol, and an aromatic second are respectively added according to a ratio.
  • the temperature is refluxed for 1 hour to 3 hours; thereafter, the temperature is further increased, and the mixture is heated from 140 ° C to 160 ° C to 300 ° C to 350 ° C over 2 hours to 4 hours, during which unreacted acetic anhydride and side reactions are distilled off.
  • the product is acetic acid; in the final polycondensation stage, the reaction system is depressurized, and it is judged by observing the increase of the torque as the end point of the reaction; at this time, the prepolymer in the melt state is discharged through the discharge port and cooled to room temperature; The prepolymer is transferred to a solid phase polymerization apparatus, and the temperature is raised from room temperature to 260 ° C to 280 ° C over 5 hours to 7 hours, and the solid phase polymerization is carried out at this temperature for 9 hours to 11 hours; The product was derived to obtain a liquid crystal polyester.
  • the filler is selected from the group consisting of a plate filler; the plate filler is one or more selected from the group consisting of talc, mica, graphite, and kaolin; preferably mica.
  • the mica has an average particle diameter of from 0.5 micrometers to 200 micrometers.
  • a filler When a filler is added, more than 100 parts by weight of a filler is added to 100 parts by weight of the liquid crystal polyester, and the mechanical strength of the liquid crystal polyester composition may be lowered.
  • the method of adding the filler is not particularly limited, and a method well known in the art can be cited.
  • the various additives are added to the liquid crystal polyester composition; the various additives may be selected from one or more of a filler, a plasticizer, a stabilizer, a colorant, a lubricant, a mold release agent, and an antioxidant.
  • an inorganic or organic filler in the form of particles, flakes or the like may be mixed in the liquid crystal polyester composition according to the present invention.
  • particulate filler examples include silicates such as calcium silicate, aluminum silicate, clay, diatomaceous earth, wollastonite, various metal powders such as iron oxide, titanium oxide, zinc oxide, antimony trioxide, aluminum oxide, and sulfuric acid.
  • silicates such as calcium silicate, aluminum silicate, clay, diatomaceous earth, wollastonite
  • various metal powders such as iron oxide, titanium oxide, zinc oxide, antimony trioxide, aluminum oxide, and sulfuric acid.
  • Calcium, carbon black, silica, quartz sand, glass beads, ground glass hollow microspheres and glass powder examples of the particulate filler.
  • sheet filler examples include glass flakes and various metal foils.
  • Other organic fillers include heat-resistant high-strength fibers made of, for example, aromatic polyesters, aromatic polyimides, polyamides, and the like.
  • fillers may be surface-treated with a commonly known surface treating agent as needed.
  • a suitable plasticizer is a phthalate.
  • Suitable stabilizers include organic phosphites such as triphenyl phosphite, tris-(2,6-dimethylphenyl) phosphite, tri-decylphenyl phosphite, dimethylphenylphosphonic acid Ester, trimethyl phosphate, etc., organic phosphite, alkylated monohydric or polyhydric phenol, alkylation reaction product of polyhydric phenol and diene, butylated reaction product of p-cresol or dicyclopentadiene , alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylene-bisphenols, benzyl compounds, polyol esters, benzotriazoles, benzophenones Or a variety of combinations.
  • organic phosphites such as triphenyl phosphite, tris-(2,6-dimethylphenyl) phosphite, tri-decylphenyl
  • Suitable release agents include metal stearates, alkyl stearates, pentaerythritol stearate, paraffin, montan wax, and the like.
  • Suitable colorants include various pigments, dyes such as metal oxides of inorganic pigments and zinc oxides of mixed metal oxides, titanium oxide, iron oxides, sulfides such as zinc sulfide, etc.; aluminates, silicates, chromic acid Salt, ferrite, etc., carbon black, ultramarine; organic pigments such as azo, diazo, anthraquinone, phthalocyanine, quinoline, naphthalene, ketone, azine, and the like.
  • Suitable lubricants include higher fatty acids, higher fatty esters, metal salts of higher fatty acids, and the like.
  • Suitable antioxidants include organic phosphites, alkylated monohydric or polyhydric phenols, alkylation products of polyphenols and dienes, butylated reaction products of p-cresol or dicyclopentadiene, alkane Alkalized hydroquinones, hydroxylated thiodiphenyl ethers, alkylene-bisphenols, benzyl compounds, polyol esters, and the like.
  • thermoplastic compositions such as one or more kinds of polypropylene, Polyamide, polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyether sulfone, polyphenyl ether and their modification Substances, thermoplastic resins such as polyetherimides, thermosetting resins such as phenolic resins, epoxy resins, polyimide resins and cyanide resins.
  • the liquid crystal polyester according to the present invention can be processed into a liquid crystal polyester composition by melt molding methods well known in the art such as extrusion molding, injection molding, press molding, and blow molding.
  • the liquid crystal polyester composition obtained by the extrusion molding process has the following specific steps: after the liquid crystal polyester, the filler, the 4-hydroxyacetophenone and/or various additives are uniformly mixed by a high-speed mixer according to the ratio, It is added to a twin-screw extruder and melt-mixed at a screw speed of 280 RPM to 320 RPM.
  • the temperature of the barrel is 290 ° C to 355 ° C, and it is extruded, cooled, and pelletized to obtain a liquid crystal polyester composition.
  • the invention has the following beneficial effects:
  • the high temperature heat resistance stability of the obtained liquid crystal polyester composition is obtained by adding the content of 4-hydroxyacetophenone in the liquid crystal polyester composition formulation to 0.1 ppm to 500 ppm based on the total weight of the liquid crystal polyester composition. Unexpectedly significant improvements have been made and liquidity has improved.
  • Fig. 1 is a schematic view showing a molded article in which a liquid crystal polyester is filled and formed by using a spiral molding die having a width of 5 mm and a thickness of 1 mm.
  • Test method for the weight content of the 4-hydroxyacetophenone 500 mg of the liquid crystal polyester composition sample was added to a 25 ml volumetric flask, 2.5 ml of a 5 mol/L NaOH/CH 3 OH mixed solution was added, and 10 ml of the solution was added. Water dimethyl sulfoxide; maintain a nitrogen atmosphere at a temperature of 60 ° C, and shake the volumetric flask for more than 24 h. After the liquid crystal resin in the sample is completely hydrolyzed, water is added to dissolve the aromatic monomer salt formed by hydrolysis, and neutralized with hydrochloric acid.
  • Test Method for Melt Viscosity of the Liquid Crystal Polyester Composition The liquid crystal polyester composition was tested using a Dynisco LCR 7000 capillary rheometer at a test temperature of liquid crystal polyester composition at a melting point of +20 ° C and a shear rate of 1000 seconds. -1 , using a die with an inner diameter of 1 mm and a length of 40 mm.
  • Test method for melting point of the liquid crystal polyester composition by using a NETZSCH DSC 200 F3 type differential scanning calorimeter (DSC), the endothermic peak temperature was observed at a temperature rise condition of 20 ° C / min from room temperature. After T m1 , it was kept at a temperature 20 ° C higher than T m1 for 5 minutes, then cooled to room temperature under a temperature drop condition of 20 ° C / minute, and then measured again at a temperature rising condition of 20 ° C / minute, and observed at this time.
  • the endothermic peak temperature T m2 is the melting point of the liquid crystal polyester composition.
  • a test method for fluidity of the liquid crystal polyester composition after drying the liquid crystal polyester composition at 120 ° C for 4 hours, it is added to an injection molding machine, and the cylinder temperature is set to be 20 ° C higher than the melting point of the liquid crystal polyester composition.
  • the mold temperature was set to 120 ° C, and the liquid crystal polyester composition was filled and formed at a injection pressure of 3 MPa and an injection rate of 50 mm/s using a spiral molding die having a width of 5 mm and a thickness of 1 mm, as shown in FIG. 1;
  • the length is the melt flow length, and the longer the flow length, the more excellent the fluidity of the liquid crystal polyester composition.
  • Test method for high temperature heat resistance stability of the liquid crystal polyester composition after drying the liquid crystal polyester composition at 120 ° C for 4 hours, it is added to a HAAKE Polylab OS type internal mixer for mixing, and the temperature is higher than that of the liquid crystal polyester.
  • the melting point of the composition is 20 ° C higher, the rotation speed of the rotor is 50 rpm, and the mixing time is 1 hour; after the completion of the mixing, the molten liquid crystal polyester composition is taken out from the internal mixer and cooled to room temperature; the same sample is dense.
  • HBA Hydroxybenzoic acid
  • TA Terephthalic acid
  • IA Isophthalic acid
  • HNA 2-hydroxy-6-naphthoic acid
  • NDA 2,6-naphthalenedicarboxylic acid
  • Mica used in the present invention grade: Y150422, Zhangzhou Ge Rui Mining Co., Ltd.
  • a repeating unit derived from an aromatic hydroxycarboxylic acid, a repeating unit derived from an aromatic diol, and an aromatic derived are respectively added according to a ratio.
  • a repeating unit of the dicarboxylic acid, and adding a certain proportion of acetic anhydride as an acylating agent then introducing nitrogen into the reaction vessel for replacement; stirring is started, and the reaction mixture is heated from room temperature to 140 ° C to 160 ° C in a nitrogen stream.
  • the reaction product is acetic acid; in the final polycondensation stage, the reaction system is decompressed, and the end point of the reaction is judged by observing the increase of the torque; at this time, the prepolymer in the melt state is discharged through the discharge port and cooled to room temperature; further Transfer the prepolymer to a solid phase polymerization device, raise the temperature from room temperature to 260 ° C to 280 ° C over 5 hours to 7 hours, and hold the solid phase polymerization at this temperature for 9 hours to 11 hours; After deriving the product to obtain a liquid crystal polyester.
  • the liquid crystal polyester, filler, 4-hydroxybenzene B prepared by the examples A1-A4 according to the ratio of Table 2
  • the ketone and/or various additives are uniformly mixed by a high-speed mixer, then added to a twin-screw extruder, melt-mixed at a screw speed of 280 RPM-320 RPM, and the temperature of the barrel is 290 ° C - 355 ° C.
  • the melting point, flow length, melt viscosity and specific volume logarithmic viscosity of the obtained liquid crystal polyester composition are shown in Table 2.
  • the present invention is based on the addition of 4-hydroxyacetophenone in the liquid crystal polyester composition formulation based on the total amount of the liquid crystal polyester composition.
  • the weight is from 0.1 ppm to 500 ppm, the obtained liquid crystal polyester composition is unexpectedly remarkably improved in high-temperature heat resistance stability, and fluidity is also improved.

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Abstract

一种液晶聚酯组合物，其特征在于，基于液晶聚酯组合物的总重量，4-羟基苯乙酮的重量含量为0.1ppm-500ppm。本发明通过选用在液晶聚酯组合物配方中添加4-羟基苯乙酮的含量基于液晶聚酯组合物的总重量为0.1ppm-500ppm时，得到的液晶聚酯组合物的高温耐热稳定性得到意想不到的显著改善，流动性也得到了提高。

Description

一种液晶聚酯组合物 技术领域
本发明涉及高分子材料领域，特别涉及一种液晶聚酯组合物。
背景技术
液晶聚酯(LCP)作为一种特种工程类材料，与通用树脂相比，具有较高的熔点和高耐热稳定性，然而液晶聚酯仍然存在着在高温下加工时热分解或因受外力热剪切而分子链断链，导致各方面性能下降的现象。为了改善液晶聚酯的耐热稳定性，本领域专业人员做了许多尝试。
US5397502公开了一种耐热稳定性改善的液晶聚合物组合物，组合物包含15～3000ppm的碱金属或50～3000ppm的镁或钙；液晶聚合物含有对羟基苯甲酸、对苯二酚、联苯二酚、对苯二甲酸、2，6-萘二甲酸和联苯二甲酸重复单元。金属物质的引入提高了组合物的熔点及热变形温度，使耐热性得到改善。然而专利中提到使液晶聚合物与功能性化合物在高温下接触并持续足够长的时间使得其熔体粘度下降至少10％。本领域专业技术人员所公知，液晶树脂长时间在高于其熔融温度下处理，由于热分解会会导致熔体粘度和分子量的降低，由此带来的还有力学性能的下降，以及副反应的发生，这可能会增大树脂起泡的风险。
CN1408816公开了一种热稳定性改善且焊接过程中不产生气泡的液晶聚酯树脂组合物，其是通过向100重量份液晶聚酯中加入0.01-0.2重量份亚磷酸酯化合物来实现的。但是该专利并未提及其流动性是否有改善。
到目前为止，关于在液晶聚酯组合物中添加4-羟基苯乙酮对所述液晶聚酯组合物的流动性、高温耐热稳定性的影响未见报道。
本发明人经过大量实验惊讶地发现，选用在液晶聚酯组合物配方中添加4-羟基苯乙酮的含量基于液晶聚酯组合物的总重量为0.1ppm-500ppm时，得到的液晶聚酯组合物的高温耐热稳定性得到意想不到的显著改善，流动性也得到了提高。
发明内容
为了克服现有技术的缺点与不足，本发明的首要目的在于提供一种高温耐热稳定性得到显著改善，流动性提高，且不影响其它方面性能的液晶聚酯组合物。
本发明是通过如下技术方案实现的：
一种液晶聚酯组合物，基于液晶聚酯组合物的总重量，4-羟基苯乙酮的重量含量为0.1ppm-500ppm。
优选地，基于液晶聚酯组合物的总重量，4-羟基苯乙酮的重量含量优选为0.5ppm-300ppm，更优选为1ppm-100ppm。
其中，4-羟基苯乙酮的重量含量的测试方法：取500mg液晶聚酯组合物样品加入25ml容量瓶中，加入2.5ml浓度为5mol/L的NaOH/CH3OH混合溶液，并加入10ml除水二甲基亚砜；在60℃的温度下保持氮气氛围，对容量瓶进行震荡24h以上，待样品中的液晶树脂水解完全后，加水溶解水解形成的芳族单体盐，并用盐酸中和过量的碱，冷冻干燥所得样品，该样品为液晶聚酯完全水解物与组合物中无机填料的混合物；将水解后的样品溶于丙酮中，采用美国安捷伦公司1260型高效液相色谱仪，测试样品中的4-羟基苯乙酮；并采用外标法对水解样品中的4-羟基苯乙酮进行定量。
而当在液晶聚酯组合物配方中添加4-羟基苯乙酮的重量含量超过500ppm，会使得液晶聚酯组合物的力学性能下降。
其中，所述液晶聚酯组合物，按重量份计，包括如下组分：
液晶聚酯                100份；
填充剂                  5份-100份。
其中，所述液晶聚酯组合物的熔点为150℃-400℃；所述熔点的测试方法为：通过NETZSCH公司DSC 200 F3型差示扫描量热仪DSC，在从室温开始以20℃/分钟的升温条件测试，观测到吸热峰温度Tm1后，在比Tm1高20℃的温度下保持5分钟，然后在20℃/分钟的降温条件下冷却至室温，然后再次以20℃/分钟的升温条件进行测定，此时观测到的吸热峰温度Tm2即为液晶聚酯组合物的熔点。
其中，所述液晶聚酯，按摩尔百分比计，包含如下重复单元：
衍生自芳香族羟基羧酸的重复单元     30mol％-100mol％；
衍生自芳香族二醇的重复单元         0mol％-35mol％；
衍生自芳香族二羧酸的重复单元       0mol％-35mol％。
优选地，所述液晶聚酯，按摩尔百分比计，包括如下重复单元：
衍生自芳香族羟基羧酸的重复单元     50mol％-100mol％；
衍生自芳香族二醇的重复单元         0mol％-25mol％；
衍生自芳香族二羧酸的重复单元       0mol％-25mol％。
其中，所述衍生自芳香族羟基羧酸的重复单元选自衍生自4-羟基苯甲酸的重复单元和/或2-羟基-6-萘甲酸的重复单元；所述衍生自芳香族二醇的重复单元选自对苯二酚的重复单元和/或4,4’-二羟基联苯的重复单元；所述衍生自芳香族二羧酸的重复单元选自对苯二甲酸的重复单元、间苯二甲酸的重复单元、2,6-萘二甲酸的重复单元中一种或几种。
上述液晶聚酯的制备方法，可以采用本领域技术人员熟知的标准缩聚技术方法，包括如下步骤：
在装配有搅拌器、温度计、氮气导入管和回流冷凝装置的反应釜中按照配比分别加入衍生自芳香族羟基羧酸的重复单元、衍生自芳香族二醇的重复单元和衍生自芳香族二羧酸的重复单元，并加入一定比例的醋酸酐为酰化剂；然后将氮气通入反应釜中进行置换；开动搅拌，在氮气流中将反应混合物由室温加热到140℃-160℃，在此温度下回流1小时-3小时；此后继续升温，将混合物经2小时-4小时从140℃-160℃加热到300℃-350℃，在此过程中蒸出未反应的醋酸酐和副反应产物醋酸；终缩聚阶段，对反应体系进行减压，并通过观察扭矩升高作为反应结束的终点判断；此时将熔体状态的预聚物经放料口排出，并冷却至室温；进一步将预聚物转移至固相聚合装置，经5小时-7小时将温度由室温升高至260℃-280℃，在此温度下保温9小时-11小时进行固相聚合反应；反应结束后将产物导出，从而得到液晶聚酯。
其中，所述填充剂选自板状填充剂；所述板状填充剂选自滑石、云母、石墨、高岭土中的一种或几种；优选为云母。
优选地，所述云母的平均粒径为0.5微米-200微米。
当添加填充剂，相对于液晶聚酯100重量份，添加超过100份以上的填充剂，液晶聚酯组合物的机械强度可能降低。添加填充剂的方法不特别限制，并且可以列举在本领域中公知的方法。
此外，除了上述组分以外，可以以不损害本发明目的的量向本发明中使用的 液晶聚酯组合物中加入公知的各种添加剂；各种添加剂可以选自填料、增塑剂、稳定剂、着色剂、润滑剂、脱模剂、抗氧剂中的一种或几种。
为了改善机械强度，可以在根据本发明的液晶聚酯组合物中混入颗粒、薄片等形式的无机或有机填料。
颗粒状填料的实例包括硅酸盐如硅酸钙、硅酸铝、粘土、硅藻土、硅灰石、各种金属粉末如氧化铁、氧化钛、氧化锌、三氧化锑、氧化铝和硫酸钙、炭黑、二氧化硅、石英砂、玻璃珠、研磨的玻璃空心微珠和玻璃粉末。
薄片填料的实例包括玻璃薄片和各种金属箔。其他有机填料包括例如芳香族聚酯、芳香族聚酰亚胺、聚酰胺等制成的耐热高强度纤维。
根据需要，这些填料可以用通常已知的表面处理剂进行表面处理。
合适的增塑剂为邻苯二甲酸酯。
合适的稳定剂包括有机亚磷酸酯，如亚磷酸三苯酯，亚磷酸三-(2,6-二甲基苯基)酯，亚磷酸三-壬基苯基酯，二甲基苯膦酸酯，磷酸三甲酯等，有机亚磷酸酯，烷基化的一元酚或者多元酚，多元酚和二烯的烷基化反应产物，对甲酚或者二环戊二烯的丁基化反应产物，烷基化的氢醌类，羟基化的硫代二苯基醚类，亚烷基-双酚，苄基化合物，多元醇酯类，苯并三唑类，二苯甲酮类的一种或者多种组合。
合适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。
合适的着色剂包括各种颜料，染料，如无机颜料的金属氧化物和混合金属氧化物的氧化锌，氧化钛，氧化铁，硫化物如硫化锌等；铝酸盐，硅酸盐，铬酸盐，铁酸盐等，炭黑，群青；有机颜料如偶氮类，重氮类，蒽醌类、酞菁、喹啉类，萘，酮，嗪类等等。
合适的润滑剂包括高级脂肪酸、高级脂肪酯、高级脂肪酸的金属盐等。
合适的抗氧剂包括有机亚磷酸酯，烷基化的一元酚或者多元酚，多元酚和二烯的烷基化反应产物，对甲酚或者二环戊二烯的丁基化反应产物，烷基化的氢醌类，羟基化的硫代二苯基醚类，亚烷基-双酚，苄基化合物，多元醇酯类等。
各种添加剂不限于上述几种，可任选含有对液晶聚酯的热稳定性和物理性质无害的其它种类组分以及热塑性组合物中常见的其它物质，如一种或多种的聚丙烯、聚酰胺、聚酯、聚苯硫醚、聚醚酮、聚碳酸酯、聚醚砜、聚苯基醚及其改性 物质，热塑性树脂如聚醚酰亚胺，热固性树脂如酚醛树脂、环氧树脂、聚酰亚胺树脂和氰化物树脂。
根据本发明的液晶聚酯经过本领域公知的熔体模塑成型方法例如挤出成型、注射成型、压制成型和吹塑成型均可加工成液晶聚酯组合物。
其中，通过挤出成型工艺得到的液晶聚酯组合物，具体步骤如下：按照配比将液晶聚酯、填充剂、4-羟基苯乙酮和/或各种添加剂用高速混合机混合均匀后，加入双螺杆挤出机，在280RPM-320RPM的螺杆转速下熔融混合，螺筒温度为290℃-355℃，挤出，冷却、切粒，即得液晶聚酯组合物。
本发明与现有技术相比，具有如下有益效果：
本发明通过选用在液晶聚酯组合物配方中添加4-羟基苯乙酮的含量基于液晶聚酯组合物的总重量为0.1ppm-500ppm时，得到的液晶聚酯组合物的高温耐热稳定性得到意想不到的显著改善，流动性也得到了提高。
附图说明
图1为使用宽5mm、厚1mm螺旋状成型模具，将液晶聚酯填充成型的成型品示意图。
具体实施方式
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。
所述4-羟基苯乙酮的重量含量的测试方法：取500mg液晶聚酯组合物样品加入25ml容量瓶中，加入2.5ml浓度为5mol/L的NaOH/CH3OH混合溶液，并加入10ml除水二甲基亚砜；在60℃的温度下保持氮气氛围，对容量瓶进行震荡24h以上，待样品中的液晶树脂水解完全后，加水溶解水解形成的芳族单体盐，并用盐酸中和过量的碱，冷冻干燥所得样品，该样品为液晶聚酯完全水解物与组合物中无机填料的混合物；将水解后的样品溶于丙酮中，采用美国安捷伦公司1260型高效液相色谱仪，测试样品中的4-羟基苯乙酮；并采用外标法对水解样品中的4-羟基苯乙酮进行定量。
所述液晶聚酯组合物的熔融粘度的测试方法：采用Dynisco LCR7000型毛细管流变仪对液晶聚酯组合物进行测试，测试温度为液晶聚酯组合物熔点+20℃，剪切速率为1000秒-1，使用内径1mm，长度40mm的口模测量。
所述液晶聚酯组合物的熔点的测试方法：通过NETZSCH公司DSC 200 F3 型差示扫描量热仪(DSC)，在从室温开始以20℃/分钟的升温条件测试，观测到吸热峰温度Tm1后，在比Tm1高20℃的温度下保持5分钟，然后在20℃/分钟的降温条件下冷却至室温，然后再次以20℃/分钟的升温条件进行测定，此时观测到的吸热峰温度Tm2为液晶聚酯组合物的熔点。
所述液晶聚酯组合物的比容对数粘度的测试方法：将液晶聚酯组合物溶解于五氟苯酚中，制成浓度为0.01g/mL的溶液，测试温度为60℃，采用内径为0.7mm的乌氏粘度计测量；并由公式：比容对数粘度＝[ln(ηr)]/C计算得到，其中ηr为相对粘度(t溶液/t溶剂)，C为溶液浓度。
所述液晶聚酯组合物的流动性的测试方法：将液晶聚酯组合物在120℃干燥4小时后，加入注射成型机，料筒温度设定为比液晶聚酯组合物的熔点高20℃，模具温度设为120℃，在3MPa注射压力和50mm/s的注射速率下，使用宽5mm、厚1mm螺旋状成型模具，将液晶聚酯组合物填充成型，如图1所示；测定成型品的长度，即为熔体流动长度，流动长度越长则说明液晶聚酯组合物的流动性越优异。
所述液晶聚酯组合物的高温耐热稳定性的测试方法：将液晶聚酯组合物在120℃干燥4小时后，加入HAAKE Polylab OS型密炼仪进行密炼，密炼温度比液晶聚酯组合物的熔点高20℃，转子的转速为50rpm，密炼时间为1小时；密炼完成后，将熔融的液晶聚酯组合物从密炼机内取出，并冷却到室温；同一样品在密炼前与密炼后均取样进行熔融粘度和比容对数粘度的测试，并进行比较分析；由于密炼是在液晶聚酯组合物熔融温度之上进行，此时将有热分解反应发生；且密炼仪转子的旋转对聚合物熔体的分子链有剪切作用，通常会伴随分子量的降低。因此比较密炼前后熔融粘度和比容对数粘度的变化，可以较直观的反映液晶聚酯组合物在高温下的高温耐热稳定性，粘度降低值较小，代表高温耐热稳定性较好。
本发明中使用的液晶聚酯含有的重复单元对应的单体的名称和缩写分别如下：
对羟基苯甲酸(HBA)；
4,4’-二羟基联苯(BP)；
对苯二甲酸(TA)；
间苯二甲酸(IA)；
2-羟基-6-萘甲酸(HNA)；
对苯二酚(HQ)；
2,6-萘二甲酸(NDA)；
本发明中使用的4-羟基苯乙酮：阿拉丁试剂(上海)有限公司；
本发明中使用的云母：牌号：Y150422，滁州格锐矿业有限责任公司。
实施例A1-A4:液晶聚酯的制备
在装配有搅拌器、温度计、氮气导入管和回流冷凝装置的反应釜中按照配比分别加入衍生自芳香族羟基羧酸的重复单元、、衍生自芳香族二醇的重复单元和衍生自芳香族二羧酸的重复单元，并加入一定比例的醋酸酐为酰化剂；然后将氮气通入反应釜中进行置换；开动搅拌，在氮气流中将反应混合物由室温加热到140℃-160℃，在此温度下回流1小时-3小时；此后继续升温，将混合物经2小时-4小时从140℃-160℃加热到300℃-350℃，在此过程中蒸出未反应的醋酸酐和副反应产物醋酸；终缩聚阶段，对反应体系进行减压，并通过观察扭矩升高作为反应结束的终点判断；此时将熔体状态的预聚物经放料口排出，并冷却至室温；进一步将预聚物转移至固相聚合装置，经5小时-7小时将温度由室温升高至260℃-280℃，在此温度下保温9小时-11小时进行固相聚合反应；反应结束后将产物导出，从而得到液晶聚酯。
表1实施例A1-A4的具体配比及其测试性能结果
Figure PCTCN2016109984-appb-000001
实施例1-12及对比例1-6：液晶聚酯组合物的制备
按表2的配比将由实施例A1-A4制备所得液晶聚酯、填充剂、4-羟基苯乙 酮和/或各种添加剂用高速混合机混合均匀后，加入双螺杆挤出机，在280RPM-320RPM的螺杆转速下熔融混合，螺筒温度为290℃-355℃，挤出，冷却、切粒，即得液晶聚酯组合物。所得液晶聚酯组合物的熔点、流动长度、熔融粘度和比容对数粘度列于表2中。
表2
Figure PCTCN2016109984-appb-000002
续表2
Figure PCTCN2016109984-appb-000003
从表2的实施例1-12及对比例1-6的比较可以看出，本发明通过选用在液晶聚酯组合物配方中添加4-羟基苯乙酮的含量基于液晶聚酯组合物的总重量为0.1ppm-500ppm时，得到的液晶聚酯组合物的高温耐热稳定性得到意想不到的显著改善，流动性也得到了提高。

Claims (11)

  1. 一种液晶聚酯组合物，其特征在于，基于液晶聚酯组合物的总重量，4-羟基苯乙酮的重量含量为0.1ppm-500ppm。
  2. 根据权利要求1所述的液晶聚酯组合物，其特征在于，4-羟基苯乙酮的重量含量的测试方法：取500mg液晶聚酯组合物样品加入25ml容量瓶中，加入2.5ml浓度为5mol/L的NaOH/CH3OH混合溶液，并加入10ml除水二甲基亚砜；在60℃的温度下保持氮气氛围，对容量瓶进行震荡24h以上，待样品中的液晶树脂水解完全后，加水溶解水解形成的芳族单体盐，并用盐酸中和过量的碱，冷冻干燥所得样品，该样品为液晶聚酯完全水解物与组合物中无机填料的混合物；将水解后的样品溶于丙酮中，采用美国安捷伦公司1260型高效液相色谱仪，测试样品中的4-羟基苯乙酮；并采用外标法对水解样品中的4-羟基苯乙酮进行定量。
  3. 根据权利要求1所述的液晶聚酯组合物，其特征在于，基于液晶聚酯组合物的总重量，4-羟基苯乙酮的重量含量优选为0.5ppm-300ppm，更优选为1ppm-100ppm。
  4. 根据权利要求1-3任一项所述的液晶聚酯组合物，其特征在于，所述液晶聚酯组合物，按重量份计，包括如下组分：
    液晶聚酯        100份；
    填充剂          5份-100份。
  5. 根据权利要求4所述的液晶聚酯组合物，其特征在于，所述液晶聚酯组合物的熔点为150℃-400℃；所述熔点的测试方法为：通过NETZSCH公司DSC 200 F3型差示扫描量热仪DSC，在从室温开始以20℃/分钟的升温条件测试，观测到吸热峰温度Tm1后，在比Tm1高20℃的温度下保持5分钟，然后在20℃/分钟的降温条件下冷却至室温，然后再次以20℃/分钟的升温条件进行测定，此时观测到的吸热峰温度Tm2即为液晶聚酯组合物的熔点。
  6. 根据权利要求4所述的液晶聚酯组合物，其特征在于，所述液晶聚酯，按摩尔百分比计，包含如下重复单元：
    衍生自芳香族羟基羧酸的重复单元    30mol％-100mol％；
    衍生自芳香族二醇的重复单元        0mol％-35mol％；
    衍生自芳香族二羧酸的重复单元      0mol％-35mol％。
  7. 根据权利要求6所述的液晶聚酯组合物，其特征在于，所述液晶聚酯，按摩尔百分比计，包括如下重复单元：
    衍生自芳香族羟基羧酸的重复单元    50mol％-100mol％；
    衍生自芳香族二醇的重复单元        0mol％-25mol％；
    衍生自芳香族二羧酸的重复单元      0mol％-25mol％。
  8. 根据权利要求6或7所述的液晶聚酯组合物，其特征在于，所述衍生自芳香族羟基羧酸的重复单元选自衍生自4-羟基苯甲酸的重复单元和/或2-羟基-6-萘甲酸的重复单元；所述衍生自芳香族二醇的重复单元选自对苯二酚的重复单元和/或4,4’-二羟基联苯的重复单元；所述衍生自芳香族二羧酸的重复单元选自对苯二甲酸的重复单元、间苯二甲酸的重复单元、2,6-萘二甲酸的重复单元中一种或几种。
  9. 根据权利要求4所述的液晶聚酯组合物，其特征在于，所述填充剂选自板状填充剂；所述板状填充剂选自滑石、云母、石墨、高岭土中的一种或几种；优选为云母。
  10. 根据权利要求9所述的液晶聚酯组合物，其特征在于，所述云母的平均粒径为0.5微米-200微米。
  11. 根据权利要求4所述的液晶聚酯组合物，其特征在于，还包含各种添加剂；所述各种添加剂选自填料、增塑剂、稳定剂、着色剂、润滑剂、脱模剂、抗氧剂中的一种或几种。
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