CN110903612A - Liquid crystal polyester composition and preparation method thereof - Google Patents
Liquid crystal polyester composition and preparation method thereof Download PDFInfo
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- CN110903612A CN110903612A CN201911322303.4A CN201911322303A CN110903612A CN 110903612 A CN110903612 A CN 110903612A CN 201911322303 A CN201911322303 A CN 201911322303A CN 110903612 A CN110903612 A CN 110903612A
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- 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
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- 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
Abstract
The invention belongs to the field of materials, and discloses a liquid crystal polyester composition which mainly comprises liquid crystal polyester and titanium dioxide, wherein the melting point of the liquid crystal polyester is more than or equal to 280 ℃, and the dielectric loss tangent angle is lower than 0.002. The titanium dioxide is used as a dielectric material and combined with the liquid crystal polyester, and the high dielectric constant of the titanium dioxide and the liquid crystal polyester with the melting point of more than or equal to 280 ℃ and the dielectric loss tangent angle of less than 0.002 are utilized to act together, so that the obtained composition has high dielectric constant and low dielectric loss, the dielectric constant is more than 6.0, and the dielectric loss tangent angle is less than 0.005; meanwhile, the obtained composition has the advantages of further improved mechanical properties, good fluidity, high mechanical strength, high temperature resistance and no bubbling in a reflow soldering process.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a liquid crystal polyester composition and a preparation method thereof.
Background
With the rapid development of electronic information technology and nanotechnology, embedded capacitors have been widely used in various microelectronic systems. Among them, the increasing miniaturization and weight reduction of electronic components have put higher demands on the integration, safety, and lifetime of devices. Under the condition of constant electric field intensity and working frequency, the energy storage effect of the capacitor depends on the dielectric constant (Dk) of the material, and the heating performance depends on the dielectric loss tangent angle (Df) of the material. Therefore, in the case of a micro capacitor whose volume is limited, a dielectric material having a higher dielectric constant and a lower dielectric loss is necessary for developing a capacitor element having a large power and a high safety factor.
The traditional high-dielectric ceramic material has high production cost, brittle quality and difficult processing and miniaturization design. The polymer material has the advantages of good mechanical strength, light weight, flexibility, low loss, low cost and the like, and is commonly used for electronic communication products. However, due to the miniaturization of electronic communication products, high requirements are imposed on the processability of the material, such as strength, toughness and fluidity, and the material is required to maintain stable performance at 260 ℃ or higher, not to deform, not to decompose and not to foam when processed by reflow soldering. The current high dielectric low loss polymer materials cannot simultaneously meet the above requirements.
Therefore, it is desirable to provide a polymer dielectric material that satisfies high dielectric constant, low dielectric loss, high fluidity, high mechanical strength, and high temperature resistance at the same time.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a liquid crystal polyester composition which can simultaneously meet the characteristics of high dielectric constant, low dielectric loss, high fluidity, high mechanical strength and high temperature resistance.
A liquid crystal polyester composition mainly comprises liquid crystal polyester and titanium dioxide, wherein the melting point of the liquid crystal polyester is more than or equal to 280 ℃, and the dielectric loss tangent angle is less than 0.002.
The Liquid Crystalline Polyester (LCP) refers to a wholly aromatic condensation polymer having relatively rigid and linear polymer chains. They are oriented to form liquid crystalline phases which are distinguished by outstanding properties in harsh environments, exhibit high heat resistance and resistance, low dielectric losses, low water absorption and very high dimensional stability. The titanium dioxide and the prepared composite have the advantages of high dielectric constant, low dielectric loss and excellent mechanical property by utilizing the excellent electrical property of the titanium dioxide.
Preferably, the liquid crystal polyester composition further comprises a reinforcing material.
Preferably, the liquid crystal polyester composition comprises the following components in parts by weight:
50-90 parts of liquid crystal polyester
10-50 parts of titanium dioxide
5-40 parts of reinforcing materials.
Further preferably, the liquid crystal polyester composition comprises the following components in parts by weight:
50-65 parts of liquid crystal polyester
20-40 parts of titanium dioxide
10-30 parts of reinforcing materials.
Preferably, the titanium dioxide is rutile type, the dielectric constant of the titanium dioxide is high, the titanium dioxide has excellent electrical properties, and ions of the titanium dioxide interact with each other under the action of an external electric field to form a strong local internal electric field. The dielectric constant of the rutile type titanium dioxide is different along with the direction of the titanium dioxide crystal, and is 2.4 times of that of the anatase type titanium dioxide, so that the dielectric constant of the crystal polyester resin composition can be effectively improved.
Preferably, the particle size of the titanium dioxide is 0.1-0.5 μm; further preferably, the particle size of the titanium dioxide is 0.2 to 0.3 μm. When the particle size of the titanium dioxide is too small, the dispersion is not uniform, so that the dielectric property distribution is not uniform, and the fluidity and the impact property are reduced; if the volume average particle diameter is too high, the mechanical strength is affected. When the particle size of the titanium dioxide is 0.1-0.5 mu m, the dispersion effect is good, the dielectric property distribution is uniform, and other properties are not influenced.
Preferably, the titanium dioxide has an oil absorption value of 10 to 30g/100 g. If the oil absorption value of titanium dioxide is too low, dispersion is not uniform, resulting in non-uniform dielectric property distribution, and reduced fluidity and impact properties. If the oil absorption value is too high, the mechanical strength is influenced, and when the oil absorption value of the titanium dioxide is 10-30g/100g, the dispersion effect is good, the dielectric properties are uniformly distributed, and other properties are not influenced.
The liquid crystal polyester is mainly obtained by reacting a raw material monomer, fatty acid anhydride, an end-capping agent, a catalyst and a solvent, wherein the raw material monomer comprises at least one of aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid or aromatic diol.
Preferably, the aromatic hydroxycarboxylic acid is at least one of p-hydroxybenzoic acid, m-hydroxybenzoic acid, 2-hydroxy-3-naphthoic acid, 2-hydroxy-6-naphthoic acid or 1-hydroxy-5-naphthoic acid; further preferably, the aromatic hydroxycarboxylic acid is p-hydroxybenzoic acid or 2-hydroxy-6-naphthoic acid.
Preferably, the aromatic dicarboxylic acid is at least one of terephthalic acid, 4 '-diphenyldicarboxylic acid, 4' -dicarboxylic acid-diphenyl ether, isophthalic acid, 2,6 '-naphthalenedicarboxylic acid, or 4, 4' -dicarboxylic acid-diphenylsulfide; more preferably, the aromatic dicarboxylic acid is 4,4 '-biphenyldicarboxylic acid and 2, 6' -naphthalenedicarboxylic acid.
Preferably, the aromatic diol is at least one of 4,4 ' -dihydroxybiphenyl, 1,5 ' -dihydroxynaphthalene, 4,4 ' -dihydroxybenzophenone, hydroquinone, resorcinol, 4,4 ' -dihydroxydiphenyl ether, and 2,6 ' -dihydroxynaphthalene; further preferably, the aromatic diols are 4, 4' -dihydroxybiphenyl and hydroquinone.
The fatty acid anhydride is selected from one or more of acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, pivalic anhydride, 2-ethylhexanoic anhydride, monochloroacetic anhydride, dichloroacetic anhydride, trichloroacetic anhydride, monobromoacetic anhydride, dibromoacetic anhydride, tribromoacetic anhydride, monofluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, glutaric anhydride, maleic anhydride, succinic anhydride, or β -bromopropionic anhydride.
Preferably, the solvent is fatty acid, and the fatty acid is one or more of acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, 2-ethylhexanoic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monobromoacetic acid, dibromoacetic acid, tribromoacetic acid, monofluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, glutaric acid, maleic acid, succinic acid or β -bromopropionic anhydride.
Preferably, the reinforcing material comprises one or more of fibers, platelets, needles, powder, cross-like morphology. Preferably, the reinforcing material is at least one of glass fiber, quartz fiber, aramid fiber, potassium titanate whisker, barium titanate, boron nitride and silicon carbide. Further preferably, the reinforcing material is glass fiber or quartz fiber, wherein the dielectric loss of the glass fiber is less than 0.005.
Preferably, the liquid crystal polyester composition further comprises a toner, and the particle size of the toner is 20-1000nm, and further preferably, the particle size of the toner is 40-300 nm. When the particle size is too large or too small, the toner will be uniformly distributed in the liquid crystal polymer composition, forming agglomerates, resulting in an increase in dielectric loss of the material.
Preferably, the toner has an Oil Absorption Number (OAN) of 0 to 300cm3Per 100g, further preferably, the toner has an Oil Absorption Number (OAN) of 10 to 150cm3100g of the total weight. If the oil absorption value of the toner is more than 300cm3Per 100g, there is a risk of blistering of the liquid crystalline polymer composition through SMT.
Preferably, the toner has a nitrogen adsorption volume of 0 to 200m2Perg, it is further preferable that the nitrogen adsorption volume of the toner is 10 to 100m2(ii) in terms of/g. If the nitrogen adsorption volume of the toner is more than 200m2The liquid crystalline polymer composition is at risk of blistering through SMT.
Preferably, the mass of the toner is 0.1 to 5% of the total mass of the liquid crystal polyester composition, and more preferably, the mass of the toner is 0.1 to 3% of the total mass of the liquid crystal polyester composition. If the mass fraction of the toner is more than 5%, the fluidity, mechanical properties, impact strength and the like of the liquid crystal polyester composition are rapidly deteriorated, and the dielectric loss is rapidly increased.
Preferably, the toner is carbon black and/or carbon nanotubes.
Preferably, the liquid crystal polyester composition may further include other components such as an antistatic agent, a lubricant, a plasticizer, a heat stabilizer, a light stabilizer, and an antioxidant. When other components are blended in the liquid crystal polymer composition of the present invention, the amount phase thereof is 5% by mass or less of the liquid crystal polymer composition.
A method for preparing a liquid crystal polyester composition, comprising the steps of:
(1) preparing liquid crystal polyester;
(2) and (2) mixing the liquid crystal polyester prepared in the step (1) with materials such as titanium dioxide, a reinforcing material and the like, and extruding the mixture through an extruder to obtain the high-dielectric low-loss liquid crystal polyester composition.
The retention time of the materials in the extruder in the step (2) is 3-30min, and preferably, the retention time of the materials in the extruder in the step (2) is 5-20 min.
Compared with the prior art, the invention has the following beneficial effects:
the titanium dioxide is used as a dielectric material, is combined with the liquid crystal polyester and a reinforcing material, and the high dielectric constant of the titanium dioxide and the liquid crystal polyester with the melting point of more than or equal to 280 ℃ and the dielectric loss tangent angle of less than 0.002 are utilized to act together, so that the obtained composition has the advantages of high dielectric constant and low dielectric loss, the dielectric constant is more than 6.0, and the dielectric loss tangent angle is less than 0.005; meanwhile, the obtained composition has the advantages of further improved mechanical properties, good fluidity, high mechanical strength, high temperature resistance and no bubbling in a reflow soldering process.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
In the examples of the present invention, titanium dioxide 1 was purchased from Nippon Stone Co., Ltd, type TIPAQUECR-58-2, rutile type, particle size of 0.28 μm, and oil absorption of 18cm3100g of; titanium dioxide 2 was purchased from degussa corporation under model P25, with a ratio of anatase to rutile of about 80: 20, particle diameter of 21nm, oil absorption of 35cm3100g of; carbon black was purchased from cabot corporation, type: m120, particle size of 75nm, specific surface area of 25M2G, oil absorption number 72cm3100g of; glass fibre 1 purchased from Chongqing International TokyoComposite materials, Inc., model number ECS309-3-K/HL, dielectric constant 4.5, dielectric loss 0.001; glass fiber 2 was purchased from Chongqing International composite corporation as ECS3098C with a dielectric constant of 6.6 and a dielectric loss of 0.007.
Example 1
In a reactor equipped with a stainless steel type C stirrer, a torque meter, a nitrogen introduction tube, a thermometer, a pressure gauge and a reflux condenser, 994.5g of p-hydroxybenzoic acid, 299.0g of terephthalic acid, 99.7g of isophthalic acid, 446.9g of 4, 4' -dihydroxybiphenyl, 1347.6g of acetic anhydride, 200.0g of acetic acid were charged. The reactor was purged by evacuation and flushing with dry nitrogen and 0.18g of 1-methylimidazole was added. The temperature was raised to 150 ℃ over 60 minutes with stirring at 75rpm under nitrogen, and refluxed for 60 minutes by holding at this temperature. After 13.0g of benzylamine and 1.84g of calcium acetate were added to the reactor, the temperature was raised to 340 ℃ within 20 min. During this time, the by-product acetic acid was removed by distillation. After keeping the temperature at 340 ℃ for 30min, the pressure is gradually reduced to about 100pa within 20min, the vacuum is maintained until the torque is increased by more than 30%, the reaction is ended, and the prepolymer is taken out. The resulting prepolymer was cooled to room temperature and then pulverized with a coarse pulverizer. The pulverized prepolymer is subjected to solid phase polymerization by: the liquid crystalline polyester LCP1 was prepared by heating from room temperature to 250 ℃ for 3 hours, 250 ℃ to 295 ℃ for 5 hours under nitrogen and held at 295 ℃ for 2.5 hours. The test shows that the melting point of the obtained liquid crystal polyester is 335 ℃, the intrinsic viscosity is 5.5dl/g, the dielectric constant is 3.1, and the dielectric loss tangent angle is 0.0012.
Example 2
In a reactor equipped with a stainless steel type C stirrer, a torque meter, a nitrogen introduction tube, a thermometer, a pressure gauge and a reflux condenser, 994.5g of p-hydroxybenzoic acid, 399.0g of terephthalic acid, 480g of 1, 5' -dihydroxynaphthalene, 1347.6g of acetic anhydride, 200.0g of acetic acid were charged. The reactor was purged by evacuation and flushing with dry nitrogen and 0.18g of 1-methylimidazole was added. The temperature was raised to 150 ℃ over 60 minutes with stirring at 75rpm under nitrogen, and refluxed for 60 minutes by holding at this temperature. After 13.0g of benzylamine and 1.84g of calcium acetate were added to the reactor, the temperature was raised to 340 ℃ within 20 min. During this time, the by-product acetic acid was removed by distillation. After keeping the temperature at 340 ℃ for 30min, the pressure is gradually reduced to about 100pa within 20min, the vacuum is maintained until the torque is increased by more than 30%, the reaction is ended, and the prepolymer is taken out. The resulting prepolymer was cooled to room temperature and then pulverized with a coarse pulverizer. The pulverized prepolymer is subjected to solid phase polymerization by: the liquid crystalline polyester LCP2 was prepared by heating from room temperature to 250 ℃ for 3 hours, 250 ℃ to 295 ℃ for 5 hours under nitrogen and held at 295 ℃ for 2.5 hours. The test shows that the melting point of the obtained liquid crystal polyester is 325 ℃, the intrinsic viscosity is 7dl/g, the dielectric constant is 3.1, and the dielectric loss tangent angle is 0.0015.
Example 3
In a reactor equipped with a stainless steel type C stirrer, a torque meter, a nitrogen introduction tube, a thermometer, a pressure gauge and a reflux condenser, 600g of p-hydroxybenzoic acid, 376g of 2-hydroxy-6-naphthoic acid, 299.0g of terephthalic acid, 446.9g of 4, 4' -dihydroxybiphenyl, 1347.6g of acetic anhydride and 200.0g of acetic acid were charged. The reactor was purged by evacuation and flushing with dry nitrogen and 0.18g of 1-methylimidazole was added. The temperature was raised to 150 ℃ over 60 minutes with stirring at 75rpm under nitrogen, and refluxed for 60 minutes by holding at this temperature. After 13.0g of benzylamine and 1.84g of calcium acetate were added to the reactor, the temperature was raised to 340 ℃ within 20 min. During this time, the by-product acetic acid was removed by distillation. After keeping the temperature at 340 ℃ for 30min, the pressure is gradually reduced to about 100pa within 20min, the vacuum is maintained until the torque is increased by more than 30%, the reaction is ended, and the prepolymer is taken out. The resulting prepolymer was cooled to room temperature and then pulverized with a coarse pulverizer. The pulverized prepolymer is subjected to solid phase polymerization by: the liquid crystalline polyester LCP3 was prepared by heating from room temperature to 250 ℃ for 3 hours, 250 ℃ to 295 ℃ for 5 hours under nitrogen and held at 295 ℃ for 2.5 hours. The test shows that the melting point of the obtained liquid crystal polyester is 310 ℃, the intrinsic viscosity is 7dl/g, the dielectric constant is 3.1, and the dielectric loss tangent angle is 0.0009.
Example 4
60 parts of LCP1 prepared in example 1 and 40 parts of titanium dioxide 1(TIPAQUECR-58-2) were mixed uniformly and fed from the main feed port of a twin-screw extruder (model CET50 manufactured by Beijing Korea mechanical Co., Ltd.). 25 parts of glass fiber 1 was fed from the fifth stage side feed port. Processing temperature: a first area: at 330 ℃; and a second zone: 335 ℃; and (3) three zones: 340 ℃; and (4) four areas: 345 ℃; and a fifth zone: 345 ℃; a sixth zone: 345 ℃; seven areas: 345 ℃; and eight regions: 340 ℃; nine areas: 340 ℃; ten areas: 335 ℃; a machine head: 365 ℃. The rotating speed of the twin-screw is 400r/min, the vacuum degree is-0.1 MPa, the total feeding amount is 150 kg/h, and the retention time of the materials in the extruder is controlled to be 6 minutes by adjusting the screw combination. Water-cooling, drawing into strips, and cutting into granules to obtain the liquid crystal polyester composition.
Example 5
60 parts of LCP2 prepared in example 2 and 40 parts of titanium dioxide 2(P25) were mixed uniformly and fed from the main feed port of a twin-screw extruder (model CET50 manufactured by Beijing Kuolong mechanical Co., Ltd.). 25 parts of glass fiber 1 was fed from the fifth stage side feed port. Processing temperature: a first area: at 330 ℃; and a second zone: 335 ℃; and (3) three zones: 340 ℃; and (4) four areas: 345 ℃; and a fifth zone: 345 ℃; a sixth zone: 345 ℃; seven areas: 345 ℃; and eight regions: 340 ℃; nine areas: 340 ℃; ten areas: 335 ℃; a machine head: 365 ℃. The rotating speed of the twin-screw is 400r/min, the vacuum degree is-0.1 MPa, the total feeding amount is 150 kg/h, and the retention time of the materials in the extruder is controlled to be 6 minutes by adjusting the screw combination. Water-cooling, drawing into strips, and cutting into granules to obtain the liquid crystal polyester composition.
Example 6
90 parts of LCP3 prepared in example 3, 50 parts of titanium dioxide 1(TIPAQUECR-58-2) and 1 part of carbon black were mixed uniformly and fed from the main feed inlet of a twin-screw extruder (model CET50 manufactured by Beijing Korea mechanical Co., Ltd.). 40 parts of glass fiber 2 was fed from the fifth stage side feed port. Processing temperature: a first area: at 330 ℃; and a second zone: 335 ℃; and (3) three zones: 340 ℃; and (4) four areas: 345 ℃; and a fifth zone: 345 ℃; a sixth zone: 345 ℃; seven areas: 345 ℃; and eight regions: 340 ℃; nine areas: 340 ℃; ten areas: 335 ℃; a machine head: 365 ℃. The rotating speed of the twin-screw is 400r/min, the vacuum degree is-0.1 MPa, the total feeding amount is 150 kg/h, and the retention time of the materials in the extruder is controlled to be 6 minutes by adjusting the screw combination. Water-cooling, drawing into strips, and cutting into granules to obtain the liquid crystal polyester composition.
Example 7
45 parts of LCP1 prepared in example 1 and 40 parts of titanium dioxide 1(TIPAQUECR-58-2) were mixed uniformly and fed from the main feed port of a twin-screw extruder (model CET50 manufactured by Beijing Korea mechanical Co., Ltd.). 25 parts of glass fiber 1 was fed from the fifth stage side feed port. Processing temperature: a first area: at 330 ℃; and a second zone: 335 ℃; and (3) three zones: 340 ℃; and (4) four areas: 345 ℃; and a fifth zone: 345 ℃; a sixth zone: 345 ℃; seven areas: 345 ℃; and eight regions: 340 ℃; nine areas: 340 ℃; ten areas: 335 ℃; a machine head: 365 ℃. The rotating speed of the twin-screw is 400r/min, the vacuum degree is-0.1 MPa, the total feeding amount is 150 kg/h, and the retention time of the materials in the extruder is controlled to be 6 minutes by adjusting the screw combination. Water-cooling and drawing into strips, and pelletizing to obtain the liquid crystal polyester composition.
Example 8
60 parts of LCP1 prepared in example 1 and 8 parts of titanium dioxide 1(TIPAQUECR-58-2) were mixed uniformly and fed from the main feed port of a twin-screw extruder (model CET50 manufactured by Beijing Korea mechanical Co., Ltd.). 25 parts of glass fiber 1 was fed from the fifth stage side feed port. Processing temperature: a first area: at 330 ℃; and a second zone: 335 ℃; and (3) three zones: 340 ℃; and (4) four areas: 345 ℃; and a fifth zone: 345 ℃; a sixth zone: 345 ℃; seven areas: 345 ℃; and eight regions: 340 ℃; nine areas: 340 ℃; ten areas: 335 ℃; a machine head: 365 ℃. The rotating speed of the twin-screw is 400r/min, the vacuum degree is-0.1 MPa, the total feeding amount is 150 kg/h, and the retention time of the materials in the extruder is controlled to be 6 minutes by adjusting the screw combination. Water-cooling, drawing into strips, and cutting into granules to obtain the liquid crystal polyester composition.
Example 9
43 parts of LCP1 from example 1, 10 parts of LCP2 from example 2, 30 parts of titanium dioxide 1(TIPAQUECR-58-2) and 2 parts of carbon black were mixed homogeneously and fed from the main feed inlet of a twin-screw extruder (model CET50 from Beijing Keron mechanical Co., Ltd.). 15 parts of glass fiber 1 was fed from the fifth stage side feed port. Processing temperature: a first area: at 330 ℃; and a second zone: 335 ℃; and (3) three zones: 340 ℃; and (4) four areas: 345 ℃; and a fifth zone: 345 ℃; a sixth zone: 345 ℃; seven areas: 345 ℃; and eight regions: 340 ℃; nine areas: 340 ℃; ten areas: 335 ℃; a machine head: 365 ℃. The rotating speed of the twin-screw is 400r/min, the vacuum degree is-0.1 MPa, the total feeding amount is 150 kg/h, and the retention time of the materials in the extruder is controlled to be 6 minutes by adjusting the screw combination. Water-cooling, drawing into strips, and cutting into granules to obtain the liquid crystal polyester composition.
Comparative example 1
In a reactor equipped with a stainless steel type C stirrer, a torque meter, a nitrogen introduction tube, a thermometer, a pressure gauge and a reflux condenser, 966.9g of p-hydroxybenzoic acid, 564.5g of 2-hydroxy-6-naphthoic acid, 1347.6g of acetic anhydride and 200.0g of acetic acid were charged. The reactor was purged by evacuation and flushing with dry nitrogen and 0.18g of 1-methylimidazole was added. The temperature was raised to 120 ℃ over 60 minutes with stirring at 75rpm under nitrogen, and refluxed for 60 minutes by holding at this temperature. The temperature was raised to 310 ℃ within 20 min. After keeping the temperature at 300 ℃ for 30min, the pressure is gradually reduced to about 100Pa within 20min, the vacuum is maintained until the torque is increased by more than 30%, the reaction is ended, and the prepolymer is taken out. The resulting prepolymer was cooled to room temperature and then pulverized with a coarse pulverizer. The pulverized prepolymer is subjected to solid phase polymerization by: heating from room temperature to 220 deg.C in nitrogen atmosphere for 2 hours, heating from 220 deg.C to 245 deg.C in 3 hours, and keeping at 245 deg.C for 2 hours to obtain liquid crystal polyester LCP 4. The test shows that the melting point of the obtained liquid crystal polyester is 285 ℃, the intrinsic viscosity is 4dl/g, the dielectric constant is 2.9, and the dielectric loss tangent angle is 0.0028.
Comparative example 2
In a reactor equipped with a stainless steel type C stirrer, a torque meter, a nitrogen introduction tube, a thermometer, a pressure gauge and a reflux condenser, 966.9g of p-hydroxybenzoic acid, 564.5g of 2-hydroxy-6-naphthoic acid and 1347.6g of acetic anhydride were charged. The reactor was purged by evacuation and flushing with dry nitrogen and 0.18g of 1-methylimidazole was added. The temperature was raised to 150 ℃ over 60 minutes with stirring at 75rpm under nitrogen, and refluxed for 60 minutes by holding at this temperature. The temperature was raised to 340 ℃ within 20 min. During this time, the by-product acetic acid was removed by distillation. After keeping the temperature at 320 ℃ for 30min, the pressure is gradually reduced to about 100Pa within 20min, the vacuum is maintained until the torque is increased by more than 30%, the reaction is ended, and the prepolymer is taken out. The resulting prepolymer was cooled to room temperature and then pulverized with a coarse pulverizer. The pulverized prepolymer is subjected to solid phase polymerization by: heating from room temperature to 220 deg.C in nitrogen atmosphere for 2 hours, heating from 220 deg.C to 245 deg.C in 3 hours, and keeping at 245 deg.C for 2 hours to obtain liquid crystal polyester LCP 5. The melting point of the obtained liquid crystal polyester is 275 ℃, the intrinsic viscosity is 4dl/g, the dielectric constant is 2.9, and the dielectric loss tangent angle is 0.0025.
Comparative example 3
Comparative example 3 differs from example 4 in that "35 parts of titanium dioxide" was replaced with "15 parts of LCP1 and 20 parts of glass fiber 1" and the remaining raw materials and preparation method were the same as in example 4.
Comparative example 4
Comparative example 4 differs from example 4 in that "liquid crystalline polyester LCP 1" was replaced with "LCP 4 made in comparative example 1" and the remaining raw materials and preparation method were the same as in example 4.
Comparative example 5
Comparative example 5 differs from example 4 in that "liquid crystalline polyester LCP 1" was replaced with "LCP 5 made in comparative example 2" and the remaining raw materials and preparation method were the same as in example 4.
Comparative example 6
Comparative example 6 is different from example 4 in that the preparation method "residence time controlled at 6 minutes" is replaced by "residence time controlled at 1 minute", and the rest of the raw materials and the preparation method are the same as example 4. .
Product effectiveness testing
The liquid-crystalline polyester compositions obtained in examples 4 to 9 and comparative examples 3 to 6 were tested.
(1) The test conditions of the dielectric constant Dk and the dielectric loss tangent angle Df are as follows: the frequency was measured at 10GHz using the apparatus Agilent N5230A, clamp SPDR. .
(2) Tensile property: the test temperature was 23 ℃ and the test rate 2 mm/min, according to ISO 527.
(3) Notched impact strength: the test was carried out according to ISO 180 using type A notches (0.25mm base radius) and type 1 specimen dimensions (length 80mm, width 10mm, thickness 4 mm). Samples were cut from the center of the multipurpose strip using a single gear milling machine and the test temperature was 23 ℃.
(4) Reflow number of blisters: a mold having a length of 21mm, a width of 22mm, a thickness of 1-2mm and 8 pieces per mold is provided for injection molding. Each composition was injection molded 25 times for a total of 200 samples according to standard injection molding conditions. The wave-soldering temperature is 260 ℃ and 280 ℃, and the residence time at 280 ℃ exceeds 60 seconds. The number of blisters or deformations in the appearance of the part was visually checked. The high temperature resistance of the material was evaluated.
(5) Thin wall flow length: a mold having a spiral vent with a periphery of 0.5 x 10mm was provided for injection molding. The screw length was measured by injection molding at a molding temperature at which the melting point of the polyamide composition was 20 ℃. When the difference of the flow length of the three continuous dies is not more than 5 percent, taking the average value of the three values as the flow length of the thin wall.
(6) Melting point: the temperature was raised at a rate of 10 ℃ per minute from 50 ℃ under a nitrogen atmosphere using a differential scanning calorimetry analyzer "DSC 822" manufactured by METTLER TOLEDO, and the peak temperature of the melting peak appearing was determined as melting point (. degree.C.). When there are a plurality of melting peaks, the peak temperature of the melting peak at the highest temperature is determined as the melting point.
TABLE 1 test results for liquid crystalline polyester compositions
As can be seen from the test results of the liquid crystal polyester compositions prepared in examples 4 to 9 and comparative examples 3 to 6, the liquid crystal polyester compositions prepared in examples 4 to 9 had high dielectric constant, low dielectric loss, high fluidity, high strength, a dielectric constant of more than 6.0, and a dielectric loss tangent angle of less than 0.005, which could not be satisfied by the liquid crystal polyester compositions prepared in comparative examples 3 to 6; meanwhile, the liquid crystal polyester compositions prepared in examples 4 to 9 have further improved mechanical properties, good fluidity and high mechanical strength, and are obviously superior to the liquid crystal polyester compositions prepared in comparative examples 3 to 6.
Claims (10)
1. The liquid crystal polyester composition is characterized by mainly comprising liquid crystal polyester and titanium dioxide, wherein the melting point of the liquid crystal polyester is more than or equal to 280 ℃, and the dielectric loss tangent angle is less than 0.002.
2. The liquid crystalline polyester composition of claim 1, further comprising a reinforcing material.
3. The liquid crystalline polyester composition of claim 2, comprising the following components in parts by weight:
50-90 parts of liquid crystal polyester
10-50 parts of titanium dioxide
5-40 parts of reinforcing materials.
4. The liquid crystalline polyester composition of any of claims 1 to 3, wherein the titanium dioxide is in the rutile form.
5. The liquid crystalline polyester composition according to any one of claims 1 to 3, wherein the titanium dioxide has a particle size of 0.1 to 0.5 μm.
6. The liquid-crystalline polyester composition according to claim 2 or 3, wherein the reinforcing material is at least one of glass fiber, aramid fiber, potassium titanate whisker, boron nitride or silicon carbide.
7. The liquid-crystalline polyester composition according to any one of claims 1 to 3, further comprising a toner, wherein the mass of the toner is 0.1 to 5% of the mass of the liquid-crystalline polyester composition.
8. The liquid-crystalline polyester composition according to claim 7, wherein the toner has a particle diameter of 20 to 1000nm and an oil absorption value of 0 to 300cm3100g, nitrogen adsorption volume of 0-200m2/g。
9. A method for preparing a liquid crystal polyester composition, comprising the steps of:
(1) preparing liquid crystal polyester;
(2) and (2) mixing the liquid crystal polyester prepared in the step (1) with titanium dioxide and a reinforcing material, and extruding the mixture through an extruder to obtain the liquid crystal polyester composition.
10. The method according to claim 9, wherein the residence time of the material in the extruder in the step (2) is 3 to 30 min.
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