CN113683759B - High-modulus thermotropic liquid crystal polyarylate film and preparation method and application thereof - Google Patents
High-modulus thermotropic liquid crystal polyarylate film and preparation method and application thereof Download PDFInfo
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- 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
- C08G63/6822—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from hydroxy carboxylic acids
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- 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
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
- H04R7/00—Diaphragms for electromechanical transducers; Cones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
- H04R2307/00—Details of diaphragms or cones for electromechanical transducers, their suspension or their manufacture covered by H04R7/00 or H04R31/003, not provided for in any of its subgroups
- H04R2307/025—Diaphragms comprising polymeric materials
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Abstract
The invention belongs to the technical field of high-molecular copolymers, and particularly relates to a high-modulus thermotropic liquid crystal polyarylate film, and a preparation method and application thereof. The liquid crystalline polyarylate film of the present invention comprises the liquid crystalline polymer made from the following monomers: p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4- (4-carboxy-3-fluorophenyl) -2-fluorophenol. The preparation steps comprise prepolymerization, solid-phase polycondensation, mixing, extrusion, traction, winding and heat treatment. By introducing the novel monomer 4- (4-carboxyl-3-fluorophenyl) -2-fluorophenol, the obtained film has good tensile strength, dielectric constant and dielectric loss factor, the tensile modulus is remarkably improved, the tensile modulus can reach 12GPa and above, and the requirement of the earphone diaphragm for the high-end earphone can be met.
Description
Technical Field
The invention belongs to the technical field of high-molecular copolymers, and particularly relates to a high-modulus thermotropic liquid crystal polyarylate film, and a preparation method and application thereof.
Background
The earphone is one of the portable devices with higher daily use frequency, and the good earphone not only can enable people to enjoy high tone quality and listen to richer details, but also can prevent the hearing of people from being damaged. The earphone diaphragm is used as a key factor influencing the tone quality of the earphone, and the requirements on the material of the earphone diaphragm are light weight, high modulus and proper damping.
The common diaphragm materials at present include paper diaphragms, wood diaphragms, polymer diaphragms, metal diaphragms and the like; although the paper and wood vibrating diaphragms are light in weight, the modulus is low, and the vibration consistency is poor; although the metal diaphragm has higher modulus, the metal diaphragm has larger mass and is not easy to drive as a sound production unit; the polymer vibrating diaphragm is compared in that paper/wooden vibrating diaphragm has better modulus, has lighter quality in comparison with metal vibrating diaphragm, is the vibrating diaphragm material that uses more frequently at present.
The common polymer diaphragm mainly comprises a polyether-ether-ketone diaphragm with the modulus of 2.2GPa and a polyurethane diaphragm with the modulus of 1.6-1.8GPa, and the common polymer diaphragm is only modified continuously to reach 3.1GPa at present. With the continuous pursuit of people for the degree of sound reduction, the polymer diaphragm with the above modulus can not meet the requirement of the high-end earphone market. LCP (liquid crystal polymer) has been used as a vibrating diaphragm material due to a series of excellent characteristics of high modulus, low mass, strong damping, low dielectric, high strength and the like, and a patent (CN 111647282A) discloses an LCP vibrating diaphragm material, which adopts a lyotropic LCP solution, glass fiber powder, a filling agent, a reinforcing agent and a toughening agent to mix to obtain a modified mixture, and the LCP solution, the modified mixture and the LCP solution are sequentially coated on a coating substrate to obtain an LCP intermediate film; the diaphragm material is obtained by shaping the LCP intermediate film at the temperature of 100-250 ℃, and the diaphragm material is mainly used for modifying by adding glass fiber powder into an LCP solution and improving the rigidity of the LCP by matching with a filler, a reinforcing agent and a toughening agent in proper proportion. The processing mode of the film preparation by adopting the lyotropic LCP is limited, the film preparation needs to be carried out in solution, the quantity of additives needs to be strictly controlled for modifying the LCP, the preparation difficulty is increased, and in addition, the modulus of the modified diaphragm material is increased to 3.68GPa, compared with polyether-ether-ketone and polyurethane diaphragms, the modified diaphragm material is improved to a certain extent, but when the modified diaphragm material is applied in a 5G scene under high-frequency and high-transmission, the response delay can still be caused due to insufficient rigidity, and the sound quality of the earphone is further influenced. Therefore, there is a need to develop a new liquid crystal polymer film material to promote the development of the high-end earphone market.
Disclosure of Invention
The present invention has been made keeping in mind the above problems occurring in the prior art, and an object of the present invention is to provide a high modulus thermotropic liquid crystalline polyarylate film, in which the rigidity of the liquid crystalline polymer film can be effectively improved by incorporating a novel monomer, 4- (4-carboxy-3-fluorophenyl) -2-fluorophenol, into the liquid crystalline polymer.
The above object of the present invention can be achieved by the following technical solutions: a high modulus thermotropic liquid crystalline polyarylate film comprising a liquid crystalline polymer made from monomers comprising:
p-hydroxybenzoic acid, having the formula:
6-hydroxy-2-naphthoic acid, the structural formula of which is:
4- (4-carboxy-3-fluorophenyl) -2-fluorophenol having the formula:
wherein the mol percentages of the three monomers are respectively 64.5-86mol%, 11.8-35.1mol% and 0.4-2.2mol%, and the sum of the mol percentages of the three monomers is 100mol%.
The second object of the present invention is to provide a method for preparing the above high modulus thermotropic liquid crystalline polyarylate film, which comprises the steps of:
s1: putting monomers of p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4- (4-carboxyl-3-fluorophenyl) -2-fluorophenol, an acetylation reagent of acetic anhydride, a catalyst of 2-aminopyrimidine and an antioxidant of stannous chloride into a Hastelloy polymerization kettle for prepolymerization to prepare a prepolymer;
s2: discharging the prepolymer from the Hastelloy reactor, crushing, and performing solid phase polycondensation under the protection of nitrogen to prepare high polymer liquid crystal polyarylester;
s3: mixing the prepared polyarylester by a screw extruder, and exhausting; melt extrusion, and side blowing cooling; drawing and winding to prepare a polyarylate nascent film;
s4: and carrying out heat treatment on the prepared nascent film to prepare a finished polyarylate film.
Preferably, the amount of acetic anhydride added is 1.2 to 2.5 times the total molar number of hydroxyl groups in p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid and 4- (4-carboxy-3-fluorophenyl) -2-fluorophenol.
Preferably, the 2-aminopyrimidine is added in an amount of 50 to 200ppm based on the total weight of p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid and 4- (4-carboxy-3-fluorophenyl) -2-fluorophenol.
Preferably, the adding amount of the stannous chloride is 0.1-0.3 percent of the total weight of the p-hydroxybenzoic acid, the 6-hydroxy-2-naphthoic acid and the 4- (4-carboxyl-3-fluorophenyl) -2-fluorophenol.
Preferably, the step S1 specifically includes: putting the raw materials into a Hastelloy polymerization kettle, and keeping the temperature of the mixture at 120-140 ℃ for 2-6h; heating to 290-320 ℃ at the speed of 0.3-1.0 ℃/min, and preserving heat for 2-3h; and (3) flushing 0.1-1.0MPa of nitrogen into the polymerization kettle, discharging the prepolymer through a discharge valve with 8-10 holes and the diameter of 2-4mm, crushing, sieving with a 20-30-mesh sieve, and drying at 130-150 ℃ for 1-3h to obtain the prepolymer.
Preferably, the step S2 specifically includes: and carrying out solid phase polycondensation on the prepared prepolymer in a rotary kiln at the temperature of 190-300 ℃ for 12-48h under the protection of nitrogen to prepare the liquid crystal polyarylate.
Preferably, the extrusion temperature of the screw extruder in the step S3 is 290-340 ℃.
Preferably, the temperature of the cross air blow in the step S3 is 20-50 ℃.
Preferably, the heat treatment temperature in the step S4 is 220-300 ℃ and the time is 8-48h.
The weight average molecular weight of the high molecular liquid crystal polyarylate prepared by the polymerization reaction of the invention is 3.4-4.2 multiplied by 10 4 。
It is still another object of the present invention to provide a use of the above high modulus thermotropic liquid crystalline polyarylate film for an earphone diaphragm.
Compared with the prior art, the invention has the beneficial effects that: the dielectric property and the mechanical property of the thermotropic liquid crystal polyarylester film can be comparable with those of the existing liquid crystal film, and simultaneously, due to the introduction of the novel monomer 4- (4-carboxyl-3-fluorophenyl) -2-fluorophenol, the tensile modulus of the liquid crystal film can be effectively improved, the tensile modulus reaches 12GPa or above, and the requirements of earphone diaphragms for high-end earphones can be met.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples. In the present invention, unless otherwise specified, the starting materials or reagents used are those conventionally used, and the methods used are those conventionally used.
A high modulus thermotropic liquid crystalline polyarylate film comprising a liquid crystalline polymer made from monomers comprising:
p-hydroxybenzoic acid, having the structural formula:
6-hydroxy-2-naphthoic acid, the structural formula of which is:
4- (4-carboxy-3-fluorophenyl) -2-fluorophenol having the formula:
wherein the mol percentages of the three monomers are respectively 64.5-86mol%, 11.8-35.1mol% and 0.4-2.2mol%, and the sum of the mol percentages of the three monomers is 100mol%.
The preparation method of the liquid crystal polyarylate film comprises the following steps:
s1: putting monomers of p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4- (4-carboxyl-3-fluorophenyl) -2-fluorophenol, an acetylation reagent of acetic anhydride, a catalyst of 2-aminopyrimidine and an antioxidant of stannous chloride into a Hastelloy polymerization kettle for prepolymerization to prepare a prepolymer;
s2: discharging the prepolymer from the Hastelloy kettle, crushing, and carrying out solid phase polycondensation under the protection of nitrogen to prepare high polymer liquid crystal polyarylester;
s3: mixing the prepared polyarylate by a screw extruder, and exhausting; melt extrusion, and side blowing cooling; drawing and winding to prepare a polyarylate nascent film;
s4: and carrying out heat treatment on the prepared nascent film to prepare a finished polyarylate film.
In the above production method, the amount of acetic anhydride added is preferably 1.2 to 2.5 times the total molar number of hydroxyl groups in p-hydroxybenzoic acid 6-hydroxy-2-naphthoic acid and 4- (4-carboxy-3-fluorophenyl) -2-fluorophenol.
In the above production method, it is preferable that the 2-aminopyrimidine is added in an amount of 50 to 200ppm based on the total weight of p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid and 4- (4-carboxy-3-fluorophenyl) -2-fluorophenol.
In the above preparation method, the stannous chloride is preferably added in an amount of 0.1% to 0.3% based on the total weight of the p-hydroxybenzoic acid, the 6-hydroxy-2-naphthoic acid and the 4- (4-carboxy-3-fluorophenyl) -2-fluorophenol.
In the above preparation method, preferably, the step S1 specifically includes: putting the raw materials into a Hastelloy polymerization kettle, and keeping the temperature of the mixture at 120-140 ℃ for 2-6h; heating to 290-320 ℃ at the speed of 0.3-1.0 ℃/min, and preserving heat for 2-3h; and (3) flushing 0.1-1.0MPa of nitrogen into the polymerization kettle, discharging the prepolymer through a discharge valve with 8-10 holes and the diameter of 2-4mm, crushing, sieving with a 20-30-mesh sieve, and drying at 130-150 ℃ for 1-3h to obtain the prepolymer.
In the above preparation method, preferably, the step S2 specifically includes: and carrying out solid phase polycondensation on the prepared prepolymer in a rotary kiln at the temperature of 190-300 ℃ for 12-48h under the protection of nitrogen to prepare the liquid crystal polyarylate.
In the above preparation method, preferably, the extrusion temperature of the screw extruder in the step S3 is 290 to 340 ℃.
In the above production method, preferably, the cross-air blowing temperature in the step S3 is 20 to 50 ℃.
In the above preparation method, preferably, the heat treatment temperature in the step S4 is 220 to 300 ℃ and the time is 8 to 48 hours.
The embodiments of the present invention will be described in detail by the following examples and comparative examples. The monomer formulations of examples 1-4 of the invention are shown in Table 1:
table 1: monomer ratios in examples 1-4
Example 1
Putting p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4- (4-carboxyl-3-fluorophenyl) -2-fluorophenol, acetic anhydride accounting for 1.2 times of the total molar weight of the hydroxyl groups of the three monomers, 2-aminopyrimidine accounting for 50ppm of the total weight of the three monomers and stannous chloride accounting for 0.1 percent of the total weight of the three monomers into a hastelloy polymerization kettle according to the proportion of the No. 1 monomer, and keeping the mixture at 120 ℃ for 6 hours; heating to 290 ℃ at the speed of 0.3 ℃/min, and keeping the temperature for 2h; flushing 0.1MPa nitrogen into a polymerization kettle, discharging the prepolymer through an 8-hole discharge valve with the diameter of 2mm, crushing, sieving with a 20-mesh sieve, and drying at 130 ℃ for 3 hours to obtain the prepolymer;
subjecting the prepolymer to solid phase polycondensation in a rotary kiln at 190 deg.C for 48h under nitrogen protection to obtain liquid crystalline polyarylate having a weight average molecular weight of 4.17 × 10 4 ；
Mixing the prepared polyarylester at 290 ℃ by a double-screw extruder, and exhausting; extruding the obtained melt from a ring-shaped die with the diameter of 33.5mm and the die gap interval of 0.6mm, carrying out blowing under the conditions of a blowing ratio of 5.3 and a drawing ratio of 2.4, carrying out air blowing at the lower side of 20 ℃ for cooling and shaping, then carrying out drawing and winding to prepare a polyarylate nascent film with the average thickness of 38 mu m;
heating the polyarylate primary film and aluminum foil with a thickness of 50 μm at 280 deg.C under a pressure of 10kg/cm 2 Pressing the film at a speed of 3m/min in a hot pressing device provided with a heat-resistant rubber roller and a heating metal roller to prepare a laminated body consisting of a thermoplastic liquid crystal polymer film/an aluminum foil, and placing the laminated body in a heat treatment furnace at the temperature of 300 ℃ for 30s; under the protection of nitrogen, the mixture is subjected to heat treatment at 220 ℃ for 48 hours; thereafter, the aluminum foil was peeled off to obtain a polyarylate finished film having an average thickness of 38. Mu.m.
Example 2
Putting p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4- (4-carboxyl-3-fluorophenyl) -2-fluorophenol, acetic anhydride accounting for 1.8 times of the total molar weight of the hydroxyl groups of the three monomers, 2-aminopyrimidine accounting for 80ppm of the total weight of the three monomers and stannous chloride accounting for 0.15 percent of the total weight of the three monomers into a hastelloy polymerization kettle according to the proportion of the No. 2 monomer, and keeping the mixture at 125 ℃ for 3 hours; heating to 300 ℃ at the speed of 0.5 ℃/min, and preserving heat for 3h; flushing 0.4MPa nitrogen into a polymerization kettle, discharging the prepolymer through an 8-hole discharge valve with the diameter of 4mm, crushing, sieving with a 20-mesh sieve, and drying at 135 ℃ for 2 hours to obtain the prepolymer;
the prepolymer is put under the protection of nitrogenThen, solid-phase polycondensation was carried out in a rotary kiln at 200 ℃ for 36 hours to obtain a liquid-crystalline polyarylate having a weight average molecular weight of 3.92X 10 4 ；
Mixing the prepared polyarylester by a double-screw extruder at 320 ℃ and exhausting; mixing the prepared polyarylester at 290 ℃ by a double-screw extruder, and exhausting; extruding the obtained melt from a ring-shaped die with the diameter of 33.5mm and the die gap interval of 0.6mm, carrying out blowing under the conditions of a blowing ratio of 5.3 and a drawing ratio of 2.4, carrying out air blowing at the lower side of 20 ℃ for cooling and shaping, then carrying out drawing and winding to prepare a polyarylate nascent film with the average thickness of 38 mu m;
heating the polyarylate primary film and aluminum foil with a thickness of 50 μm at 280 deg.C under a pressure of 10kg/cm 2 Pressing the film at a speed of 3m/min in a hot pressing device provided with a heat-resistant rubber roller and a heating metal roller to prepare a laminated body consisting of a thermoplastic liquid crystal polymer film/an aluminum foil, and placing the laminated body in a heat treatment furnace at the temperature of 300 ℃ for 30s; under the protection of nitrogen, the mixture is subjected to heat treatment at 240 ℃ for 36h; thereafter, the aluminum foil was peeled off to obtain a polyarylate finished film having an average thickness of 38. Mu.m.
Example 3
Putting p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4- (4-carboxyl-3-fluorophenyl) -2-fluorophenol, acetic anhydride accounting for 2.3 times of the total molar weight of the hydroxyl groups of the three monomers, 2-aminopyrimidine accounting for 100ppm of the total weight of the three monomers and stannous chloride accounting for 0.2 percent of the total weight of the three monomers into a hastelloy polymerization kettle according to the proportion of the No. 3 monomer, and keeping the mixture at 130 ℃ for 4 hours; heating to 310 ℃ at the speed of 0.8 ℃/min, and keeping the temperature for 2h; flushing 0.6MPa nitrogen into a polymerization kettle, discharging the prepolymer through an 8-hole discharge valve with the diameter of 3mm, crushing, sieving with a 25-mesh sieve, and drying at 140 ℃ for 2 hours to obtain the prepolymer;
subjecting the prepolymer to solid phase polycondensation in a rotary kiln at 200 deg.C for 24h under nitrogen protection to obtain liquid crystalline polyarylate having a weight average molecular weight of 3.6 × 10 4 ；
Mixing the prepared polyarylate by a double-screw extruder at 330 ℃ and exhausting; mixing the prepared polyarylester at 290 ℃ by a double-screw extruder, and exhausting; extruding the obtained melt from a ring-shaped die with the diameter of 33.5mm and the die gap interval of 0.6mm, carrying out blowing under the conditions of a blowing ratio of 5.3 and a drawing ratio of 2.4, carrying out air blowing at the lower side of 20 ℃ for cooling and shaping, then carrying out drawing and winding to prepare a polyarylate nascent film with the average thickness of 38 mu m;
heating the polyarylate primary film and aluminum foil with a thickness of 50 μm at 280 deg.C under a pressure of 10kg/cm 2 Pressing the film at a speed of 3m/min in a hot press equipped with a heat-resistant rubber roller and a heating metal roller to prepare a laminate of a thermoplastic liquid crystal polymer film/aluminum foil, and placing the laminate in a heat treatment furnace at 300 ℃ for 30 seconds; under the protection of nitrogen, the mixture is subjected to heat treatment at 280 ℃ for 18h; thereafter, the aluminum foil was peeled off to obtain a polyarylate finished film having an average thickness of 38. Mu.m.
Example 4
Putting p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4- (4-carboxyl-3-fluorophenyl) -2-fluorophenol, acetic anhydride accounting for 2.5 times of the total molar weight of the hydroxyl groups of the three monomers, 2-aminopyrimidine accounting for 200ppm of the total weight of the three monomers and stannous chloride accounting for 0.3 percent of the total weight of the three monomers into a hastelloy polymerization kettle according to the proportion of the No. 4 monomer, and keeping the mixture at 140 ℃ for 2 hours; heating to 320 ℃ at the speed of 1.0 ℃/min, and keeping the temperature for 2h; 1.0MPa nitrogen is filled into a polymerization kettle, the prepolymer is discharged through a 10-hole discharge valve with the diameter of 4mm, crushed, sieved by a 30-mesh sieve and dried for 1h at 150 ℃ to prepare the prepolymer;
subjecting the prepolymer to solid phase polycondensation in a rotary kiln at 300 deg.C for 12h under nitrogen protection to obtain liquid crystalline polyarylate having a weight average molecular weight of 3.54 × 10 4 ；
Mixing the prepared polyarylate by a double-screw extruder at 340 ℃ and exhausting; mixing the prepared polyarylester at 290 ℃ through a double-screw extruder, and exhausting; extruding the obtained melt out of a ring-shaped die with the diameter of 33.5mm and the die gap interval of 0.6mm, carrying out blowing under the conditions of a blowing ratio of 5.3 and a drawing ratio of 2.4, carrying out air blowing at the lower side of 20 ℃ for cooling and shaping, then carrying out traction and rolling to obtain a polyarylate primary film with the average thickness of 38 mu m;
heating the polyarylate primary film and aluminum foil with a thickness of 50 μm at 280 deg.C under a pressure of 10kg/cm 2 Pressing the film at a speed of 3m/min in a hot press equipped with a heat-resistant rubber roller and a heating metal roller to prepare a laminate of a thermoplastic liquid crystal polymer film/aluminum foil, and placing the laminate in a heat treatment furnace at 300 ℃ for 30 seconds; under the protection of nitrogen, the mixture is subjected to heat treatment at 300 ℃ for 8 hours; thereafter, the aluminum foil was peeled off to obtain a polyarylate finished film having an average thickness of 38. Mu.m.
Comparative example 1
This comparative example differs from example 3 only in that the molar amounts of the three monomers were 79mol% of p-hydroxybenzoic acid, 20.8mol% of 6-hydroxy-2-naphthoic acid, and 0.2mol% of 4- (4-carboxy-3-fluorophenyl) -2-fluorophenol, respectively, and the other was the same as example 3, wherein the liquid-crystalline polyarylate prepared by polymerization had a weight average molecular weight of 3.43X 10 4 。
Comparative example 2
This comparative example is different from example 3 only in that the molar percentages of the three monomers are 79mol% of p-hydroxybenzoic acid, 18.5mol% of 6-hydroxy-2-naphthoic acid, and 2.5mol% of 4- (4-carboxy-3-fluorophenyl) -2-fluorophenol, respectively, and the rest are the same as in example 3, wherein the liquid-crystalline polyarylate prepared by polymerization has a weight average molecular weight of 3.64X 10 4 。
Comparative example 3
This comparative example is different from example 3 in that each of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid was used in a molar percentage of 73mol% and 27mol%, respectively, and the other examples were the same as example 3, wherein the liquid crystalline polyarylate prepared by polymerization had a weight average molecular weight of 3.41X 10 4 。
Comparative example 4
This comparative example differs from example 3 only in that the polymerization reaction used potassium acetate as a catalyst in the conventional art, wherein the liquid-crystalline polyarylate obtained by the polymerization reaction had a weight average molecular weight of 2.48X 10 4 。
The following performance tests were conducted for the above examples and comparative examples, and the test results are shown in table 2:
(1) Tensile strength: ASTM D882;
(2) Dielectric constant and dielectric dissipation factor: SPDR,15GHz;
(3) Tensile modulus: ASTM D882.
Table 2: results of property test of the liquid-crystalline polyarylate films prepared in examples 1 to 4 and comparative examples 1 to 4:
as can be seen from Table 2, the polyarylate film prepared by the formula of the present invention has good dielectric properties and mechanical properties, and especially compared with the film prepared by the conventional formula in comparative example 3, the tensile modulus of the film is significantly improved; meanwhile, the proportion of the novel monomer 4- (4-carboxyl-3-fluorophenyl) -2-fluorophenol introduced into the monomer formula is preferably in the range of 0.4-2.2mol%, the modulus of the film is improved in a limited range below the range, and the dielectric loss factor of the film is increased and the high-frequency transmission speed is influenced above the range. The film product under the condition is used for the high-end earphone diaphragm, and the tone quality effect of the film product can be influenced by different degrees. In addition, the catalyst 2-aminopyrimidine adopted by the invention can better promote the polymerization reaction, and the obtained liquid crystal polyarylate has narrow molecular distribution range and moderate weight-average molecular weight, and meets the film preparation requirement.
The diameter of the annular die and the die gap interval can be set by a person skilled in the art according to actual film making equipment, and then the inflation ratio and the draft ratio are adjusted to obtain films with different thicknesses, wherein the range of the inflation ratio can be 2.0-10, and the range of the draft ratio can be 1.8-15, which is not described in detail herein.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (9)
1. A high modulus thermotropic liquid crystalline polyarylate film comprising a liquid crystalline polymer, said liquid crystalline polymer being made from monomers comprising:
p-hydroxybenzoic acid, having the formula:
6-hydroxy-2-naphthoic acid, the structural formula of which is:
4- (4-carboxy-3-fluorophenyl) -2-fluorophenol having the formula:
wherein the mol percentages of the three monomers are respectively 64.5-86mol%, 11.8-35.1mol% and 0.4-2.2mol%, and the sum of the mol percentages of the three monomers is 100mol%;
the preparation method of the high-modulus thermotropic liquid crystal polyarylate film comprises the following steps
S1: putting monomers of p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4- (4-carboxyl-3-fluorophenyl) -2-fluorophenol, an acetylation reagent of acetic anhydride, a catalyst of 2-aminopyrimidine and an antioxidant of stannous chloride into a Hastelloy polymerization kettle for prepolymerization to prepare a prepolymer;
s2: discharging the prepolymer from the Hastelloy reactor, crushing, and performing solid phase polycondensation in a nitrogen atmosphere to prepare high polymer liquid crystal polyarylester;
s3: mixing the prepared polyarylate polymer by a screw extruder, and exhausting; melt extrusion, and side blowing cooling; drawing and winding to prepare a polyarylate nascent film;
s4: and carrying out heat treatment on the prepared nascent film to prepare a finished polyarylate film.
2. The high modulus thermotropic liquid crystalline polyarylate film of claim 1, wherein the amount of acetic anhydride added is 1.2 to 2.5 times the total molar number of hydroxyl groups in p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4- (4-carboxy-3-fluorophenyl) -2-fluorophenol.
3. The high modulus thermotropic liquid crystalline polyarylate film of claim 1, wherein the 2-aminopyrimidine is added in an amount of 50 to 200ppm based on the total weight of p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4- (4-carboxy-3-fluorophenyl) -2-fluorophenol.
4. The method for preparing a high modulus thermotropic liquid crystalline polyarylate film according to claim 1, wherein the stannous chloride is added in an amount of 0.1 to 0.3% based on the total weight of p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid and 4- (4-carboxy-3-fluorophenyl) -2-fluorophenol.
5. The high modulus thermotropic liquid crystalline polyarylate film of claim 1, wherein the step S1 is specifically: putting the raw materials into a Hastelloy polymerization kettle, and keeping the temperature of the mixture at 120-140 ℃ for 2-6h; heating to 290-320 ℃ at the speed of 0.3-1.0 ℃/min, and preserving heat for 2-3h; charging 0.1-1.0MPa nitrogen into the polymerization kettle, discharging the prepolymer through a discharge valve with 8-10 holes with the diameter of 2-4mm, crushing, sieving with a 20-30 mesh sieve, and drying at 130-150 ℃ for 1-3h to obtain the prepolymer.
6. The high modulus thermotropic liquid crystalline polyarylate film of claim 1, wherein the step S2 is specifically: and carrying out solid phase polycondensation on the prepared prepolymer in a rotary kiln at the temperature of 190-300 ℃ for 12-48h under the protection of nitrogen to prepare the liquid crystal polyarylate.
7. The high modulus thermotropic liquid crystalline polyarylate film of claim 1, wherein the extrusion temperature of the screw extruder in the step S3 is 290 to 340 ℃ and the cross air temperature is 20 to 50 ℃.
8. The high modulus thermotropic liquid crystalline polyarylate film of claim 1, wherein the heat treatment temperature in the step S4 is 220 to 300 ℃ for 8 to 48 hours.
9. Use of a high modulus thermotropic liquid crystalline polyarylate film as defined in any one of claims 1 to 8 wherein said high modulus thermotropic liquid crystalline polyarylate film is used in an earphone diaphragm.
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