CN113773479B - High-impact-strength liquid crystal polyarylate and preparation method and application thereof - Google Patents
High-impact-strength liquid crystal polyarylate and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of high molecular polymers, and particularly relates to high-impact-strength liquid crystal polyarylate as well as a preparation method and application thereof. The liquid crystalline polyarylate of the present invention is prepared from the following monomers: p-hydroxybenzoic acid, hydroquinone, diphenic acid and 4- (4-carboxyl-3-fluorophenyl) -2-fluorobenzoic acid. The preparation steps are prepolymerization and solid phase polycondensation. According to the invention, by introducing the novel monomer 4- (4-carboxyl-3-fluorophenyl) -2-fluorobenzoic acid, the p-hydroxybenzoic acid, the hydroquinone and the biphenyldicarboxylic acid for copolymerization, the impact strength of the liquid crystal polyarylate can be obviously improved, the impact strength can reach more than 170J/m, better melt tension can be obtained, the melt tension can reach more than 61mN, the requirements of electronic thin-wall parts on the impact resistance can be met, and stable film preparation can be realized.
Description
Technical Field
The invention belongs to the technical field of high polymer polymerization, and particularly relates to high-impact-strength liquid crystal polyarylate as well as a preparation method and application thereof.
Background
As communication speeds become faster and faster, 5G communication is moving to the world. Since this new technology is applied to the high frequency range, the requirements of low dielectric constant and dielectric loss, good mechanical properties, and low moisture absorption are put on the material of the device. LCP is recognized as the preferred material for 5G communication due to its excellent dielectric properties, low hygroscopicity, dimensional stability, etc.
Despite the above-mentioned excellent properties, LCP's are still required to have further improved impact strength when used in certain devices (e.g., electronic thin-walled molded parts), and certain melt tensions (above 25 mN) are required for film processing. CN109796730A reports that a wholly aromatic liquid crystalline polyester resin is used as a base resin component and is modified with a reactive ethylene copolymer to improve the impact strength of a liquid crystalline polyester resin composite; in addition, CN1760232B reports that the whiteness and the impact performance of the obtained product can be improved by adding dihydric phosphate in the synthesis process of thermotropic liquid crystal polyester; CN109824876B reports that TLCP polyarylate chains can be slightly branched by using different temperature rising rates at different stages of polymerization reaction, and the prepared TLCP resin shows higher melt tension. The technology only aims at the single performance of impact resistance or melt tension, and the research of combining the two performances is not reported yet. The inventors have essentially improved the impact resistance and melt tension of LCP's by introducing novel monomers for chemical copolymerization with significant success.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a high-impact-strength liquid crystal polyarylate, wherein the specific proportion of the monomer 4- (4-carboxyl-3-fluorophenyl) -2-fluorobenzoic acid, p-hydroxybenzoic acid, hydroquinone and biphenyldicarboxylic acid is introduced into the liquid crystal polyarylate for copolymerization, so that the impact resistance of the liquid crystal polyarylate can be greatly improved, the obtained liquid crystal polyarylate has better melt tension, and the requirement of stable film preparation can be met.
A high impact strength liquid crystalline polyarylate prepared from the following monomers:
p-hydroxybenzoic acid, having the formula:
hydroquinone, the structural formula of which is:
biphenyldicarboxylic acid having the formula:
4- (4-carboxy-3-fluorophenyl) -2-fluorobenzoic acid having the formula:
the mole percentages of the monomers are respectively expressed by A, B, C and D, the unit is mol%, and the correlation is as follows: 63 ≦ A ≦ 80;20 ≦ B + C + D ≦ 37; b = C + D;1.2 ≦ D ≦ 3.0; a + B + C + D =100.
The second object of the present invention is to provide a method for preparing the above liquid crystalline polyarylate, said method comprising the steps of:
s1: putting monomers of p-hydroxybenzoic acid, hydroquinone, diphenic acid, 4- (4-carboxyl-3-fluorophenyl) -2-fluorobenzoic acid, an acetylation reagent of acetic anhydride, a catalyst of 2-methylamino benzothiazole 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 performing solid phase polycondensation in a nitrogen atmosphere to obtain the liquid crystal polyarylate.
Preferably, the amount of the acetic anhydride added is 1.5 to 2.5 times the total number of moles of hydroxyl groups in the hydroxyl group-containing monomer.
Preferably, the 2-methylaminobenzothiazole is added in an amount of 60 to 300ppm based on the total weight of the four monomers.
Preferably, the addition amount of the stannous chloride is 0.14-0.30% of the total weight of the four monomers.
Preferably, the step S1 specifically includes: putting the raw materials into a hastelloy polymerization kettle, and keeping the temperature at 135-150 ℃ for 3-8h; heating to 300-320 ℃ at the speed of 0.5-1.0 ℃/min, and preserving heat for 1-3h; and (3) charging 0.4-0.9MPa 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 145-160 ℃ 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 195-320 ℃ for 12-48h under the protection of nitrogen to prepare the liquid crystal polyarylate.
It is still another object of the present invention to provide a use of the above liquid crystalline polyarylate for preparing a film.
The liquid crystalline polyarylate film of the present invention can be prepared by the following method:
(1) Blow molding process
And (2) putting the liquid crystal polyarylate into a screw extruder for melting plasticization, then extruding the liquid crystal resin in the molten state into a cylindrical tube blank through an annular die head, simultaneously injecting compressed air into the tube blank to further blow the tube blank, and cooling, drawing and rolling to obtain the liquid crystal polyarylate film.
(2) T-die method
And (3) putting the liquid crystal polyarylate into a screw extruder for melting plasticization, then extruding through a T die head, casting onto a cooling roller, cooling, shaping, further performing uniaxial or biaxial stretching, trimming and rolling to obtain the liquid crystal polyarylate film.
Compared with the prior art, the invention has the following beneficial effects:
under the synergistic action of a catalyst 2-methylaminobenzothiazole and an antioxidant stannous chloride, by introducing a novel monomer 4- (4-carboxyl-3-fluorophenyl) -2-fluorobenzoic acid, p-hydroxybenzoic acid, hydroquinone and diphenic acid for copolymerization, the impact strength of the liquid crystal polyarylate (more than 170J/m) is improved, and better melt tension (more than 61 mN) can be obtained, so that the liquid crystal polyarylate meets the requirement of an electronic thin-wall part on the impact resistance, and stable film preparation can be realized.
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 impact strength liquid crystalline polyarylate prepared from the following monomers:
p-hydroxybenzoic acid, having the structural formula:
hydroquinone, the structural formula of which is:
biphenyldicarboxylic acid having the formula:
4- (4-carboxy-3-fluorophenyl) -2-fluorobenzoic acid having the formula:
the mole percentages of the monomers are respectively expressed by A, B, C and D, the unit is mol%, and the correlation is as follows: 63 ≦ A ≦ 80, 20 ≦ B + C + D ≦ 37; b = C + D;1.2 ≦ D ≦ 3.0; a + B + C + D =100.
The preparation method of the high-impact strength liquid crystal polyarylate comprises the following steps:
s1: putting monomers of p-hydroxybenzoic acid, hydroquinone, diphenic acid, 4- (4-carboxyl-3-fluorophenyl) -2-fluorobenzoic acid, acetylation reagent acetic anhydride, a catalyst of 2-methylaminobenzothiazole and an antioxidant stannous chloride into a Hastelloy polymerization kettle for prepolymerization to prepare a prepolymer;
s2: and discharging the prepolymer from the Hastelloy reactor, crushing, and performing solid-phase polycondensation in a nitrogen atmosphere to obtain the liquid crystal polyarylate.
In the above production method, acetic anhydride is preferably added in an amount of 1.5 to 2.5 times the total molar number of hydroxyl groups in the hydroxyl group-containing monomer.
In the above preparation method, the preferred amount of 2-methylaminobenzothiazole to be added is 60 to 300ppm based on the total weight of the four monomers.
In the above preparation method, the amount of stannous chloride added is preferably 0.14 to 0.30% of the total weight of the four monomers.
In the above preparation method, the preferable step S1 is specifically: putting the raw materials into a Hastelloy polymerization kettle, and keeping the temperature at 135-150 ℃ for 3-8h; heating to 300-320 ℃ at the speed of 0.5-1.0 ℃/min, and preserving heat for 1-3h; and (3) charging 0.4-0.9MPa 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 145-160 ℃ for 1-3h to obtain the prepolymer.
In the above preparation method, the preferable step S2 is specifically: and carrying out solid phase polycondensation on the prepared prepolymer in a rotary kiln at 195-320 ℃ for 12-48h under the protection of nitrogen to prepare the liquid crystal polyarylate.
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 5
The preparation of liquid crystalline polyarylate was carried out according to the monomer formulation in example 1, with the following specific procedure: putting monomers of p-hydroxybenzoic acid, hydroquinone, diphenic acid, 4- (4-carboxyl-3-fluorophenyl) -2-fluorobenzoic acid, acetic anhydride accounting for 1.5 times of the total mole number of hydroxyl in the hydroxyl-containing monomers, 2-methylamino benzothiazole accounting for 60ppm of the total weight of the four monomers and stannous chloride accounting for 0.14 percent of the total weight of the four monomers into a Hastelloy polymerization kettle, and keeping the mixture at 135 ℃ for 3 hours; heating to 300 ℃ at the speed of 0.5 ℃/min, and keeping the temperature for 1h; flushing 0.4MPa 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 145 ℃ for 1h to obtain the prepolymer; and carrying out solid phase polycondensation on the prepared prepolymer in a rotary kiln at 195 ℃ for 12h under the protection of nitrogen to prepare the liquid crystal polyarylate.
Example 6
The preparation of liquid crystalline polyarylate was carried out according to the monomer formulation in example 2, the specific procedure was: putting monomers of p-hydroxybenzoic acid, hydroquinone, diphenic acid, 4- (4-carboxyl-3-fluorophenyl) -2-fluorobenzoic acid, acetic anhydride accounting for 1.8 times of the total mole number of hydroxyl in the hydroxyl-containing monomers, 2-methylamino benzothiazole accounting for 130ppm of the total weight of the four monomers and stannous chloride accounting for 0.20 percent of the total weight of the four monomers into a Hastelloy polymerization kettle, and keeping the monomers at 140 ℃ for 5 hours; heating to 305 ℃ at the speed of 0.6 ℃/min, and keeping the temperature for 2 hours; flushing 0.6MPa nitrogen into a polymerization kettle, discharging the prepolymer through an 8-hole discharge valve with the diameter of 2mm, crushing, sieving with a 25-mesh sieve, and drying at 150 ℃ for 2 hours to obtain the prepolymer; and carrying out solid-phase polycondensation on the prepared prepolymer in a rotary kiln at 240 ℃ for 16h under the protection of nitrogen to prepare the liquid crystal polyarylate.
Example 7
The preparation of liquid crystalline polyarylate was carried out according to the monomer formulation in example 3, the specific procedure was: putting monomers of p-hydroxybenzoic acid, hydroquinone, diphenic acid, 4- (4-carboxyl-3-fluorophenyl) -2-fluorobenzoic acid, acetic anhydride accounting for 2.0 times of the total mole number of hydroxyl in the hydroxyl-containing monomers, 2-methylamino benzothiazole accounting for 210ppm of the total weight of the four monomers and stannous chloride accounting for 0.24 percent of the total weight of the four monomers into a Hastelloy polymerization kettle, and keeping the mixture at 145 ℃ for 6 hours; heating to 310 ℃ at the speed of 0.8 ℃/min, and keeping the temperature for 2h; flushing 0.7MPa nitrogen into a polymerization kettle, discharging the prepolymer through a 9-hole discharge valve with the diameter of 3mm, crushing, sieving with a 25-mesh sieve, and drying at 155 ℃ for 3 hours to obtain the prepolymer; and carrying out solid-phase polycondensation on the prepared prepolymer in a rotary kiln at 280 ℃ for 24 hours under the protection of nitrogen to prepare the liquid crystal polyarylate.
Example 8
The preparation of liquid crystalline polyarylate was carried out according to the monomer formulation in example 4, with the specific procedure: putting monomers of p-hydroxybenzoic acid, hydroquinone, diphenic acid, 4- (4-carboxyl-3-fluorophenyl) -2-fluorobenzoic acid, acetic anhydride accounting for 2.5 times of the total mole number of hydroxyl in the hydroxyl-containing monomers, 2-methylamino benzothiazole accounting for 300ppm of the total weight of the four monomers and stannous chloride accounting for 0.30 percent of the total weight of the four monomers into a Hastelloy polymerization kettle, and keeping the mixture at 150 ℃ for 8 hours; heating to 320 ℃ at the speed of 1.0 ℃/min, and preserving heat for 3h; flushing 0.9MPa nitrogen into a polymerization kettle, discharging the prepolymer through a 10-hole discharge valve with the diameter of 4mm, crushing, sieving with a 30-mesh sieve, and drying at 160 ℃ for 3 hours to obtain the prepolymer; and carrying out solid phase polycondensation on the prepared prepolymer in a rotary kiln at 320 ℃ for 48h under the protection of nitrogen to prepare the liquid crystal polyarylate.
Comparative example 1
This comparative example differs from example 7 only in that 74mol% of p-hydroxybenzoic acid, 13mol% of hydroquinone, 12.2mol% of biphenyldicarboxylic acid and 0.8mol% of 4- (4-carboxy-3-fluorophenyl) -2-fluorobenzoic acid were used as monomers, and the other preparation procedures were the same as in example 7.
Comparative example 2
This comparative example differs from example 7 only in that the monomer ratios of 74mol% of p-hydroxybenzoic acid, 13mol% of hydroquinone, 9.6mol% of biphenyldicarboxylic acid and 3.4mol% of 4- (4-carboxy-3-fluorophenyl) -2-fluorobenzoic acid were used, and the other preparation procedures were the same as in example 7.
Comparative example 3
This comparative example is different from example 7 only in that 74mol% of p-hydroxybenzoic acid, 13mol% of hydroquinone and 13mol% of biphenyldicarboxylic acid were used as monomers, and the other preparation processes were the same as example 7.
Comparative example 4
This comparative example differs from example 7 only in that instead of 2-methylaminobenzothiazole, an equimolar amount of the catalyst sodium acetate is used and the procedure is otherwise the same as in example 7.
Application example
The liquid crystal polyarylate prepared by the method is prepared into a film by adopting a blow molding method, and the specific process is as follows:
putting the liquid crystal polyarylate into a double-screw extruder with the temperature of 320 ℃ for melting plasticization, then extruding the liquid crystal resin in a molten state into a cylindrical tube blank through an annular die head, simultaneously injecting compressed air into the tube blank to further blow up the tube blank, and cooling by side blowing at 45 ℃; then drafting and winding to prepare a liquid crystal polyarylate nascent film;
heating the nascent film and aluminum foil with thickness of 50 μm at 280 deg.C under pressure of 10kg/cm 2 At a speed of 3m/minPreparing a laminate of a thermoplastic liquid crystalline polyarylate film/aluminum foil by pressure-bonding the laminate to a hot rolling device equipped with a heat-resistant rubber roll and a heating metal roll, 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 250 ℃ for 18h; and then, peeling the aluminum foil to obtain the finished liquid crystal polyarylate film.
The following performance tests were conducted for examples 5 to 8 and comparative examples 1 to 4, and the test results are shown in Table 2:
(1) Tensile strength: the liquid crystalline polyarylate was molded into a dumbbell-shaped specimen having a thickness of 2.0mm by an injection molding machine. The tensile strength was measured according to ISO 527-2 at a traction rate of 5 mm/min.
(2) Dielectric constant and dielectric dissipation factor: a bar-shaped specimen having a length of 85mm, a width of 1.75mm and a thickness of 1.75mm was prepared from the liquid-crystalline polyarylate by using an injection molding machine. The test was carried out according to IEC62631-2-1 at 5 GHz.
(3) Impact strength: liquid crystalline polyarylate was prepared into test pieces having a length of 64mm, a width of 12.7mm and a thickness of 2.0mm using an injection molding machine, and the Izod impact strength was measured according to ASTM D256.
(4) Melt tension: a liquid crystalline polyarylate was melt-extruded at a screw rotation speed of 20r/min and at a temperature 5 ℃ or higher than the melting temperature in a torque rheometer (model HAAK PolyLab OS) having a screw diameter of 19mm, and the sample was drawn into a filament shape by automatically increasing the speed by a variable speed winder, and the tension (unit: mN) at the time of breaking was measured.
Table 2: results of property test of the liquid-crystalline polyarylates prepared in examples 5 to 8 and comparative examples 1 to 4:
film formation of liquid crystalline polyarylate: "+ +" indicates the best film forming stability, "+" indicates better film forming, and "-" indicates poor film forming.
As can be seen from Table 2, the liquid crystalline polyarylate prepared by the formulation and the preparation method of the present invention has excellent impact strength and melt tension, and when the monomer 4- (4-carboxy-3-fluorophenyl) -2-fluorobenzoic acid is controlled within the mol% of the protection range (1.2 to 3.0) of the present invention, a balance between the impact strength and the melt tension can be obtained, and when the monomer is out of the range, one of the properties is reduced to a different extent. In addition, the conventional catalyst is adopted to replace the catalyst 2-methylamino benzothiazole, side reactions are increased in the polymerization process, and the obtained liquid crystal polyarylate has low melt tension and can not meet the film preparation requirement.
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 (10)
1. A high impact strength liquid crystalline polyarylate, wherein said liquid crystalline polyarylate is prepared from the following monomers:
p-hydroxybenzoic acid, having the structural formula:
hydroquinone, the structural formula of which is:
biphenyldicarboxylic acid having the formula:
4- (4-carboxy-3-fluorophenyl) -2-fluorobenzoic acid having the formula:
the mole percentages of the monomers are respectively expressed by A, B, C and D, the unit is mol%, and the correlation is as follows: 63 ≦ a ≦ 80, 20 ≦ B + C + D ≦ 37; b = C + D;1.2 ≦ D ≦ 3.0; a + B + C + D =100.
2. A method for preparing a high impact strength liquid crystalline polyarylate as claimed in claim 1, wherein said method comprises the steps of:
s1: putting monomers of p-hydroxybenzoic acid, hydroquinone, diphenic acid, 4- (4-carboxyl-3-fluorophenyl) -2-fluorobenzoic acid, acetylation reagent acetic anhydride, a catalyst of 2-methylaminobenzothiazole and an antioxidant stannous chloride into a Hastelloy polymerization kettle for prepolymerization to prepare a prepolymer;
s2: discharging the prepolymer from the Hastelloy kettle, crushing, and performing solid phase polycondensation in a nitrogen atmosphere to obtain the liquid crystal polyarylate.
3. The method of producing a high impact strength liquid crystalline polyarylate as claimed in claim 2, wherein said acetic anhydride is added in an amount of 1.5 to 2.5 times the total mole number of the hydroxyl groups in the hydroxyl group containing monomer.
4. The method of preparing a high impact strength liquid crystalline polyarylate of claim 2 wherein said 2-methylaminobenzothiazole is added in an amount of 60 to 300ppm based on the total weight of the four monomers.
5. The method of preparing a high impact strength liquid crystalline polyarylate as claimed in claim 2, wherein the stannous chloride is added in an amount of 0.14 to 0.30% by weight based on the total weight of the four monomers.
6. The method of preparing a high impact strength liquid crystalline polyarylate as claimed in claim 2, wherein said step S1 is specifically: putting the raw materials into a hastelloy polymerization kettle, and keeping the temperature at 135-150 ℃ for 3-8h; heating to 300-320 ℃ at the speed of 0.5-1.0 ℃/min, and preserving heat for 1-3h; and (3) charging 0.4-0.9MPa 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 145-160 ℃ for 1-3h to obtain the prepolymer.
7. The method for preparing a high impact strength liquid crystalline polyarylate as claimed in claim 2, wherein said step S2 is specifically: and carrying out solid phase polycondensation on the prepared prepolymer in a rotary kiln at 195-320 ℃ for 12-48h under the protection of nitrogen to prepare the liquid crystal polyarylate.
8. Use of the high impact strength liquid crystalline polyarylate as claimed in claim 1 for the preparation of a film.
9. Use of the high impact strength liquid crystalline polyarylate in the preparation film according to claim 8, wherein the liquid crystalline polyarylate film is prepared by a blow molding method; the liquid crystal polyarylate film is prepared by putting liquid crystal polyarylate in a screw extruder for melting plasticization, extruding the liquid crystal resin in a molten state into a cylindrical tube blank through an annular die head, simultaneously injecting compressed air into the tube blank to further blow up the tube blank, and cooling, drawing and rolling the tube blank.
10. The use of a high impact strength liquid crystalline polyarylate in the preparation of a film according to claim 8 wherein the liquid crystalline polyarylate film is prepared by a T-molding method; the method specifically comprises the steps of putting liquid crystal polyarylate into a screw extruder for melting and plasticizing, then extruding through a T die head, casting onto a cooling roller, cooling and shaping, and further carrying out uniaxial or biaxial stretching, edge cutting and rolling to obtain the liquid crystal polyarylate film.
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