CN107674205B - Thermosetting wholly aromatic polyester imide liquid crystal and preparation method thereof - Google Patents

Thermosetting wholly aromatic polyester imide liquid crystal and preparation method thereof Download PDF

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CN107674205B
CN107674205B CN201711036416.9A CN201711036416A CN107674205B CN 107674205 B CN107674205 B CN 107674205B CN 201711036416 A CN201711036416 A CN 201711036416A CN 107674205 B CN107674205 B CN 107674205B
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wholly aromatic
liquid crystal
thermosetting
aromatic polyester
polyester imide
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CN107674205A (en
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顾嫒娟
黄婷
管清宝
梁国正
袁莉
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Guangxi Feimate Technology Co ltd
Hefei Keyiguo Information Technology Co ltd
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Suzhou University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/16—Polyester-imides
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C09K19/3804—Polymers with mesogenic groups in the main chain
    • C09K19/3823—Polymers with mesogenic groups in the main chain containing heterocycles having at least one nitrogen as ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Abstract

The invention relates to a thermosetting wholly aromatic polyester imide liquid crystal and a preparation method thereof. By condensing a phosphoric ester, a metal salt, a reactive terminal group and a wholly aromatic monomer (X) R1‑Ar‑R2Uniformly mixing the obtained product with a wholly aromatic monomer (Y) containing imide groups in a polar solvent, introducing nitrogen for protection, carrying out alcohol acid direct esterification reaction at the temperature of 100-150 ℃, and carrying out the reaction for 2-6 h to obtain a thermosetting wholly aromatic polyester imide liquid crystal with the molecular weight of 1000-7000 g/mol; the thermosetting wholly aromatic polyester imide liquid crystal has the characteristics of low melting point, excellent processability and excellent thermodynamic performance.

Description

Thermosetting wholly aromatic polyester imide liquid crystal and preparation method thereof
Technical Field
The invention relates to a thermosetting wholly aromatic polyester imide liquid crystal and a preparation method thereof, belonging to the field of high-performance polymers.
Background
The thermosetting wholly aromatic polyester imide liquid crystal has the advantages of high glass transition temperature, high decomposition temperature and chemical resistance of general wholly aromatic polyester imide, good processing performance, dimensional stability, self-reinforcement and the like of thermotropic liquid crystal polymer materials, and becomes a material with excellent comprehensive performance applied to the aerospace and electronic industries.
The current processes for the preparation of thermosetting polyesterimides are largely divided into melt polymerization and solution polymerization, melt polymerization presents several problems, firstly, esterification and transesterification reactions generally need to take place at 250-320 ℃ (see ① Guan, Q.; Norder, B.; Chu L.; Besseling, N.A. M.; Picken, S. J.; Dingens, T. J., All-Aromatic (AB) n-multiblock copolymer vie-step polymerization chemistry. Macromolecules, 2016, 49 (22), 8549 8562. ② Knijnenberg, A.; Weiser, E.S.; Stir, T. L.; Mendes, E.E., Dingens, T. J., Synthesis of thermosetting polyester imides, and, secondly, polymerization reactions need to take place in a higher activity in a vacuum environment than polymerization in a high temperature environment, such as to promote the polymerization reaction in a high activity of the polymer chain reaction, such as the condensation polymerization reaction requires a high activity of the molecular chain polymerization reaction at room temperature, 36 deg.C., and the high activity of the molecular chain polymerization reaction requires no further high temperature, such as a high activity of the molecular chain polymerization reaction at room temperature, high temperature, and high temperature, high temperature.
The preparation of thermosetting polyesterimides by the solution polymerization process is generally carried out in two stages. Firstly, preparing a polyamic acid precursor; in the second step, an imide cyclization reaction of the polyamic acid is performed. However, the cyclization reaction of the polyamic acid into the polyimide needs to be carried out at a high temperature (250 to 300 ℃). Therefore, how to prepare the crosslinkable and cured wholly aromatic polyester imide liquid crystal by using the low temperature solution polymerization method still remains a challenge and a topic with great application value.
Disclosure of Invention
In order to overcome the defects of the existing materials and technologies, the invention aims to provide a crosslinkable and curable wholly aromatic polyester imide liquid crystal and a preparation method thereof.
The invention adopts the following technical scheme:
a preparation method of a thermosetting wholly aromatic polyester imide liquid crystal comprises the following steps: dropwise adding a solution containing a phosphate condensing agent and metal salt into a preheated mixed solution containing a monomer, an active end group and a polar solvent, and then reacting for 2-6 h at 100-150 ℃ in nitrogen to obtain a polymer solution; then pouring the polymer solution into an organic solvent, washing and drying to obtain a thermosetting wholly aromatic polyester imide liquid crystal;
the monomer is a wholly aromatic monomer and a wholly aromatic monomer containing an imide group;
the chemical structural formula of the wholly aromatic monomer is R1-Ar1-R2，Ar1Is a wholly aromatic radical, R1、R2Is an end group;
the chemical structural formula of the wholly aromatic monomer containing the imide group is as follows:
Figure 646832DEST_PATH_IMAGE001
ar is a wholly aromatic radical, R3、R4Are end groups.
The invention also discloses a preparation method of the thermosetting wholly aromatic polyester imide liquid crystal precursor solution, which comprises the following steps: dropwise adding a solution containing a phosphate condensing agent and metal salt into a preheated mixed solution containing a monomer, an active end group and a polar solvent, and then reacting for 2-6 h at 100-150 ℃ in nitrogen to obtain a thermosetting wholly aromatic polyesterimide liquid crystal precursor solution;
the monomer is a wholly aromatic monomer and a wholly aromatic monomer containing an imide group;
the chemical structural formula of the wholly aromatic monomer is R1-Ar1-R2，Ar1Is a wholly aromatic radical, R1、R2Is an end group;
the chemical structural formula of the wholly aromatic monomer containing the imide group is as follows:
Figure 563972DEST_PATH_IMAGE001
ar is a wholly aromatic radical, R3、R4Are end groups.
In the technical scheme, the phosphate condensing agent is one or more of phenyl chlorophosphate, triphenyl phosphite, tris (4-chlorophenyl) phosphite and diphenyl hydrogen phosphite; the metal salt is one or more of anhydrous lithium chloride, magnesium chloride, calcium chloride and zinc chloride; the active end group is one or more of 3-aminophenylacetylene, maleic anhydride and 5- (phenylethynyl) isobenzofuran-1, 3-diketone; the organic solvent is one or more of methanol, ethyl acetate and petroleum ether; the polar solvent is one or more of pyridine, methyl pyrrolidone and N, N-dimethylacetamide; in the solution containing the phosphate condensing agent and the metal salt, the solvent is one or more of pyridine, methyl pyrrolidone and N, N-dimethylacetamide.
In the above technical scheme, Ar is1Is one of the following three structures:
Figure 343709DEST_PATH_IMAGE002
、
Figure 270077DEST_PATH_IMAGE003
、
Figure 84449DEST_PATH_IMAGE004
；
ar is one of the following three structures:
Figure 64169DEST_PATH_IMAGE002
、
Figure 331202DEST_PATH_IMAGE003
、
Figure 61261DEST_PATH_IMAGE004
；
the R is1、R2、R3、R4Independently selected from-COOH or-OH.
In the present invention, the wholly aromatic monomer may be represented by X, and the wholly aromatic monomer having an imide group may be represented by Y, and both have different chemical structures.
In the technical scheme, the molar ratio of the wholly aromatic monomer to the wholly aromatic monomer containing the imide group in the monomers is n to (1-n), wherein n is more than or equal to 0 and less than 1; the molar ratio of the phosphate condensing agent to the monomer is (1-5) to 1; in the solution containing the phosphate condensing agent and the metal salt, the molar ratio of the metal salt to the solvent is 1: 6-1: 30, and the metal salt has the function of increasing the solubility of the solvent and improving the reaction uniformity. The amount of reactive end groups of the present invention is designed according to the molecular weight of the intended synthesis and the molar amount of monomer.
In the technical scheme, a phosphate ester condensing agent and metal salt are added into a solvent, and stirred for 30-45 min at 10-40 ℃ to obtain a solution containing the phosphate ester condensing agent and the metal salt; the preheating is carried out for 5-10 min at 100-150 ℃ under the protection of nitrogen; the dripping time is 30-60 min.
The preparation method of the present invention can be exemplified as follows:
(1) adding a phosphate ester condensing agent and metal salt into a solvent, stirring for 30-45 min at 10-40 ℃, and uniformly mixing to obtain a clear solution A;
(2) the wholly aromatic monomer (X) R1-Ar1-R2Adding the wholly aromatic monomer (Y) containing imide groups and the active end group into a polar solvent; preheating for 5-10 min at 100-150 ℃ under the protection of nitrogen to obtain a clear solution B;
(3) dropwise adding the solution A into the solution B for 30-60 min; introducing nitrogen flow, and reacting for 2-6 h at 100-150 ℃ to obtain a polymer solution C;
(4) and (4) pouring the polymer solution C obtained in the step (3) into an organic solvent, washing, drying and grinding to obtain powder, namely the thermosetting wholly aromatic polyester imide liquid crystal with the molecular weight of 1000-7000 g/mol.
The invention also discloses a thermosetting wholly aromatic polyester imide liquid crystal prepared by the preparation method of the thermosetting wholly aromatic polyester imide liquid crystal; the molecular weight of the thermosetting wholly aromatic polyester imide liquid crystal is 1000-7000 g/mol.
The invention also discloses the thermosetting wholly aromatic polyester imide liquid crystal precursor solution prepared by the preparation method of the thermosetting wholly aromatic polyester imide liquid crystal precursor solution.
The invention also discloses a thermosetting wholly aromatic polyester imide liquid crystal film and a preparation method thereof, wherein the preparation method comprises the following steps: dropwise adding a solution containing a phosphate condensing agent and metal salt into a preheated mixed solution containing a monomer, an active end group and a polar solvent, and then reacting for 2-6 h at 100-150 ℃ in nitrogen to obtain a polymer solution; then pouring the polymer solution into an organic solvent, and washing, drying and grinding to obtain polymer powder; finally, pre-hot pressing and curing the polymer powder to obtain a thermosetting wholly aromatic polyester imide liquid crystal film; for example, the obtained polymer powder is spread in a mould, placed at 250 ℃ and 2bar for 15min, naturally cooled and demoulded, and then subjected to a multi-step curing process of 200 ℃/1h +230 ℃/1h +270 ℃/1h +300 ℃/1h to obtain the thermosetting wholly aromatic polyester imide liquid crystal film;
the monomer is a wholly aromatic monomer and a wholly aromatic monomer containing an imide group;
the chemical structural formula of the wholly aromatic monomer is R1-Ar1-R2，Ar1Is a wholly aromatic radical, R1、R2Is an end group;
the chemical structural formula of the wholly aromatic monomer containing the imide group is as follows:
Figure 730139DEST_PATH_IMAGE005
ar is a wholly aromatic radical, R3、R4Are end groups.
The invention also discloses an application of the thermosetting wholly aromatic polyester imide liquid crystal film in preparation of a polymer film.
The invention also discloses application of the thermosetting wholly aromatic polyester imide liquid crystal precursor solution in preparation of thermosetting wholly aromatic polyester imide liquid crystals or application in preparation of polymer liquid crystal materials.
The invention also discloses application of the thermosetting wholly aromatic polyester imide liquid crystal in preparation of a polymer liquid crystal material.
Compared with the prior art, the invention has the beneficial effects that:
1. different from the method for preparing the thermosetting polyesterimide liquid crystal by a melt polymerization method at a high temperature (250-320 ℃), the method for preparing the thermosetting polyesterimide liquid crystal by the solution method at a temperature of 100-150 ℃, so that the raw material selection range can be expanded, for example, the active end groups of 3-aminophenylacetylene, maleic anhydride and 5- (phenylethynyl) isobenzofuran-1, 3-dione which cannot be used in the prior art can be used for obtaining products with excellent performance.
2. Different from the traditional solution polymerization method for preparing the thermosetting polyester imide liquid crystal, the method takes the imide aromatic monomer as a reaction initiator, so that the imide cyclization reaction of polyamic acid does not need to occur at high temperature (250-320 ℃).
3. Different from the thermosetting wholly aromatic polyester imide liquid crystal prepared by a melting method, the thermosetting wholly aromatic polyester imide liquid crystal prepared by a solution polymerization method has lower melting point and better processability while obtaining high glass transition temperature and high thermal stability.
Drawings
FIG. 1 nuclear magnetic resonance carbon spectrum of wholly aromatic polyesterimide liquid crystal oligomer powder provided in example 1 and example 2 ((C))13C-NMR）；
FIG. 2 is a Gel Permeation Chromatogram (GPC) of a wholly aromatic polyesterimide liquid crystal oligomer powder provided in example 1 and example 2;
FIG. 3 is a Differential Scanning Calorimetry (DSC) curve obtained by heating the wholly aromatic polyesterimide liquid crystal oligomer powder provided in examples 1 and 2 and the wholly aromatic polyesterimide liquid crystal oligomer powder provided in comparative example 1 at a temperature increase rate of 20 ℃/min in a nitrogen atmosphere;
FIG. 4 is a Differential Scanning Calorimetry (DSC) curve obtained by curing the wholly aromatic polyesterimide liquid crystal oligomer powders provided in examples 1 and 2 and the wholly aromatic polyesterimide liquid crystal oligomer powder provided in comparative example 1;
FIG. 5 is a polarization microscopic (POM) photograph of the wholly aromatic polyesterimide liquid crystal oligomer powder provided in example 1 and the wholly aromatic polyesterimide liquid crystal oligomer powder provided in comparative example 1;
FIG. 6 is a graph showing the Rheology (Rheology) of the wholly aromatic polyesterimide liquid crystal oligomer powder provided in example 1 and the wholly aromatic polyesterimide liquid crystal oligomer powder provided in comparative example 1;
FIG. 7 is a thermogram of weight loss (TG) -temperature of the thermosetting wholly aromatic polyester imide liquid crystal films provided in examples 1 and 2 and the thermosetting wholly aromatic polyester imide liquid crystal film provided in comparative example 1 measured at a temperature increase rate of 10 ℃/min under a nitrogen atmosphere;
FIG. 8 is a graph showing a loss factor (Tan. delta.) versus temperature curve of the thermosetting wholly aromatic polyesterimide liquid crystal films provided in examples 1 and 2 and the thermosetting wholly aromatic polyesterimide liquid crystal film provided in comparative example 1;
FIG. 9 is a photograph showing that the thermosetting wholly aromatic polyester imide liquid crystal powders provided in examples 1 and 2 and the thermosetting wholly aromatic polyester imide liquid crystal powder provided in comparative example 1 were added to a mixed solvent of chloroform and pentafluorophenol (volume ratio: 1).
Detailed Description
The technical solution of the present invention will be further described with reference to the accompanying drawings, examples and comparative examples.
Example 1
(1) Preparation of wholly aromatic polyester imide liquid crystal oligomer
In a 1L single-neck flask, 114.50g of diphenyl chlorophosphate, 13.30g of anhydrous lithium chloride and 660mL of pyridine were charged, and the mixture was stirred at 25 ℃ for 30min to obtain clear solution A. In a 1.5L three-necked flask, 23.48g of p-hydroxybenzoic acid, 16.94g of 6-hydroxy-2-naphthoic acid, 20.77g N- (3' -hydroxyphenyl) trimellitimide, 1.33g of 3-aminophenylacetylene, 3.33g of 2- (3-ethynylphenyl) -1, 3-dioxoisoindoline-5-carboxylic acid and 330mL of pyridine were charged, and preheated at 120 ℃ for 5 minutes under nitrogen protection to obtain clear solution B. The flask was equipped with a reflux condenser, a thermometer, and a nitrogen inlet tube. Dripping the solution A into the solution B for 60 min; a nitrogen stream was passed through and the mixture was refluxed for 3h at 120 ℃. The final reaction solution was directly poured into a beaker containing 200mL of methanol and filtered to obtain the reaction product. Then, cleaning the mixture by using hot water and methanol, drying the mixture for 24 hours at the temperature of 100 ℃, and grinding the mixture to obtain fine powder, namely the wholly aromatic polyester imide liquid crystal oligomer; the carbon spectrum, gel permeation chromatography, polarization micrograph, differential scanning calorimetry curve, rheogram and solubility of the compound are shown in the attached figures 1, 2, 3, 4, 5, 6 and 9.
(2) Preparation of thermosetting wholly aromatic polyester imide liquid crystal film
And (2) spreading the wholly aromatic polyester imide liquid crystal oligomer powder obtained in the step (1) in a mould, placing in a flat vulcanizing machine at 250 ℃ for pressure maintaining (2 bar) for 15min, naturally cooling to 30 ℃, and demoulding. Curing according to the process of 200 ℃/1h +230 ℃/1h +270 ℃/1h +300 ℃/1h to obtain a thermosetting wholly aromatic polyester imide liquid crystal film; the thermal weight loss-temperature curve and the loss factor (Tan delta) -temperature curve are shown in the attached figures 7 and 8.
Example 2
(1) Preparation of wholly aromatic polyester imide liquid crystal oligomer
In a 1L single-neck flask, 114.50g of diphenyl chlorophosphate, 13.30g of anhydrous lithium chloride and 660mL of pyridine were charged, and the mixture was stirred at 25 ℃ for 30min to obtain clear solution A. 13.30g of p-hydroxybenzoic acid, 16.94g of 6-hydroxy-2-naphthoic acid, 20.77g N- (3' -hydroxyphenyl) trimellitimide, 3.99g of 3-aminophenylacetylene, 1.60g of 2- (3-ethynylphenyl) -1, 3-dioxoisoindoline-5-carboxylic acid and 330mL of pyridine were placed in a 1.5L three-necked flask, and preheated at 120 ℃ for 5 minutes under nitrogen protection to obtain clear solution B. The flask was equipped with a reflux condenser, a thermometer, and a nitrogen inlet tube. Dripping the solution A into the solution B for 30 min; a moderate nitrogen flow was passed and the reflux was condensed at 120 ℃ for 3 h. The final reaction solution was poured directly into 200mL of methanol to obtain a powder. Then, cleaning with hot water, drying at 110 ℃ for 24h, and grinding to obtain fine powder, namely the wholly aromatic polyester imide liquid crystal oligomer; the carbon spectrum, gel permeation chromatography, differential scanning calorimetry curve and solubility of the compound are shown in the attached figures 1, 2, 3, 4 and 9.
(2) Preparation of thermosetting wholly aromatic polyester imide liquid crystal film
Spreading the obtained wholly aromatic polyester imide liquid crystal oligomer powder in a mould, placing the mould in a flat vulcanizing machine at 250 ℃ for pressure maintaining (2 bar) for 15min, naturally cooling to 30 ℃, demoulding, and obtaining a thermosetting wholly aromatic polyester imide liquid crystal film through a multi-step curing process of 200 ℃/1h +230 ℃/1h +270 ℃/1h +300 ℃/1 h; the thermal weight loss-temperature curve and the loss factor (Tan delta) -temperature curve are shown in the attached figures 7 and 8.
Referring to the attached figure 1, it is the nuclear magnetic resonance carbon spectrum of the wholly aromatic polyesterimide liquid crystal oligomer prepared in example 1 and example 2 of the present invention. The spectrum shows the signal of the carbon atom (81 ppm) on the active end group phenylacetylene and the signal of the carbon atom (112-138 ppm) on the benzene ring, which indicates that the active end group phenylacetylene is successfully introduced into the molecular chain of the embodiment 1 and the embodiment 2.
Referring to FIG. 2, it is a Gel Permeation Chromatogram (GPC) of the wholly aromatic polyesterimide liquid crystal oligomer prepared in example 1 and example 2 of the present invention. It can be seen that the wholly aromatic polyesterimide liquid crystal oligomers prepared in example 1 and example 2 had molecular weights of 5195 and 4925, respectively, and PDI of 2.43 and 2.50, respectively, which were consistent with the expected value (5000). It is worth to say that the molecular weight of the aromatic polyester polymer prepared by the existing melt polycondensation method is generally higher, the polymer is generally known to have poor solubility, and is not only difficult to dissolve in common solvents, but also difficult to dissolve even if fresh solvents such as pentafluorophenol, hexafluoroisopropanol or a mixed solvent of the pentafluorophenol and the hexafluoroisopropanol are adopted (see the documents: H Kricheldorf; V Linzer; C Bruhn. Eur. J., 1994, 30: 549-.
Example 3
(1) Preparation of wholly aromatic polyester imide liquid crystal oligomer
A150 mL single-neck flask was charged with diphenyl chlorophosphate 8.6g, anhydrous lithium chloride 1.47g, and methyl pyrrolidone 100mL, and stirred at 10 ℃ for 45min to obtain clear solution A.
A500 mL three-necked flask was charged with 1.76g of 3-hydroxybenzoic acid, 1.27g of 6-hydroxy-2-naphthoic acid, 1.55g of 1.55g N- (3' -hydroxyphenyl) trimellitimide, 0.10g of 3-aminophenylacetylene, 0.25g of 2- (3-ethynylphenyl) -1, 3-dioxoisoindoline-5-carboxylic acid, and 45mL of methylpyrrolidone, and preheated at 150 ℃ for 5min under nitrogen protection to obtain a clear solution B. The flask was equipped with a reflux condenser, a thermometer, and a nitrogen inlet tube. Dripping the solution A into the solution B for 45 min; a moderate nitrogen flow was passed and the reflux was condensed at 150 ℃ for 2 h. The final reaction solution was poured directly into 200mL of ethyl acetate to obtain a powder. And then, cleaning with hot water, drying at 110 ℃ for 24h, and grinding to obtain fine powder, namely the wholly aromatic polyester imide liquid crystal oligomer.
(2) Preparation of thermosetting wholly aromatic polyester imide liquid crystal film
Spreading the obtained wholly aromatic polyester imide liquid crystal powder in a mould, placing in a flat vulcanizing machine at 245 ℃ for 30min under pressure (2 bar), naturally cooling to 30 ℃, demoulding, and performing a multi-step curing process: 200 ℃/2h +230 ℃/2h +270 ℃/2h +300 ℃/2h to obtain the thermosetting wholly aromatic polyester imide liquid crystal film.
Example 4
(1) Preparation of wholly aromatic polyester imide liquid crystal oligomer
In a 100mL single-neck flask, 9.93g triphenyl phosphite, 1.27g anhydrous lithium chloride, and 70mL N, N-dimethylacetamide were added, and stirred at 40 ℃ for 30min to obtain clear solution A.
In a 250mL three-necked flask, 2.57g of 4' -hydroxy- [1,1' -biphenyl ] -4-carboxylic acid, 1.27g of 6-hydroxy-2-naphthoic acid, 1.56g N- (3 ' -hydroxyphenyl) trimellitimide, 0.1g of 3-aminophenylacetylene, 0.25g of 2- (3-ethynylphenyl) -1, 3-dioxoisoindoline-5-carboxylic acid and 30mL of N, N-dimethylacetamide were charged and preheated at 100 ℃ for 10min under nitrogen protection to obtain clear solution B. The flask was equipped with a reflux condenser, a thermometer, and a nitrogen inlet tube. Dripping the solution A into the solution B for 30 min; a moderate nitrogen flow was passed and the reflux was condensed at 100 ℃ for 6 h. The final reaction solution was poured directly into 200mL of methanol to obtain a powder. And then, cleaning with hot water, drying at 100 ℃ for 24h, and grinding to obtain fine powder, namely the wholly aromatic polyester imide liquid crystal oligomer.
(2) Preparation of thermosetting wholly aromatic polyester imide liquid crystal film
Spreading the obtained wholly aromatic polyester imide liquid crystal powder in a mould, placing in a flat vulcanizing press at 235 ℃ for pressure maintaining (2 bar) for 15min, naturally cooling to 30 ℃, demoulding, and curing in multiple steps: 200 ℃/1h +240 ℃/1h +270 ℃/1h +300 ℃/1h to obtain the thermosetting wholly aromatic polyester imide liquid crystal film.
Example 5
(1) Preparation of wholly aromatic polyester imide liquid crystal oligomer
In a 100mL single-neck flask, 8.6g of diphenyl chlorophosphate, 14.13g of zinc chloride and 60mL of N, N-dimethylacetamide were added, and the mixture was stirred at 30 ℃ for 35min to obtain a clear solution A.
In a 250mL three-necked flask, 1.95g naphthalene-2, 7-dicarboxylic acid, 1.08g naphthalene-2, 6-diol, 3.08g2- (6-hydroxynaphthalen-2-yl) -1, 3-dioxoisoindoline-5-carboxylic acid, 0.37g 3-aminophenylacetylene, 1.17g 4- (1, 3-dioxo-5- (phenylethynyl) isoindolin-2-yl) benzoic acid, and 25mL N, N-dimethylacetamide were charged and preheated at 110 ℃ for 5min under nitrogen to obtain clear solution B. The flask was equipped with a reflux condenser, a thermometer, and a nitrogen inlet tube. Dripping the solution A into the solution B for 60 min; a moderate nitrogen flow was passed and the reflux was condensed at 110 ℃ for 4 h. The final reaction solution was poured directly into 200mL of diethyl ether to obtain a powder. And then, cleaning with hot water, drying at 110 ℃ for 24h, and grinding to obtain fine powder, namely the wholly aromatic polyester imide liquid crystal oligomer.
(2) Preparation of thermosetting wholly aromatic polyester imide liquid crystal film
Spreading the obtained wholly aromatic polyester imide liquid crystal oligomer powder in a mould, placing in a flat-plate vulcanizing instrument at 190 ℃ for pressure maintaining (2 bar) for 45min, naturally cooling to 30 ℃, demoulding, and curing in multiple steps: 230 ℃/2h +270 ℃/2h +300 ℃/2h to obtain the thermosetting wholly aromatic polyester imide liquid crystal film.
Example 6
(1) Preparation of wholly aromatic polyester imide liquid crystal oligomer
In a 150mL single-neck flask, 10g of diphenyl chlorophosphate, 23g of diphenyl chlorophosphate, 7.06g of zinc chloride, 3.87g of calcium chloride, 75mL of methylpyrrolidone, and 25mL of N, N-dimethylacetamide were added, and the mixture was stirred at 25 ℃ for 30min to obtain a clear solution A.
In a 500mL three-necked flask, 1.73g of p-hydroxybenzoic acid, 3.54g of 3.54g N- (3' -hydroxyphenyl) trimellitimide, 0.57g of 2- (6-hydroxynaphthalen-2-yl) -1, 3-dioxoisoindoline-5-carboxylic acid, 0.45g of 2- (3-ethynylphenyl) -1, 3-dioxoisoindoline-5-carboxylic acid, and 15mL of N, N-dimethylacetamide were added, and the mixture was preheated at 120 ℃ for 5min under nitrogen protection to obtain clear solution B. The flask was equipped with a reflux condenser, a thermometer, and a nitrogen inlet tube. Dripping the solution A into the solution B for 40 min; a moderate nitrogen flow was passed and the reflux was condensed at 120 ℃ for 3 h. The final reaction solution was poured directly into 200mL of methanol to obtain a powder. And then, cleaning with hot water, drying at 110 ℃ for 24h, and grinding to obtain fine powder, namely the wholly aromatic polyester imide liquid crystal oligomer.
(2) Preparation of thermosetting wholly aromatic polyester imide liquid crystal film
Spreading the obtained wholly aromatic polyester imide liquid crystal oligomer powder in a mould, placing in a flat-plate vulcanizing instrument at 300 ℃ for 30min for pressure maintaining (2 bar), naturally cooling to 30 ℃, demoulding, and curing in multiple steps: 230 ℃/2h +270 ℃/2h +300 ℃/2h +330 ℃/2h +370 ℃/2h to obtain the thermosetting wholly aromatic polyester imide liquid crystal film.
Example 7
(1) Preparation of wholly aromatic polyester imide liquid crystal oligomer
In a 150mL single-neck flask, 9.93g triphenyl phosphite, 5.35g anhydrous lithium chloride, 80mL pyridine, 25mL N, N-dimethylacetamide and stirred at 40 ℃ for 30min to obtain clear solution A.
In a 250mL three-necked flask, 1.0g of p-hydroxybenzoic acid, 1.45g of 4' -hydroxy- [1,1' -biphenyl ] -4-carboxylic acid, 2.05g N- (3 ' -hydroxyphenyl) trimellitimide, 0.32g of 2- (3-ethynylphenyl) -5-hydroxyiso-1, 3-dione, 0.35g of 2- (3-ethynylphenyl) -1, 3-dioxoisoindoline-5-carboxylic acid and 20mL of N, N-dimethylacetamide were added, and the mixture was preheated at 100 ℃ for 5min under nitrogen protection to obtain a clear solution B. The flask was equipped with a reflux condenser, a thermometer, and a nitrogen inlet tube. Dripping the solution A into the solution B for 35 min; a moderate nitrogen flow was passed and the reflux was condensed at 100 ℃ for 6 h. The final reaction solution was poured directly into 200mL of methanol to obtain a powder. And then, cleaning with hot water, drying at 100 ℃ for 24h, and grinding to obtain fine powder, namely the wholly aromatic polyester imide liquid crystal oligomer.
(2) Preparation of thermosetting wholly aromatic polyester imide liquid crystal film
Spreading the obtained wholly aromatic polyester imide liquid crystal oligomer powder in a mould, placing in a flat-plate vulcanizing instrument at 310 ℃ for pressure maintaining (2 bar) for 45min, naturally cooling to 30 ℃, demoulding, and curing in multiple steps: 270 ℃/1.5h +300 ℃/1.5h +330 ℃/1.5h +370 ℃/1.5h to obtain the thermosetting wholly aromatic polyester imide liquid crystal film.
Example 8
(1) Preparation of wholly aromatic polyester imide liquid crystal oligomer
In a 150mL single-neck flask, 6.7g of diphenyl chlorophosphate, 7.2g of tris (4-chlorophenyl) phosphite, 2.94g of calcium chloride, 2.65g of anhydrous lithium chloride, and 70mL of N, N-dimethylacetamide were added, and the mixture was stirred at 25 ℃ for 30min to obtain a clear solution A.
In a 250mL three-necked flask, 1.72g of cyclopentane-3, 5-diene-1, 3-diol, 2.12g N- (3' -hydroxyphenyl) trimellitimide, 0.88g of 2- (3-ethynylphenyl) -5-hydroxyiso-1, 3-dione, 0.97g of 2- (3-ethynylphenyl) -1, 3-dioxoisoindoline-5-carboxylic acid and 30mL of N, N-dimethylacetamide were charged and preheated at 120 ℃ for 5min under nitrogen protection to obtain clear solution B. The flask was equipped with a reflux condenser, a thermometer, and a nitrogen inlet tube. Dripping the solution A into the solution B for 60 min; a moderate nitrogen flow was passed and the reflux was condensed at 120 ℃ for 3.5 h. The final reaction solution was poured directly into 200mL of methanol to obtain a powder. And then, cleaning with hydrochloric acid, drying at 110 ℃ for 24h, and grinding to obtain fine powder, namely the wholly aromatic polyester imide liquid crystal oligomer.
(2) Preparation of thermosetting wholly aromatic polyester imide liquid crystal film
Spreading the obtained wholly aromatic polyester imide liquid crystal oligomer powder in a mould, placing in a flat-plate vulcanizing instrument at 300 ℃ for pressure maintaining (2 bar) for 60min, naturally cooling to 30 ℃, demoulding, and performing multi-step solidification: 200 ℃/1h +230 ℃/1h +270 ℃/1h +300 ℃/1h +330 ℃/1h +370 ℃/1h to obtain the thermosetting wholly aromatic polyester imide liquid crystal film.
Example 9
(1) Preparation of wholly aromatic polyester imide liquid crystal oligomer
In a 100mL single-neck flask, 8.6g of diphenyl hydrogenphosphite, 0.73g of magnesium chloride and 50mL of methylpyrrolidone were added, and the mixture was stirred at 25 ℃ for 45min to obtain a clear solution A.
In a 250mL three-necked flask, 1.73g of p-hydroxybenzoic acid, 3.54g of 3.54g N- (3' -hydroxyphenyl) trimellitimide, 0.57g of 2- (6-hydroxynaphthalen-2-yl) -1, 3-dioxoisoindoline-5-carboxylic acid, 0.45g of 2- (3-ethynylphenyl) -1, 3-dioxoisoindoline-5-carboxylic acid, and 15mL of methylpyrrolidone were charged and preheated at 150 ℃ for 5min under nitrogen protection to obtain clear solution B. The flask was equipped with a reflux condenser, a thermometer, and a nitrogen inlet tube. Dripping the solution A into the solution B for 35 min; a moderate nitrogen flow was passed and the reflux was condensed at 140 ℃ for 2.5 h. The final reaction solution was poured directly into 200mL of methanol to obtain a powder. And then, cleaning with hot water, drying at 110 ℃ for 24h, and grinding to obtain fine powder, namely the wholly aromatic polyester imide liquid crystal oligomer.
(2) Preparation of thermosetting wholly aromatic polyester imide liquid crystal film
Spreading the obtained wholly aromatic polyester imide liquid crystal oligomer powder in a mould, placing in a flat-plate vulcanizing instrument at 250 ℃ for pressure maintaining (2 bar) for 15min, naturally cooling to 30 ℃, demoulding, and curing in multiple steps: 200 ℃/1h +230 ℃/1h +270 ℃/1h +300 ℃/1h +330 ℃/1h +370 ℃/1h to obtain the thermosetting wholly aromatic polyester imide liquid crystal film.
Example 10
(1) Preparation of wholly aromatic polyester imide liquid crystal oligomer
In a 100mL single-neck flask, 8.6g of tris (4-chlorophenyl) phosphite, 2.63g of anhydrous lithium chloride, and 50mL of pyridine were added, and the mixture was stirred at 25 ℃ for 30min to obtain clear solution A.
In a 250mL three-necked flask, 1.76g of p-hydroxybenzoic acid, 1.27g of 6-hydroxy-2-naphthoic acid, 1.56g N- (3' -hydroxyphenyl) trimellitimide, 0.10g of 3-aminophenylacetylene, 0.25g of (3-ethynylphenyl) -1, 3-dioxoisoindoline-5-carboxylic acid and 25mL of pyridine were charged, and the mixture was preheated at 120 ℃ for 5 minutes under nitrogen protection to obtain a clear solution B. The flask was equipped with a reflux condenser, a thermometer, and a nitrogen inlet tube. Dripping the solution A into the solution B for 30 min; a moderate nitrogen flow was passed and the reflux was condensed at 130 ℃ for 5 h. The final reaction solution was directly poured into a beaker containing 200mL of methanol and filtered to obtain the reaction product. And then, cleaning the mixture by using hot water and methanol, drying the mixture for 24 hours at the temperature of 100 ℃, and grinding the mixture to obtain fine powder, namely the wholly aromatic polyester imide liquid crystal oligomer.
(2) Preparation of thermosetting wholly aromatic polyester imide liquid crystal film
Spreading the obtained wholly aromatic polyester imide liquid crystal oligomer powder in a mould, placing in a flat-plate vulcanizing instrument at 240 ℃ for pressure maintaining (2 bar) for 15min, naturally cooling to 30 ℃, demoulding, and performing a multi-step curing process: 220 ℃/2h +240 ℃/2h +280 ℃/2h +300 ℃/2h to obtain the thermosetting wholly aromatic polyester imide liquid crystal film.
Example 11
(1) Preparation of wholly aromatic polyester imide liquid crystal oligomer
In a 150mL single-neck flask, 33.6g of diphenyl chlorophosphate, 1.76g of anhydrous lithium chloride and 100mL of N, N-dimethylacetamide were added, and the mixture was stirred at 25 ℃ for 30min to obtain a clear solution A.
In a 250mL three-necked flask, 8.98g of 4'- (5-hydroxy-1, 3-dioxoisoindolin-2-yl) - [1,1' -biphenyl ] -4-carboxylic acid, 1.14g of 4- (2, 5-dioxo-2, 5-dihydro-1H-pyrrol-1-yl) benzoic acid, 1.0g of 2-1- (4-hydroxyphenyl) -1H-pyrrole-2, 5-dione, and 25mL of N, N-dimethylacetamide were added, and the mixture was preheated at 150 ℃ for 5min under nitrogen protection to obtain clear solution B. The flask was equipped with a reflux condenser, a thermometer, and a nitrogen inlet tube. Dripping the solution A into the solution B for 55 min; a moderate nitrogen flow was passed and the reflux was condensed at 150 ℃ for 3 h. The final reaction solution was directly poured into a beaker containing 200mL of methanol and filtered to obtain the reaction product. And then, cleaning the mixture by using hot water and methanol, drying the mixture for 24 hours at the temperature of 100 ℃, and grinding the mixture to obtain fine powder, namely the wholly aromatic polyester imide liquid crystal oligomer.
(2) Preparation of thermosetting wholly aromatic polyester imide liquid crystal film
And (2) spreading the wholly aromatic polyester imide liquid crystal oligomer powder obtained in the step (1) in a mould, placing in a plate vulcanizing instrument at 230 ℃ for pressure maintaining (2 bar) for 15min, naturally cooling to 30 ℃, and demoulding. Curing according to the process of 200 ℃/2h +230 ℃/2h +270 ℃/2h +300 ℃/2h to obtain the thermosetting wholly aromatic polyester imide liquid crystal film.
Example 12
(1) Preparation of wholly aromatic polyester imide liquid crystal oligomer
In a 150mL single-neck flask, 8.6g triphenyl phosphite, 5.24g anhydrous lithium chloride, 50mL N, N-dimethylacetamide, and 50mL methyl pyrrolidone were added, and stirred at 25 ℃ for 30min to obtain clear solution A.
In a 250mL three-necked flask, 0.55g of hydroquinone, 1.08g of naphthalene-2, 6-dicarboxylic acid, 1.61g of 3 '-hydroxy- [1,1' -biphenyl ] -4-carboxylic acid, 2.50g of 6- (5-hydroxy-1, 3-dioxoisoindolin-2-yl) -2-naphthoic acid and 0.23g of 2- (3-ethynylphenyl) -1, 3-dioxoisoindoline-5-carboxylic acid, 0.20g of 2- (3-ethynylphenyl) -5-hydroxyiso-1, 3-dione and 50mL of methylpyrrolidone were charged and preheated at 130 ℃ for 7min under nitrogen protection to obtain clear solution B. The flask was equipped with a reflux condenser, a thermometer, and a nitrogen inlet tube. Dripping the solution A into the solution B for 50 min; a moderate nitrogen flow was passed and the reflux was condensed at 130 ℃ for 5 h. The final reaction solution was directly poured into a beaker containing 200mL of methanol and filtered to obtain the reaction product. And then, cleaning the mixture by using hot water, petroleum ether, ethyl acetate and methanol, drying the mixture for 24 hours at the temperature of 100 ℃, and grinding the mixture to obtain fine powder, namely the wholly aromatic polyester imide liquid crystal oligomer.
(2) Preparation of thermosetting wholly aromatic polyester imide liquid crystal film
And (2) spreading the wholly aromatic polyester imide liquid crystal oligomer powder obtained in the step (1) in a mould, placing in a flat vulcanizing machine at 250 ℃ for pressure maintaining (2 bar) for 15min, naturally cooling to 30 ℃, and demoulding. Curing according to the process of 200 ℃/3h +230 ℃/3h +270 ℃/3h +300 ℃/3h to obtain the thermosetting wholly aromatic polyester imide liquid crystal film.
Example 13
(1) Preparation of wholly aromatic polyester imide liquid crystal oligomer
In a 100mL single-neck flask, 8.6g of diphenyl chlorophosphate, 2.36g of anhydrous zinc chloride and 50mL of N, N-dimethylacetamide were added, and the mixture was stirred at 25 ℃ for 30min to obtain clear solution A.
In a 250mL three-necked flask, 1.35g naphthalene-1, 7-dicarboxylic acid, 1.0g naphthalene-1, 7-diol, 3.54g2- (4-hydroxyphenyl) -1, 3-dioxoisoindoline-5-carboxylic acid, 0.66g 2- (4-hydroxyphenyl) -5- (phenylethynyl) isoindoline-1, 3-dione, 0.72g 4- (1, 3-dioxo-5- (phenylethynyl) isoindolin-2-yl) benzoic acid, and 25mL N, N-dimethylacetamide were charged and preheated at 110 ℃ for 5min under nitrogen protection to obtain clear solution B. The flask was equipped with a reflux condenser, a thermometer, and a nitrogen inlet tube. Dripping the solution A into the solution B for 30 min; a moderate nitrogen flow was passed and the reflux was condensed at 110 ℃ for 5.5 h. The final reaction solution was directly poured into a beaker containing 200mL of methanol and filtered to obtain the reaction product. And then, cleaning the mixture by using hot water, methanol and petroleum ether, drying the mixture for 24 hours at the temperature of 100 ℃, and grinding the mixture to obtain fine powder, namely the wholly aromatic polyester imide liquid crystal oligomer.
(2) Preparation of thermosetting wholly aromatic polyester imide liquid crystal film
And (2) spreading the wholly aromatic polyester imide liquid crystal oligomer powder obtained in the step (1) in a mould, placing in a flat vulcanizing machine at 250 ℃ for pressure maintaining (2 bar) for 15min, naturally cooling to 30 ℃, and demoulding. The thermosetting wholly aromatic polyester imide liquid crystal film is obtained by the curing process of 220 ℃/1h +240 ℃/1h +280 ℃/1h +320 ℃/1h +350 ℃/1h +370 ℃/1 h.
Example 14
(1) Preparation of wholly aromatic polyester imide liquid crystal oligomer
A clear solution A was obtained by placing 8.6g of diphenyl chlorophosphate, 1.46g of anhydrous lithium chloride and 50mL of pyridine in a 100mL single-neck flask and stirring at 25 ℃ for 30 min.
Into a 250mL three-necked flask, 0.62g of isophthalic acid, 0.70g of [1,1 '-biphenyl ] -2,4' -diol, 1.40g of naphthalene-1, 7-diol, 2.72g of 2- (3-carboxyphenyl) -1, 3-dioxoisoindoline-5-carboxylic acid, 0.16g of 3-aminophenylacetylene, 0.29g of 4- (2, 5-dioxo-2, 5-dihydro-1H-pyrrol-1-yl) benzoic acid and 25mL of pyridine were charged and preheated at 140 ℃ for 8min under nitrogen protection to obtain clear solution B. The flask was equipped with a reflux condenser, a thermometer, and a nitrogen inlet tube. Dripping the solution A into the solution B for 60 min; a moderate nitrogen flow was passed and the reflux was condensed at 140 ℃ for 4 h. The final reaction solution was directly poured into a beaker containing 200mL of methanol and filtered to obtain the reaction product. And then, cleaning the mixture by using hot water and methanol, drying the mixture for 24 hours at the temperature of 100 ℃, and grinding the mixture to obtain fine powder, namely the wholly aromatic polyester imide liquid crystal oligomer.
(2) Preparation of thermosetting wholly aromatic polyester imide liquid crystal film
And (2) spreading the wholly aromatic polyester imide liquid crystal oligomer powder obtained in the step (1) in a mould, placing in a plate vulcanizing instrument at 230 ℃ for pressure maintaining (2 bar) for 15min, naturally cooling to 30 ℃, and demoulding. Curing according to the process of 200 ℃/1h +230 ℃/1h +270 ℃/1h +300 ℃/1h to obtain the thermosetting wholly aromatic polyester imide liquid crystal film.
Example 15
(1) Preparation of wholly aromatic polyester imide liquid crystal oligomer
In a 100mL single-neck flask, 8.6g of diphenyl chlorophosphate, 8.35g of anhydrous calcium chloride, and 40mL of methylpyrrolidone were added, and the mixture was stirred at 25 ℃ for 30min to obtain a clear solution A.
In a 250mL three-necked flask, 2.33g of [1,1 '-biphenyl ] -2,4' -diol, 4.84g of 2- (4 '-carboxy- [1,1' -biphenyl ] -4-yl) -1, 3-dioxoisoindoline-5-carboxylic acid, 0.29g of 3-aminophenylacetylene, 0.71g of 2- (3-ethynylphenyl) -1, 3-dioxoisoindoline-5-carboxylic acid and 50mL of methylpyrrolidone were charged, and preheated at 100 ℃ for 5min under nitrogen protection to obtain clear solution B. The flask was equipped with a reflux condenser, a thermometer, and a nitrogen inlet tube. Dripping the solution A into the solution B for 45 min; a moderate nitrogen flow was passed and the reflux was condensed at 100 ℃ for 2 h. The final reaction solution was directly poured into a beaker containing 200mL of methanol and filtered to obtain the reaction product. And then, cleaning the mixture by using hot water and methanol, drying the mixture for 24 hours at the temperature of 100 ℃, and grinding the mixture to obtain fine powder, namely the wholly aromatic polyester imide liquid crystal oligomer.
(2) Preparation of thermosetting wholly aromatic polyester imide liquid crystal film
And (2) spreading the wholly aromatic polyester imide liquid crystal oligomer powder obtained in the step (1) in a mould, placing the mould in a flat vulcanizing machine at 245 ℃, maintaining the pressure (2 bar) for 15min, naturally cooling to 30 ℃, and demoulding. Curing according to the process of 195 ℃/1h +225 ℃/1h +265 ℃/1h +315 ℃/1h to obtain the thermosetting wholly aromatic polyester imide liquid crystal film.
Example 16
(1) Preparation of wholly aromatic polyester imide liquid crystal oligomer
In a 100mL single-neck flask, 9.7g of tris (4-chlorophenyl) phosphite, 3.33g of anhydrous zinc chloride, and 50mL of N, N-dimethylacetamide were added, and the mixture was stirred at 25 ℃ for 30min to obtain clear solution A.
In a 250mL three-necked flask, 1.07g of 3 '-hydroxy- [1,1' -biphenyl ] -4-carboxylic acid, 0.69g of 2-hydroxybenzoic acid, 1.82g of [1,1 '-biphenyl ] -4,4' -dicarboxylic acid, 1.91g of 5-hydroxy-2- (3-hydroxyphenyl) isoindoline-1, 3-dione, 0.12g of 3-aminophenylacetylene, 0.39g of 4- (1, 3-dioxo-5- (phenylethynyl) isoindolin-2-yl) benzoic acid, and 25mL of N, N-dimethylacetamide and 25mL of pyridine were charged, and preheated at 150 ℃ for 6min under nitrogen protection to obtain a clear solution B. The flask was equipped with a reflux condenser, a thermometer, and a nitrogen inlet tube. Dripping the solution A into the solution B for 60 min; a moderate nitrogen flow was passed and the reflux was condensed at 150 ℃ for 2.5 h. The final reaction solution was directly poured into a beaker containing 200mL of methanol and filtered to obtain the reaction product. And then, cleaning the mixture by using hot water and methanol, drying the mixture for 24 hours at the temperature of 100 ℃, and grinding the mixture to obtain fine powder, namely the wholly aromatic polyester imide liquid crystal oligomer.
(2) Preparation of thermosetting wholly aromatic polyester imide liquid crystal film
And (2) spreading the wholly aromatic polyester imide liquid crystal oligomer powder obtained in the step (1) in a mould, placing in a flat vulcanizing machine at 240 ℃, maintaining the pressure (2 bar) for 15min, naturally cooling to 30 ℃, and demoulding. Curing at the speed of 200 ℃/1h +230 ℃/1h +270 ℃/1h +300 ℃/1h +330 ℃/1h +370 ℃/1h to obtain the thermosetting wholly aromatic polyester imide liquid crystal film.
Example 17
(1) Preparation of wholly aromatic polyester imide liquid crystal oligomer
In a 100mL single-neck flask, 8.6g of diphenyl chlorophosphate, 2.19g of anhydrous lithium chloride, 50mL of pyridine and 30mL of methylpyrrolidone were added, and the mixture was stirred at 25 ℃ for 30min to obtain clear solution A.
In a 250mL three-necked flask, 3.24g of naphthalene-1, 7-dicarboxylic acid, 0.55g of catechol, 1.66g of 5-hydroxy-2- (4 '-hydroxy- [1,1' -biphenyl ] -4-yl) isoindole-1, 3-dione, 0.23g of 4- (2, 5-dioxo-2, 5-dihydro-1H-pyrrol-1-yl) benzoic acid, 0.20g of 1- (4-hydroxyphenyl) -1H-pyrrole-2, 5-dione, and 15mL of methylpyrrolidone, 25mL of pyridine were charged and preheated at 100 ℃ for 10min under nitrogen protection to obtain clear solution B. The flask was equipped with a reflux condenser, a thermometer, and a nitrogen inlet tube. Dripping the solution A into the solution B for 30 min; a moderate nitrogen flow was passed and the reflux was condensed at 120 ℃ for 4.5 h. The final reaction solution was directly poured into a beaker containing 200mL of methanol and filtered to obtain the reaction product. And then, cleaning the mixture by using hot water, methanol and ethyl acetate, drying the mixture for 24 hours at the temperature of 100 ℃, and grinding the mixture to obtain fine powder, namely the wholly aromatic polyester imide liquid crystal oligomer.
(2) Preparation of thermosetting wholly aromatic polyester imide liquid crystal film
And (2) spreading the wholly aromatic polyester imide liquid crystal oligomer powder obtained in the step (1) in a mould, placing in a flat vulcanizing machine at 225 ℃ for pressure maintaining (2 bar) for 15min, naturally cooling to 30 ℃, and demoulding. Curing according to the process of 200 ℃/1h +230 ℃/1h +270 ℃/1h +300 ℃/1h to obtain the thermosetting wholly aromatic polyester imide liquid crystal film.
Example 18
(1) Preparation of wholly aromatic polyester imide liquid crystal oligomer
In a 100mL single-neck flask, 8.6g of diphenyl chlorophosphate, 0.99g of anhydrous lithium chloride and 50mL of N, N-dimethylacetamide were added, and the mixture was stirred at 25 ℃ for 30min to obtain clear solution A.
In a 250mL three-necked flask, 3.82g of 5-hydroxy-2- (6-hydroxynaphthalen-2-yl) isoindole-1, 3-dione, 4.52g of 2- (6-carboxynaphthalen-2-yl) -1, 3-dioxoisoindoline-5-carboxylic acid, 0.40g of 2- (3-ethynylphenyl) -1, 3-dioxoisoindoline-5-carboxylic acid, 0.36g of 2- (3-ethynylphenyl) -5-hydroxyiso-1, 3-dione, and 25mL of N, N-dimethylacetamide were added and preheated at 130 ℃ for 5min under nitrogen protection to obtain clear solution B. The flask was equipped with a reflux condenser, a thermometer, and a nitrogen inlet tube. Dripping the solution A into the solution B for 50 min; a moderate nitrogen flow was passed and the reflux was condensed at 130 ℃ for 5 h. The final reaction solution was directly poured into a beaker containing 200mL of methanol and filtered to obtain the reaction product. And then, cleaning the mixture by using hot water and methanol, drying the mixture for 24 hours at the temperature of 100 ℃, and grinding the mixture to obtain fine powder, namely the wholly aromatic polyester imide liquid crystal oligomer.
(2) Preparation of thermosetting wholly aromatic polyester imide liquid crystal film
And (2) spreading the wholly aromatic polyester imide liquid crystal oligomer powder obtained in the step (1) in a mould, placing in a 200 ℃ flat-plate vulcanizing instrument for pressure maintaining (2 bar) for 15min, naturally cooling to 30 ℃, and demoulding. Curing according to the process of 210 ℃/1h +240 ℃/1h +280 ℃/1h +290 ℃/1h +300 ℃/1h to obtain the thermosetting wholly aromatic polyester imide liquid crystal film.
Example 19
(1) Preparation of wholly aromatic polyester imide liquid crystal oligomer
In a 100mL single-neck flask, 8.6g of diphenyl chlorophosphate, 2.72g of anhydrous zinc chloride and 50mL of N, N-dimethylacetamide were added, and the mixture was stirred at 25 ℃ for 30min to obtain clear solution A.
In a 250mL three-necked flask, 1.04g of phthalic acid, 4.14g of 5-hydroxy-2- (4 '-hydroxy- [1,1' -biphenyl ] -4-yl) isoindole-1, 3-dione, 2.42g of 2- (4 '-carboxy- [1,1' -biphenyl ] -4-yl) -1, 3-dioxoisoindoline-5-carboxylic acid, 1.17g of 3-aminophenylacetylene, 2.91g of 2- (3-ethynylphenyl) -1, 3-dioxoisoindoline-5-carboxylic acid, and 35mL of N, N-dimethylacetamide were charged and preheated at 130 ℃ for 5min under nitrogen protection to obtain clear solution B. The flask was equipped with a reflux condenser, a thermometer, and a nitrogen inlet tube. Dripping the solution A into the solution B for 37 min; a moderate nitrogen flow was passed and the reflux was condensed at 130 ℃ for 4 h. The final reaction solution was directly poured into a beaker containing 200mL of methanol and filtered to obtain the reaction product. And then, cleaning the mixture by using hot water and methanol, drying the mixture for 24 hours at the temperature of 100 ℃, and grinding the mixture to obtain fine powder, namely the wholly aromatic polyester imide liquid crystal oligomer.
(2) Preparation of thermosetting wholly aromatic polyester imide liquid crystal film
And (2) spreading the wholly aromatic polyester imide liquid crystal oligomer powder obtained in the step (1) in a mould, placing in a flat vulcanizing machine at 220 ℃ for pressure maintaining (2 bar) for 15min, naturally cooling to 30 ℃, and demoulding. Curing according to the process of 200 ℃/1h +230 ℃/1h +270 ℃/1h +300 ℃/1h to obtain the thermosetting wholly aromatic polyester imide liquid crystal film.
Example 20
(1) Preparation of wholly aromatic polyester imide liquid crystal oligomer
A150 mL single-neck flask was charged with diphenyl chlorophosphate 8.6g, anhydrous lithium chloride 1.72g, pyridine 30mL and methylpyrrolidone 35mL, and stirred at 25 ℃ for 30min to obtain clear solution A.
Into a 250mL three-necked flask, 0.62g of isophthalic acid, 0.70g of [1,1 '-biphenyl ] -2,4' -diol, 1.40g of naphthalene-1, 7-diol, 2.72g of 2- (3-carboxyphenyl) -1, 3-dioxoisoindoline-5-carboxylic acid, 0.16g of 3-aminophenylacetylene, 0.29g of 4- (2, 5-dioxo-2, 5-dihydro-1H-pyrrol-1-yl) benzoic acid, 30mL of pyridine, 35mL of methylpyrrolidone were charged and preheated at 140 ℃ for 8min under nitrogen protection to give clear solution B. The flask was equipped with a reflux condenser, a thermometer, and a nitrogen inlet tube. Dripping the solution A into the solution B for 54 min; a moderate nitrogen flow was passed and the reflux was condensed at 140 ℃ for 5.5 h. The final reaction solution was directly poured into a beaker containing 200mL of methanol and filtered to obtain the reaction product. And then, cleaning the mixture by using hot water and methanol, drying the mixture for 24 hours at the temperature of 100 ℃, and grinding the mixture to obtain fine powder, namely the wholly aromatic polyester imide liquid crystal oligomer.
(2) Preparation of thermosetting wholly aromatic polyester imide liquid crystal film
And (2) spreading the wholly aromatic polyester imide liquid crystal oligomer powder obtained in the step (1) in a mould, placing in a flat vulcanizing machine at 240 ℃, maintaining the pressure (2 bar) for 15min, naturally cooling to 30 ℃, and demoulding. Curing according to the process of 210 ℃/2h +230 ℃/2h +270 ℃/2h +290 ℃/2h to obtain the thermosetting wholly aromatic polyester imide liquid crystal film.
Example 21
(1) Preparation of wholly aromatic polyester imide liquid crystal oligomer
In a 100mL single-neck flask, 8.6g of diphenyl chlorophosphate, 7.62g of zinc chloride, 60mL of N, N-dimethylacetamide, and 20mL of pyridine were added, and the mixture was stirred at 30 ℃ for 35min to obtain clear solution A.
In a 250mL three-necked flask, 1.95g naphthalene-2, 7-dicarboxylic acid, 1.08g naphthalene-2, 6-diol, 3.08g2- (6-hydroxynaphthalen-2-yl) -1, 3-dioxoisoindoline-5-carboxylic acid, 0.37g 3-aminophenylacetylene, 1.17g 4- (1, 3-dioxo-5- (phenylethynyl) isoindolin-2-yl) benzoic acid, and 25mL N, N-dimethylacetamide were charged and preheated at 110 ℃ for 5min under nitrogen to obtain clear solution B. The flask was equipped with a reflux condenser, a thermometer, and a nitrogen inlet tube. Dripping the solution A into the solution B for 46 min; a moderate nitrogen flow was passed and the reflux was condensed at 110 ℃ for 4.5 h. The final reaction solution was poured directly into 200mL of diethyl ether to obtain a powder. And then, cleaning with hot water, drying at 110 ℃ for 24h, and grinding to obtain fine powder, namely the wholly aromatic polyester imide liquid crystal oligomer.
(2) Preparation of thermosetting wholly aromatic polyester imide liquid crystal film
Spreading the obtained wholly aromatic polyester imide liquid crystal oligomer powder in a mould, placing in a plate vulcanizing instrument at 230 ℃ for pressure maintaining (2 bar) for 45min, naturally cooling to 30 ℃, demoulding, and curing in multiple steps: 200 ℃/1h +230 ℃/1h +260 ℃/1h +290 ℃/1h to obtain the thermosetting wholly aromatic polyester imide liquid crystal film.
Example 22
(1) Preparation of wholly aromatic polyester imide liquid crystal oligomer
In a 150mL single-neck flask, 10g of diphenyl chlorophosphate, 23g of diphenyl chlorophosphate, 14.83g of zinc chloride, 12.08g of calcium chloride, 50mL of methylpyrrolidone, 25mL of N, N-dimethylacetamide, and 10mL of pyridine were added, and the mixture was stirred at 25 ℃ for 30min to obtain clear solution A.
In a 500mL three-necked flask, 1.73g of p-hydroxybenzoic acid, 3.54g of 3.54g N- (3' -hydroxyphenyl) trimellitimide, 0.57g of 2- (6-hydroxynaphthalen-2-yl) -1, 3-dioxoisoindoline-5-carboxylic acid, 0.45g of 2- (3-ethynylphenyl) -1, 3-dioxoisoindoline-5-carboxylic acid, and 15mL of N, N-dimethylacetamide and 10mL of pyridine were added, and the mixture was preheated at 120 ℃ for 5min under nitrogen protection to obtain clear solution B. The flask was equipped with a reflux condenser, a thermometer, and a nitrogen inlet tube. Dripping the solution A into the solution B for 40 min; a moderate nitrogen flow was passed and the reflux was condensed at 120 ℃ for 5 h. The final reaction solution was poured directly into 200mL of methanol to obtain a powder. And then, cleaning with hot water, drying at 110 ℃ for 24h, and grinding to obtain fine powder, namely the wholly aromatic polyester imide liquid crystal oligomer.
(2) Preparation of thermosetting wholly aromatic polyester imide liquid crystal film
Spreading the obtained wholly aromatic polyester imide liquid crystal oligomer powder in a mould, placing in a flat-plate vulcanizing instrument at 250 ℃ for 30min under pressure (2 bar), naturally cooling to 30 ℃, demoulding, and curing in multiple steps: 210 ℃/1h +230 ℃/1h +270 ℃/1h +300 ℃/1h +330 ℃/1h +370 ℃/1h to obtain the thermosetting wholly aromatic polyester imide liquid crystal film.
Example 23
(1) Preparation of wholly aromatic polyester imide liquid crystal oligomer
In a 150mL single-neck flask, 9.93g triphenyl phosphite, 5.18g anhydrous lithium chloride, 80mL methyl pyrrolidone, 25mL N, N-dimethylacetamide and stirring at 40 ℃ for 30min were added to obtain clear solution A.
In a 250mL three-necked flask, 1.0g of p-hydroxybenzoic acid, 1.45g of 4' -hydroxy- [1,1' -biphenyl ] -4-carboxylic acid, 2.05g N- (3 ' -hydroxyphenyl) trimellitimide, 0.32g of 2- (3-ethynylphenyl) -5-hydroxyiso-1, 3-dione, 0.35g of 2- (3-ethynylphenyl) -1, 3-dioxoisoindoline-5-carboxylic acid and 20mL of N, N-dimethylacetamide were added, and the mixture was preheated at 100 ℃ for 5min under nitrogen protection to obtain a clear solution B. The flask was equipped with a reflux condenser, a thermometer, and a nitrogen inlet tube. Dripping the solution A into the solution B for 45 min; a moderate nitrogen flow was passed and the reflux was condensed at 100 ℃ for 6 h. The final reaction solution was poured directly into 200mL of methanol to obtain a powder. And then, cleaning with hot water, drying at 100 ℃ for 24h, and grinding to obtain fine powder, namely the wholly aromatic polyester imide liquid crystal oligomer.
(2) Preparation of thermosetting wholly aromatic polyester imide liquid crystal film
Spreading the obtained wholly aromatic polyester imide liquid crystal oligomer powder in a mould, placing in a flat-plate vulcanizing instrument at 250 ℃ for pressure maintaining (2 bar) for 45min, naturally cooling to 30 ℃, demoulding, and curing in multiple steps: 200 ℃/2h +230 ℃/2h +270 ℃/2h +300 ℃/2h +330 ℃/2h +370 ℃/2h to obtain the thermosetting wholly aromatic polyester imide liquid crystal film.
Example 24
(1) Preparation of wholly aromatic polyester imide liquid crystal oligomer
In a 150mL single-neck flask, 6.7g of diphenyl chlorophosphate, 7.2g of tris (4-chlorophenyl) phosphite, 3.41g of calcium chloride, 1.34g of anhydrous lithium chloride, and 70mL of pyridine were charged, and the mixture was stirred at 25 ℃ for 30min to obtain a clear solution A.
In a 250mL three-necked flask, 1.72g of cyclopentane-3, 5-diene-1, 3-diol, 2.12g N- (3' -hydroxyphenyl) trimellitimide, 0.88g of 2- (3-ethynylphenyl) -5-hydroxyiso-1, 3-dione, 0.97g of 2- (3-ethynylphenyl) -1, 3-dioxoisoindoline-5-carboxylic acid and 30mL of pyridine were added, and preheated at 145 ℃ for 5min under nitrogen protection to obtain clear solution B. The flask was equipped with a reflux condenser, a thermometer, and a nitrogen inlet tube. Dripping the solution A into the solution B for 60 min; a moderate nitrogen flow was passed and the reflux was condensed at 145 ℃ for 3 h. The final reaction solution was poured directly into 200mL of methanol to obtain a powder. And then, cleaning with hydrochloric acid, drying at 110 ℃ for 24h, and grinding to obtain fine powder, namely the wholly aromatic polyester imide liquid crystal oligomer.
(2) Preparation of thermosetting wholly aromatic polyester imide liquid crystal film
Spreading the obtained wholly aromatic polyester imide liquid crystal oligomer powder in a mould, placing in a plate vulcanizing instrument at 250 ℃ for pressure maintaining (2 bar) for 60min, naturally cooling to 30 ℃, demoulding, and performing multi-step solidification: 210 ℃/2h +230 ℃/2h +270 ℃/2h +300 ℃/2h +330 ℃/2h +370 ℃/2h to obtain the thermosetting wholly aromatic polyester imide liquid crystal film.
Comparative example 1
(1) Preparation of wholly aromatic polyester imide liquid crystal oligomer
In a 250mL four-necked round bottom flask, 23.48g of 4-hydroxybenzoic acid, 16.94g of 6-hydroxy-2-naphthoic acid, 20.77g of 20.77g N- (3' -hydroxyphenyl) trimellitimide, 4.39g of 2- (4-hydroxyphenyl) -5- (phenylethynyl) isoindoline-1, 3-dione, 4.22g of 4- (1, 3-dioxo-5- (phenylethynyl) isoindolin-2-yl) benzoic acid, 50mL of acetic anhydride, 20mg of potassium acetate were added. The flask was fitted with a sealed glass paddle stirrer, a nitrogen inlet, a heating mantle temperature sensor inlet and an insulated distillation head. Introducing moderate nitrogen flow, and carrying out acetylation reaction for 30min at the temperature of 140 ℃. A moderate nitrogen flow was passed and the reaction mixture was heated for 4h with a heating mantle, the reaction temperature increasing from 140 ℃ to 310 ℃. At this time, the reaction system was slowly evacuated and kept for 30 min. Cooling the opaque melt to room temperature, removing the product from the flask, and grinding to obtain fine powder, thereby obtaining the wholly aromatic polyester imide liquid crystal oligomer; the differential scanning calorimetry curve, the polarization micrograph, the rheogram and the solubility of the compound are shown in attached figures 3, 4, 5, 6 and 9.
(2) Preparation of thermosetting wholly aromatic polyester imide liquid crystal film
And (3) performing postcondensation reaction in a vacuum oven at 370 ℃ for 24 hours to obtain the thermosetting wholly aromatic polyester imide liquid crystal powder. Spreading the obtained wholly aromatic polyester imide liquid crystal powder in a mold, placing in a flat vulcanizing machine at 370 ℃ for 15min under pressure (2 bar), naturally cooling to 30 ℃ and demolding; then 200 ℃/1h +230 ℃/1h +270 ℃/1h +300 ℃/1h +330 ℃/1h +370 ℃/1h to obtain a thermosetting wholly aromatic polyester imide liquid crystal film; the thermal weight loss-temperature curve and the loss factor (Tan delta) -temperature curve are shown in the attached figures 7 and 8.
Referring to FIG. 3, it is a Differential Scanning Calorimetry (DSC) curve of the wholly aromatic polyesterimide liquid crystal oligomers prepared in examples 1 and 2 according to the present invention and the wholly aromatic polyesterimide liquid crystal oligomers prepared in comparative example 1. The wholly aromatic polyester imide liquid crystal oligomer prepared in the examples 1 and 2 has a wide exothermic peak of curing reaction in a temperature range of 230-360 ℃, and the peak value is about 300 ℃. On the DSC curve of the wholly aromatic polyesterimide liquid crystal oligomer prepared in comparative example 1, the exothermic peak of the curing reaction begins to appear only when the temperature is increased to 360 ℃.
Referring to FIG. 4, it is a Differential Scanning Calorimetry (DSC) curve of the wholly aromatic polyesterimide liquid crystal oligomers prepared in examples 1 and 2 of the present invention and the wholly aromatic polyesterimide liquid crystal oligomers prepared in comparative example 1 after curing treatment. It can be found that the Differential Scanning Calorimetry (DSC) curves of the cured wholly aromatic polyesterimide liquid crystal oligomers prepared in examples 1 and 2 and the wholly aromatic polyesterimide liquid crystal oligomer prepared in comparative example 1 do not show exothermic peaks of curing reaction, which indicates that the wholly aromatic polyesterimide liquid crystal oligomers prepared in examples 1 and 2 and the wholly aromatic polyesterimide liquid crystal oligomer prepared in comparative example 1 have completed crosslinking curing reaction after multi-step curing process, but the maximum curing temperature of the wholly aromatic polyesterimide liquid crystal oligomers prepared in examples 1 and 2 is 300 ℃, and the maximum curing temperature of the wholly aromatic polyesterimide liquid crystal oligomer prepared in comparative example 1 is higher than 360 ℃. Therefore, the solution polycondensation method of the present invention is advantageous in that the crosslinking/curing reaction can be carried out at a lower temperature than the melt polycondensation method, and the selection of the raw materials such as the reactive terminal group can be expanded.
Referring to fig. 5, which is a polarized light microscopic (POM) photograph of the wholly aromatic polyesterimide liquid crystal oligomer powder provided in example 1 of the present invention and the wholly aromatic polyesterimide liquid crystal oligomer powder provided in comparative example 1, both oligomers show typical liquid crystal textures after reaching a certain temperature, respectively; from the POM photograph, it is understood that the wholly aromatic polyesterimide liquid crystal oligomer powder provided in example 1 was transformed into liquid crystal from crystal at 200 ℃ whereas the wholly aromatic polyesterimide liquid crystal oligomer powder provided in comparative example 1 was still in a crystal grain state at 280 ℃ and was not transformed into liquid crystal from crystal until the temperature was 300 ℃. Therefore, the wholly aromatic polyester imide liquid crystal oligomer powder provided by the invention has lower liquid crystal transition temperature, improves the manufacturability and is beneficial to processing and molding of materials.
Referring to fig. 6, which is a rheological diagram of a wholly aromatic polyesterimide liquid crystal oligomer provided in example 1 of the present invention and a wholly aromatic polyesterimide liquid crystal oligomer provided in comparative example 1, the test process is that a temperature rise rate of 3 ℃/min is increased from 180 ℃ to 310 ℃ in a nitrogen atmosphere, and then the temperature is kept constant at 310 ℃ for 1h, as the temperature is increased, the polymer molecular chains begin to move, the composite melt viscosity (| η |) thereof decreases, when the temperature reaches the vicinity of liquid crystal phase transition, the composite melt viscosity decreases most rapidly, when the temperature is 230 ℃, the wholly aromatic polyesterimide liquid crystal oligomer provided in example 1 has changed from crystal to liquid crystal, the composite melt viscosity reaches a minimum value of 184Pa · s, and has good processability, while the wholly aromatic polyesterimide liquid crystal oligomer provided in comparative example 1 reaches a minimum composite melt viscosity value of 4695Pa · s at 300 ℃, which is 25.5 times the minimum composite melt viscosity of the wholly aromatic polyesterimide liquid crystal oligomer provided in example 1, thus it can be known that the fully aromatic polyesterimide liquid crystal imide liquid crystal oligomer provided in example 1 has a tendency to increase at a constant temperature, and the temperature of the fully aromatic polyesterimide liquid crystal melt reaction temperature is increased, so that the fully aromatic polyesterimide liquid crystal imide liquid crystal oligomer provided in comparative example 1, the composite melt reaction is not completely solidified, the polyester melt, the polyester imide liquid crystal melt reaction temperature provides a high temperature, the fully aromatic polyesterimide liquid crystal melt reaction temperature of comparative example 1, the polyester is increased, the polyester melt reaction is increased, the temperature of example 1, the polyester melt reaction is increased, the temperature is increased, the polyester melt reaction is improved, the temperature of the polyester melt reaction is improved, the polyester is improved, the temperature of the temperature is improved, the temperature is improved.
Referring to FIG. 7, there are shown mass loss vs. temperature curves of the thermosetting wholly aromatic polyesterimide liquid crystal films prepared in examples 1 and 2 of the present invention and the thermosetting wholly aromatic polyesterimide liquid crystal film prepared in comparative example 1 in a nitrogen atmosphere. Generally by the initial thermal decomposition temperature (T di The temperature at which the weight loss is 5%) characterizes the thermal stability of the material. Preparation of thermosetting polyesterimide liquid Crystal films prepared in examples 1 and 2T di Approximately 460 ℃, indicating high thermal stability. In addition, the carbon residue of the film is as high as 65wt% (600 ℃). Therefore, the thermosetting polyester imide liquid crystal prepared by the invention has similar thermal stability with the thermosetting polyester imide liquid crystal prepared by a melting method, but the preparation temperature is lower, the process is more controllable, and the raw material selection is wider.
Referring to FIG. 8, there are shown graphs of loss factor (Tan. delta.) vs. temperature for the thermosetting wholly aromatic polyesterimide liquid crystal films prepared in examples 1 and 2 of the present invention and the thermosetting wholly aromatic polyesterimide liquid crystal film provided in comparative example 1. As is clear from the figure, the glass transition temperatures of the thermosetting wholly aromatic polyesterimide liquid crystal films prepared in examples 1 and 2 are (T g ) 190 ℃ and 223 ℃ respectively, and the thermosetting wholly aromatic polyesterimide liquid crystal film prepared in comparative example 1 has twoT g （T g1 =127℃，T g2 =260 ℃). If the polymer material has a plurality ofT g Its practical application will be limited to the lower of themT g Therefore, the heat resistance of the thermosetting wholly aromatic polyesterimide liquid crystal prepared in comparative example 1 in practical use is inferior to that of the thermosetting polyesterimide liquid crystal prepared by the solution method of the present invention.
FIG. 9 is a photograph showing the solubility of the thermosetting wholly aromatic polyesterimide liquid crystal powders of examples 1 and 2 and the thermosetting wholly aromatic polyesterimide liquid crystal powder of comparative example 1 in a mixed solvent of chloroform and pentafluorophenol (volume ratio: 1). As is clear from the photographs, the thermosetting wholly aromatic polyesterimide liquid crystal powders provided in examples 1 and 2 were soluble in the mixed solvent of chloroform and pentafluorophenol, whereas the thermosetting wholly aromatic polyesterimide liquid crystal powder provided in comparative example 1 was not soluble in the mixed solvent of chloroform and pentafluorophenol. The thermosetting wholly aromatic polyester imide liquid crystal powder prepared by the method of the invention overcomes the defect that the thermosetting wholly aromatic polyester imide liquid crystal powder prepared by the prior art (melting method) is insoluble, and provides basis and convenience for industrial application.
It can be seen that the reaction temperature of the invention is low (100-150 ℃), the reaction temperature of the existing melting method reaches 310 ℃, the polymer powder obtained by the invention has lower liquid crystal transition temperature (200 ℃), the liquid crystal transition temperature of the existing melting method is 300 ℃, particularly the curing temperature of the powder obtained by the invention is low (300 ℃), and the existing technology needs more than 370 ℃; the powder obtained by the invention has good processability which can be achieved at 300 ℃, and is especially soluble, and the film prepared by the invention has low processing temperature and high glass transition temperature, thereby achieving unexpected technical effects.

Claims (6)

1. A preparation method of a thermosetting wholly aromatic polyester imide liquid crystal is characterized by comprising the following steps: dropwise adding a solution containing a phosphate condensing agent and metal salt into a preheated mixed solution containing a monomer, an active end group and a polar solvent, and then reacting for 2-6 h at 100-150 ℃ in nitrogen to obtain a polymer solution; then pouring the polymer solution into an organic solvent, washing and drying to obtain a thermosetting wholly aromatic polyester imide liquid crystal; the active end group is one or more of 3-aminophenylacetylene, 2- (3-ethynylphenyl) -5-hydroxyiso-1, 3-diketone and 2- (3-ethynylphenyl) -1, 3-dioxoisoindoline-5-carboxylic acid;
the monomer is a wholly aromatic monomer and a wholly aromatic monomer containing an imide group;
the chemical structural formula of the wholly aromatic monomer is R1-Ar1-R2Ar1 is a wholly aromatic radical, R1、R2Is an end group;
the chemical structural formula of the wholly aromatic monomer containing the imide group is as follows:
Figure 33753DEST_PATH_IMAGE001
ar is a wholly aromatic radical, R3、R4Is an end group;
the R is1、R2、R3、R4Independently selected from-COOH or-OH;
the molecular weight of the thermosetting wholly aromatic polyester imide liquid crystal is 1000-7000 g/mol.
2. The method for preparing a thermosetting wholly aromatic polyesterimide liquid crystal according to claim 1, wherein: the phosphate ester condensing agent is one or more of diphenyl chlorophosphate, triphenyl phosphite, tris (4-chlorophenyl) phosphite and diphenyl phosphite; the metal salt is one or more of anhydrous lithium chloride, magnesium chloride, calcium chloride and zinc chloride; the organic solvent is one or more of methanol, ethyl acetate and petroleum ether; the polar solvent is one or more of pyridine, methyl pyrrolidone and N, N-dimethylacetamide; in the solution containing the phosphate condensing agent and the metal salt, the solvent is one or more of pyridine, methyl pyrrolidone and N, N-dimethylacetamide; ar1 is one of the following three structures:
Figure 699090DEST_PATH_IMAGE002
、
Figure 234239DEST_PATH_IMAGE003
、
Figure 694039DEST_PATH_IMAGE004
；
ar is one of the following three structures:
Figure 704851DEST_PATH_IMAGE002
、
Figure 409765DEST_PATH_IMAGE003
、
Figure 297955DEST_PATH_IMAGE004
；
the R is1、R2、R3、R4Independently selected from-COOH or-OH.
3. The method for preparing a thermosetting wholly aromatic polyesterimide liquid crystal according to claim 1, wherein: in the monomers, the molar ratio of the wholly aromatic monomer to the wholly aromatic monomer containing the imide group is n to (1-n), wherein n is more than 0 and less than 1; the molar ratio of the phosphate condensing agent to the monomer is (1-5) to 1; in the solution containing the phosphate condensing agent and the metal salt, the molar ratio of the metal salt to the solvent is 1: 6-30.
4. The method for preparing a thermosetting wholly aromatic polyesterimide liquid crystal according to claim 1, wherein: adding a phosphate ester condensing agent and metal salt into a solvent, and stirring for 30-45 min at 10-40 ℃ to obtain a solution containing the phosphate ester condensing agent and the metal salt; the preheating is carried out for 5-10 min at 100-150 ℃ under the protection of nitrogen; the dripping time is 30-60 min.
5. The preparation method of the thermosetting wholly aromatic polyester imide liquid crystal precursor solution is characterized by comprising the following steps of: dropwise adding a solution containing a phosphate condensing agent and metal salt into a preheated mixed solution containing a monomer, an active end group and a polar solvent, and then reacting for 2-6 h at 100-150 ℃ in nitrogen to obtain a thermosetting wholly aromatic polyesterimide liquid crystal precursor solution; the active end group is one or more of 3-aminophenylacetylene, 2- (3-ethynylphenyl) -5-hydroxyiso-1, 3-diketone and 2- (3-ethynylphenyl) -1, 3-dioxoisoindoline-5-carboxylic acid;
the monomer is a wholly aromatic monomer and a wholly aromatic monomer containing an imide group;
the chemical structural formula of the wholly aromatic monomer is R1-Ar1-R2Ar1 is a wholly aromatic radical, R1、R2Is an end group;
the chemical structural formula of the wholly aromatic monomer containing the imide group is as follows:
Figure 272864DEST_PATH_IMAGE001
ar is a wholly aromatic radical, R3、R4Is an end group;
the R is1、R2、R3、R4Independently selected from-COOH or-OH.
6. The method for preparing the thermosetting wholly aromatic polyester imide liquid crystal precursor solution as claimed in claim 5, wherein: the phosphate ester condensing agent is one or more of diphenyl chlorophosphate, triphenyl phosphite, tris (4-chlorophenyl) phosphite and diphenyl phosphite; the metal salt is one or more of anhydrous lithium chloride, magnesium chloride, calcium chloride and zinc chloride; the polar solvent is one or more of pyridine, methyl pyrrolidone and N, N-dimethylacetamide; in the solution containing the phosphate condensing agent and the metal salt, the solvent is one or more of pyridine, methyl pyrrolidone and N, N-dimethylacetamide; ar1 is one of the following three structures:
Figure 126899DEST_PATH_IMAGE002
、
Figure 337301DEST_PATH_IMAGE003
、
Figure 581463DEST_PATH_IMAGE004
；
ar is one of the following three structures:
Figure 242120DEST_PATH_IMAGE002
、
Figure 509415DEST_PATH_IMAGE003
、
Figure 320246DEST_PATH_IMAGE004
；
the R is1、R2、R3、R4Independently selected from-COOH or-OH.
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