CN115894881B - Flame-retardant liquid crystal polymer with rigidity and toughness and preparation method thereof - Google Patents

Flame-retardant liquid crystal polymer with rigidity and toughness and preparation method thereof Download PDF

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CN115894881B
CN115894881B CN202211375044.3A CN202211375044A CN115894881B CN 115894881 B CN115894881 B CN 115894881B CN 202211375044 A CN202211375044 A CN 202211375044A CN 115894881 B CN115894881 B CN 115894881B
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liquid crystal
crystal polymer
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rigidity
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CN115894881A (en
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王卫红
潘凯
李军
苑红亮
张丽平
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Changzhou Ruijie New Materials Technology Co ltd
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Abstract

The invention relates to a flame-retardant liquid crystal polymer with rigidity and toughness and a preparation method thereof, and the flame-retardant liquid crystal polymer has the following structure:wherein R is 0 Including ether linkages and/or ester groups, and phenyl groups and/or alkyl groups; r is R 1 Is one of hydrogen, methyl and ethyl, R 2 Is one of hydrogen, methyl, ethyl and phenyl; r is R 3 Is methylene, the number of the methylene is 0-7; r is R 4 Is one of phenyl, biphenyl, diphenyl ether, aromatic radical containing at least one fluorine atom and aromatic cycloalkyl; wherein the value range of n is 5-95. According to the liquid crystal polymer, thioether and/or substituent groups are introduced into the main chain, so that the flexibility of a molecular chain is improved, the acting force between the molecular chains is reduced, the liquid crystal polymer has rigidity and toughness, the fluidity of the liquid crystal polymer is improved, the liquid crystal polymer is easy to process and mold, and meanwhile, the thioether and/or the fluorine have high flame retardance, so that the liquid crystal polymer has high flame retardance, and the application range of the liquid crystal polymer is widened.

Description

Flame-retardant liquid crystal polymer with rigidity and toughness and preparation method thereof
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a flame-retardant liquid crystal polymer with rigidity and toughness and a preparation method thereof.
Background
The Liquid Crystal Polymer (LCP) is a high molecular polymer which is formed by rigid molecular chains and has liquid crystallinity under certain conditions, and the molecular arrangement of the high molecular polymer tends to be orderly, so that the high molecular polymer has the advantages of high strength, high rigidity, thermal stability, high temperature resistance and the like, but because of the influence of a large number of rigid structures, the liquid crystal polymer has poor melt fluidity and poor toughness, is unfavorable for being used in a severe environment and limits the application of the liquid crystal polymer, and in order to improve the fluidity and toughness of the liquid crystal polymer, the invention prepares the flame retardant liquid crystal polymer with rigidity and toughness through molecular structure design.
Disclosure of Invention
In order to solve the technical problems of poor flowability and poor toughness of the conventional liquid crystal polymer, the flame-retardant liquid crystal polymer with rigidity and toughness and the preparation method thereof are provided. The liquid crystal polymer has rigidity and toughness, high flame retardant property and small acting force among molecular chains by introducing thioether and/or halogen fluorine on a substituent group on a molecular main chain, thereby being beneficial to improving the fluidity of the liquid crystal polymer and being easy to process and form.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
a flame-retardant liquid crystal polymer with rigidity and toughness has the following chemical structure:
Wherein R is 0 Including ether linkages and/or ester groups, and phenyl groups and/or alkyl groups;
R 1 is one of hydrogen, methyl and ethyl;
R 2 is one of hydrogen, methyl, ethyl and phenyl;
R 3 is methylene, the number of the methylene is 0-7;
R 4 is one of phenyl, biphenyl, diphenyl ether, aromatic radical containing at least one fluorine atom and aromatic cycloalkyl;
wherein the value range of n is 5-95.
Preferably, said R 0 Has one of the following structures:
wherein R is 5 And R is 7 Is phenyl and the number of carbon atomsIs one of normal alkyl or isomeric alkyl of 4-8, R 5 And R is 7 May be the same or different;
R 6 is phenyl, biphenyl, naphthyl, diphenyl ether groupDiphenylpropy group->Diphenyl ester group->One of them, a second one of them.
The preparation method of the flame-retardant liquid crystal polymer with rigidity and toughness comprises the steps of esterifying and polycondensing an aromatic diol monomer and an aromatic diacid monomer containing a thioether group;
the chemical structure of the aromatic diacid monomer containing the thioether group is as follows:
the chemical structure of the aromatic diol is as follows: HO-R 4 -OH。
Further, the aromatic diols may be, but are not limited to, the following: hydroquinone, 4'- (1, 4-phenylene diisopropyl) diphenol, diphenyl diphenol, 2' -diphenyl dimethanol, 3 '-dimethyl-4, 4' -diphenyl diphenol, 2, 4-difluoro catechol 2, 3-difluorohydroquinone, 4 '-dihydroxydiphenyl ether, 2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1' -bis (4-hydroxyphenyl) cyclohexane.
Further, the aromatic diacid monomer containing the thioether group is obtained by reacting a dithiol aryl compound and a vinyl acid ester compound under the action of a first catalyst and a free radical initiator to generate an aromatic diester substance containing the thioether group, and then hydrolyzing to obtain the aromatic diacid monomer containing the thioether group;
the dithiol aryl compound is a dithiol compound comprising an ether bond and/or an ester group in its main chain structure, and a phenyl group and/or an alkyl group;
the vinyl acid ester compound has a structural formula as follows:
wherein R is 1 Is one of hydrogen, methyl, ethyl and phenyl;
R 2 is one of hydrogen, methyl, ethyl and phenyl;
R 3 is methylene, the number of the methylene is 0-7;
R 8 is one of methyl and ethyl.
The first catalyst is a mixture of triethylamine and dimethylphenylphosphine, and the addition amount is a conventional catalyst amount;
the free radical initiator is AIBN or benzoyl peroxide and may be added in conventional amounts, for example, from 0.1% to 3% by weight of the total monomer.
Preferably, the vinyl acid ester compound includes, but is not limited to, one of methyl acrylate, 2-phenyl-ethyl acrylate, methyl methacrylate, 2-ethylene-ethyl benzoate, methyl 2-pentenoate, and ethyl 2-ethyl-acrylate.
Specifically, the specific preparation method of the aromatic diacid monomer containing the thioether group comprises the following steps:
adding dithiol aryl compound and monoacrylate compound according to a molar ratio of 1:2.4 in a reaction vessel with a reflux device and a stirring device, adding a first catalyst and a free radical initiator, heating to 100 ℃, stirring and reacting for 10 hours to obtain an aromatic diester substance containing thioether groups, cooling to room temperature, adding excessive methanol and a proper amount of potassium hydroxide solution with concentration of 10wt%, stirring and refluxing at 60-70 ℃ for 12 hours, and ending the reaction; after the reactant is cooled to room temperature, pouring distilled water, regulating the pH value to be 2-3 by hydrochloric acid for hydrolysis, generating precipitate, filtering, washing for a plurality of times by distilled water, filtering, and drying in a vacuum oven to obtain the aromatic diacid monomer containing thioether groups.
Specifically, the preparation method of the flame-retardant liquid crystal polymer with rigidity and toughness comprises the following steps: the preparation method specifically comprises the following steps: heating the aromatic diacid monomer containing the thioether group and the aromatic diol monomer to 180-200 ℃ under the action of a second catalyst and nitrogen atmosphere, carrying out esterification reaction for 4-7h under stirring, continuously heating to 210-230 ℃ after no bubbles are generated in a reaction system, removing nitrogen after reaching the temperature, vacuumizing the reaction system until the vacuum degree is kept within 30Pa, carrying out polycondensation reaction for 3-6h, stopping the reaction when the product generates a pole climbing phenomenon, and cooling to room temperature to obtain the flame-retardant liquid crystal polymer.
Further, the molar ratio of the aromatic diol monomer to the aromatic diacid monomer containing the thioether group is 1.1-1.25:1.
Further, the second catalyst consists of a main catalyst and a cocatalyst, wherein the addition amount of the main catalyst is 0.5% of the total mass of the reaction monomers, and the addition amount of the cocatalyst is 0.2% of the total mass of the reaction monomers; the main catalyst is one of stannous octoate and antimony trioxide, and the cocatalyst is one of zinc acetate and tetrabutyl titanate.
The beneficial technical effects are as follows: the liquid crystal polymer containing the thioether groups is prepared by carrying out esterification polycondensation reaction on the aromatic diacid containing the thioether groups and the aromatic diol, and thioether and/or fluorine flexible groups are introduced into the molecular main chain, so that the rigidity of the molecular chain and acting force between the molecular chains are reduced, the processing temperature of the liquid crystal polymer is reduced, the fluidity is improved, the processing performance is improved, and the cost is reduced; the introduction of the thioether flexible group ensures that the liquid crystal has certain rigidity and toughness and high flame retardant property.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The numerical values set forth in these examples do not limit the scope of the present invention unless specifically stated otherwise. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but should be considered part of the specification where appropriate. In all examples shown and discussed herein, any specific values should be construed as merely illustrative, and not a limitation. Thus, other examples of the exemplary embodiments may have different values.
In addition, the terms "first", "second", etc. are used to define materials, and are merely for convenience in distinguishing materials used in each reaction step, and unless otherwise stated, the terms have no special meaning, and thus are not to be construed as limiting the scope of the present invention.
The experimental methods in the following examples, for which specific conditions are not noted, are generally determined according to national standards; if the national standard is not corresponding, the method is carried out according to the general international standard or the standard requirements set by related enterprises. Unless otherwise indicated, all parts are parts by weight and all percentages are percentages by weight.
Example 1
A flame-retardant liquid crystal polymer with rigidity and toughness is shown in a formula I-1, is prepared by esterifying and polycondensing an aromatic diacid monomer D1 containing a thioether group and an aromatic diol monomer A1, and has the following reaction formula:
the specific reaction process is as follows: 9.08g of an aromatic diacid containing a thio ether group and having the structure D1, 2.75g of an aromatic diol having the structure A1, 0.0592g of stannous octoate and 0.0237g of zinc acetate are added into a reaction flask with a reflux and stirring device; heating to 180 ℃ in a nitrogen atmosphere, starting stirring and reacting for 7 hours, and when the distilled liquid reaches 70-80wt% of a theoretical value, generating no bubbles in a reaction system; then heating to 220 ℃, removing nitrogen, vacuumizing the reaction system, controlling the vacuum degree within 30Pa, performing polycondensation reaction for 5 hours, stopping the reaction when the product viscosity generates the pole climbing phenomenon, and cooling to room temperature to obtain the liquid crystal polymer with the structure of formula I-1.
The method for obtaining the aromatic diacid containing a thio ether group of the D1 structure in this example comprises the following steps:
13.77g of 4-bromo-1-butanol, 4.98g of terephthalic acid and 150mL of methylene dichloride are added into a reaction bottle, nitrogen is introduced under the action of DCC (3.54 g)/DMAP (0.14 g), stirring is started, and the reaction is finished after 18h of reaction at normal temperature; filtering, washing the filtrate with 100mL of glacial acetic acid, washing the filtrate with 100mL of water, and layering to leave an organic layer; adding sodium sulfate, drying, filtering and decompressing to evaporate to obtain a crude product; ethanol was added to the crude product to give pure product 1- (1) by recrystallization.
5.66g of the product 1- (1), 18.24g of potassium thioacetate and 50 mM of MF are added into a reaction flask, and the reaction is completed after stirring for 5 hours at room temperature; 50mL of water was added, the organic phase of the product was extracted with 100mL of ethyl acetate, then dried over sodium sulfate, filtered and evaporated under reduced pressure to give the crude product, to which ethanol was added, and pure product 1- (2) was obtained by recrystallization.
5.46g of product 1- (2) are dissolved in 20ml of THF and then 0.76g of NaBH are slowly added to the reaction flask at 0 ℃ 4 And 50mL of water, then washing the mixture with water after reacting for 24 hours at room temperature, then adding 50mL of methylene chloride to extract the organic phase of the product, then adding sodium sulfate to dry, filtering and evaporating under reduced pressure to obtain a crude product, adding 12mL of ethylene glycol monopropyl ether and 2mL of ethyl acetate to the crude product, and purifying to obtain the pure product 1- (3) dithiol aryl compound.
Adding pure product 1- (3) dithiol aryl compound and methyl acrylate in a molar ratio of 1:2.4 into a reaction vessel with a reflux device and a stirring device, adding a mixture of a catalyst triethylamine and dimethylphenylphosphine and a free radical initiator AIBN, heating to 100 ℃, stirring and reacting for 10 hours to obtain an aromatic diester substance containing thioether groups, cooling to room temperature, adding excessive methanol and a proper amount of potassium hydroxide solution with concentration of 10wt%, stirring and refluxing at 60-70 ℃ for 12 hours, and ending the reaction; after the reactant is cooled to room temperature, pouring distilled water, regulating the pH value to be 2-3 by hydrochloric acid for hydrolysis, generating precipitate, filtering, washing for a plurality of times by distilled water, filtering, and drying in a vacuum oven to obtain the aromatic diacid monomer D1 containing thioether groups.
Example 2
A flame-retardant liquid crystal polymer with rigidity and toughness is shown in formula I-2, which is prepared by esterifying and polycondensing an aromatic diacid monomer D2 containing a thioether group and an aromatic diol monomer A2, and has the following reaction formula:
the specific reaction process is as follows: 15.72g of an aromatic diacid containing a thio ether group of a D2 structure, 3.07g of an aromatic diol of an A2 structure, 0.0939g of stannous octoate and 0.0376g of zinc acetate are added into a reaction bottle with a reflux and stirring device; heating to 200 ℃ in nitrogen atmosphere, starting stirring and reacting for 5 hours, and when the distilled liquid reaches 70-80wt% of theoretical value, no bubbles are generated in the reaction system; then heating to 225 ℃, removing nitrogen, vacuumizing the reaction system, controlling the vacuum degree within 30Pa, performing polycondensation reaction for 6 hours, stopping the reaction when the product viscosity generates the pole climbing phenomenon, and cooling to room temperature to obtain the liquid crystal polymer with the structure of formula I-2.
The method for obtaining the aromatic diacid containing a thio ether group of the D2 structure in the embodiment comprises the following steps:
13.02g of 6-bromo-1-hexanol, 7.74g of 4, 4-diphenylether dicarboxylic acid and 150mL of methylene chloride were added to the reaction flask, nitrogen was introduced under the action of DCC (5.19 g)/DMAP (0.21 g), stirring was turned on, and the reaction was completed after 16 hours at room temperature. The mixture was filtered, the filtrate was washed with 100mL glacial acetic acid and then 100mL water, and the layers were separated to leave an organic layer. After drying over sodium sulfate, filtration and evaporation under reduced pressure gave the crude product. Ethanol was added to the crude product to give pure product 2- (1) by recrystallization.
11.68g of the product 2- (1), 20.52g of potassium thioacetate and 80 mM LDMF were placed in a reaction flask, and the reaction was terminated after stirring at room temperature for 6 hours. 80mL of water was added, the organic phase of the product was extracted with 150mL of ethyl acetate, then dried over sodium sulfate, filtered and evaporated under reduced pressure to give the crude product, to which ethanol was added, and pure product 2- (2) was obtained by recrystallization.
5.74g of product 2- (2) are dissolved in 20ml of THF and then 0.80g of NaBH are slowly added to the reaction flask at 0 ℃ 4 And 50mL of water, then after 26 hours at room temperature, the mixture is washed with water, then 50mL of dichloromethane is added to extract the organic phase of the product, then sodium sulfate is added to dry, filtration and evaporation under reduced pressure are carried out to obtain a crude product, 12mL of ethylene glycol monopropyl ether and 2mL of ethyl acetate are added to the crude product, and then the pure product 2- (3) dithiol aryl compound is obtained by FCC purification.
Adding pure product 2- (3) dithiol aryl compound and 2-phenyl-ethyl acrylate according to the mol ratio of 1:2.4 in a reaction vessel with a reflux device and a stirring device, adding a mixture of a catalyst triethylamine and dimethylphenylphosphine and a free radical initiator AIBN, heating to 100 ℃, stirring and reacting for 10 hours to obtain an aromatic diester substance containing thioether groups, cooling to room temperature, adding excessive methanol and a proper amount of potassium hydroxide solution with the concentration of 10wt%, stirring and refluxing at 60-70 ℃ for 12 hours, and ending the reaction; after the reactant is cooled to room temperature, pouring distilled water, regulating the pH value to be 2-3 by hydrochloric acid for hydrolysis, generating precipitate, filtering, washing for a plurality of times by distilled water, filtering, and drying in a vacuum oven to obtain the aromatic diacid monomer D2 containing thioether groups.
Example 3
A flame-retardant liquid crystal polymer with rigidity and toughness is shown in a formula I-3, is prepared by esterifying and polycondensing an aromatic diacid monomer D3 and an aromatic diol monomer A3 containing thioether groups, and has the following reaction formula:
the specific reaction process is as follows: into a reaction flask with reflux and stirring device, 12.92g of aromatic diacid containing a thio ether group of D3 structure, 4.28g of aromatic diol of A3 structure, 0.0860g of antimony trioxide and 0.0344g of tetrabutyl titanate are added; heating to 190 ℃ in a nitrogen atmosphere, starting stirring and reacting for 6 hours, and when the distilled liquid reaches 70-80wt% of the theoretical value, generating no bubbles in a reaction system; then heating to 210 ℃, removing nitrogen, vacuumizing the reaction system, controlling the vacuum degree within 30Pa, performing polycondensation reaction for 4 hours, stopping the reaction when the product viscosity generates the pole climbing phenomenon, and cooling to room temperature to obtain the liquid crystal polymer with the structure of formula I-3.
The method for obtaining the aromatic diacid containing a thio ether group of the D3 structure in the embodiment comprises the following steps:
10.86g of 6-bromo-1-hexanol, 7.26g of 4,4' -biphenyl dicarboxylic acid and 150mL of methylene chloride were added to the reaction flask, nitrogen was introduced under the action of DCC (4.53 g)/DMAP (0.18 g), stirring was turned on, and the reaction was completed after 20 hours at normal temperature. The mixture was filtered, the filtrate was washed with 150mL glacial acetic acid and then with 150mL water, and the layers were separated to leave an organic layer. After drying over sodium sulfate, filtration and evaporation under reduced pressure gave the crude product. Ethanol was added to the crude product and pure product 3- (1) was obtained by recrystallization.
7.32g of the product 3- (1), 20.52g of potassium thioacetate and 60 mM of MF were placed in a reaction flask, and the reaction was terminated after stirring at room temperature for 6 hours. 60mL of water was added, the organic phase of the product was extracted with 120mL of ethyl acetate, then dried over sodium sulfate, filtered and evaporated under reduced pressure to give the crude product, to which ethanol was added, and pure product 3- (2) was obtained by recrystallization.
10.05g of product 3- (2) are dissolved in 40ml of THF and then 0.95g of NaBH are slowly added to the reaction flask at 0 ℃ 4 And 10mL of water, then after 26h reaction at room temperature, the mixture is washed with water, then 100mL of dichloromethane solvent is added to extract the organic phase of the product, then sodium sulfate is added to dry, filtration and evaporation under reduced pressure are carried out to obtain a crude product, 20mL of ethylene glycol monopropyl ether and 4mL of ethyl acetate are added to the crude product, and the pure product 3- (3) dithiol aryl compound is obtained after purification.
Adding pure 3- (3) dithiol aryl compound and methyl methacrylate according to a molar ratio of 1:2.4 into a reaction vessel with a reflux device and a stirring device, adding a mixture of triethylamine and dimethylphenylphosphine serving as catalysts and benzoyl peroxide serving as a free radical initiator, heating to 100 ℃, stirring and reacting for 10 hours to obtain an aromatic diester substance containing thioether groups, cooling to room temperature, adding excessive methanol and a proper amount of potassium hydroxide solution with concentration of 10wt%, stirring and refluxing at 60-70 ℃ for 12 hours, and ending the reaction; after the reactant is cooled to room temperature, pouring distilled water, regulating the pH value to be 2-3 by hydrochloric acid for hydrolysis, generating precipitate, filtering, washing for a plurality of times by distilled water, filtering, and drying in a vacuum oven to obtain the aromatic diacid monomer D3 containing thioether groups.
Example 4
A flame-retardant liquid crystal polymer with rigidity and toughness is prepared by esterifying and polycondensing an aromatic diacid monomer D4 containing a thioether group and an aromatic diol monomer A4, and has the following reaction formula:
the specific reaction process is as follows: 16.28g of aromatic diacid containing a thio ether group with a D4 structure, 7.96g of aromatic diol with an A4 structure, 0.1212g of stannous octoate and 0.0485g of zinc acetate are added into a reaction bottle with a reflux and stirring device; heating to 180 ℃ in a nitrogen atmosphere, starting stirring and reacting for 6 hours, and when the distilled liquid reaches 70-80wt% of a theoretical value, generating no bubbles in a reaction system; then heating to 220 ℃, removing nitrogen, vacuumizing the reaction system, controlling the vacuum degree within 30Pa, performing polycondensation reaction for 3 hours, stopping the reaction when the product viscosity generates the pole climbing phenomenon, and cooling to room temperature to obtain the liquid crystal polymer with the structure of formula I-4.
The method for obtaining the aromatic diacid containing a thio ether group of D4 structure in this example:
7.35g of 4-cyanobenzoic acid, 11.90g of 4-hydroxybenzonitrile and 150mL of acetone are added into a reaction bottle, nitrogen is introduced under the action of DCC (4.8 g)/DMAP (0.19 g), stirring is started, and the reaction is completed after 18h of reaction at normal temperature. The mixture was filtered, the filtrate was washed with 150mL glacial acetic acid and then with 150mL water, and the layers were separated to leave an organic layer. After drying over sodium sulfate, filtration and evaporation under reduced pressure gave the crude product. Ethanol is added to the crude product, and the pure product 4- (1) aromatic nitrile compound is obtained by recrystallization.
9.92g of 4- (1) arylnitrile, 2.5g of sodium hydroxide and 60mL of ethanol solvent are added into a new reaction bottle with a reflux and stirring device, the temperature is raised to 130 ℃, the reaction is finished after 15 hours, then hydrochloric acid is used for adjusting the pH value to 3-5, precipitate is generated, the precipitate is filtered, distilled water is used for washing for a plurality of times, the filtration is carried out, and the mixture is put into a vacuum oven for drying, thus obtaining the 4- (2) product.
7.15g of 4- (2), 13.58g of 6-bromo-1-hexanol and 150mL of methylene chloride were added to the reaction flask, nitrogen was introduced under the action of DCC (5.18 g)/DMAP (0.21 g), stirring was turned on, and the reaction was completed after 18 hours at normal temperature. The mixture was filtered, the filtrate was washed with 100mL glacial acetic acid and then 100mL water, and the layers were separated to leave an organic layer. After drying over sodium sulfate, filtration and evaporation under reduced pressure gave the crude product. Ethanol was added to the crude product and pure product 4- (3) was obtained by recrystallization.
To the reaction flask were added 8.62g of the product 4- (3), 18.24g of potassium thioacetate, and 80ml of LDMF, and the reaction was terminated after stirring at room temperature for 6 hours. 80mL of water was added, the organic phase of the product was extracted with 150mL of ethyl acetate, then dried over sodium sulfate, filtered and evaporated under reduced pressure to give the crude product, to which ethanol was added, and pure product 4- (4) was obtained by recrystallization.
6.32g of product 4- (4) are dissolved in 30ml of THF and then 0.88g of NaBH are slowly added to the reaction flask at 0 ℃ 4 And 60mL of water, then washing the mixture with water after reacting for 24 hours at room temperature, then adding 50mL of dichloromethane to extract the organic phase of the product, then adding sodium sulfate to dry, filtering and evaporating under reduced pressure to obtain a crude product, adding 15mL of ethylene glycol monopropyl ether and 3mL of ethyl acetate to the crude product, and purifying to obtain the pure product 4- (5) dithiol aryl compound.
Adding pure product 4- (5) dithiol aryl compound and 2-phenyl-ethyl acrylate according to the mol ratio of 1:2.4 in a reaction vessel with a reflux device and a stirring device, adding a mixture of a catalyst triethylamine and dimethylphenylphosphine and a free radical initiator benzoyl peroxide, heating to 100 ℃, stirring and reacting for 10 hours to obtain an aromatic diester substance containing thioether groups, cooling to room temperature, adding excessive methanol and a proper amount of potassium hydroxide solution with the concentration of 10wt%, stirring and refluxing at 60-70 ℃ for 12 hours, and ending the reaction; after the reactant is cooled to room temperature, pouring distilled water, regulating the pH value to be 2-3 by hydrochloric acid for hydrolysis, generating precipitate, filtering, washing for a plurality of times by distilled water, filtering, and drying in a vacuum oven to obtain the aromatic diacid monomer D4 containing thioether groups.
Example 5
A flame-retardant liquid crystal polymer with rigidity and toughness is prepared by esterifying and polycondensing an aromatic diacid monomer D5 containing a thioether group and an aromatic diol monomer A5, and has the following reaction formula:
the specific reaction process is as follows: 14.22g of an aromatic diacid containing a thiol ether group of D5 structure, 5.05g of an aromatic diol of A5 structure, 0.0965g of antimony trioxide and 0.0386g of tetrabutyltitanate are introduced into a reaction flask with reflux stirring; heating to 190 ℃ in a nitrogen atmosphere, starting stirring and reacting for 7 hours, and when the distilled liquid reaches 70-80wt% of the theoretical value, generating no bubbles in the reaction system; then heating to 225 ℃, removing nitrogen, vacuumizing the reaction system, controlling the vacuum degree within 30Pa, performing polycondensation reaction for 4 hours, stopping the reaction when the product viscosity generates the pole climbing phenomenon, and cooling to room temperature to obtain the liquid crystal polymer with the structure of formula I-5.
The method for obtaining the aromatic diacid containing a thio ether group of D5 structure in this example comprises the following steps:
12.24g of 4-bromo-1-butanol, 4.32g of 2, 6-naphthalenedicarboxylic acid and 150mL of methylene chloride were placed in a reaction flask, nitrogen was introduced under the action of DCC (4.14 g)/DMAP (0.17 g), stirring was turned on, and the reaction was completed after 18 hours at normal temperature. The mixture was filtered, the filtrate was washed with 100mL glacial acetic acid and then 100mL water, and the layers were separated to leave an organic layer. After drying over sodium sulfate, filtration and evaporation under reduced pressure gave the crude product. Ethanol was added to the crude product and pure product 5- (1) was obtained by recrystallization.
7.27g of the product 5- (1), 13.68g of potassium thioacetate and 80 mM of MF were placed in a reaction flask, and the reaction was terminated after stirring at room temperature for 5 hours. 80mL of water was added, the organic phase of the product was extracted with 120mL of ethyl acetate, then dried over sodium sulfate, filtered and evaporated under reduced pressure to give the crude product, to which ethanol was added, and pure product 5- (2) was obtained by recrystallization.
7.14g of product 5- (2) are dissolved in 40ml of THF and then 0.785g of NaBH are slowly added to the reaction flask at 0 ℃ 4 And 80mL of water, then washing the mixture with water after reacting for 24 hours at room temperature, then adding 50mL of dichloromethane to extract the organic phase of the product, then adding sodium sulfate to dry, filtering and evaporating under reduced pressure to obtain a crude product, adding 20mL of ethylene glycol monopropyl ether and 4mL of ethyl acetate to the crude product, and purifying to obtain a pure product 5- (3) dithiol aryl compound.
Adding pure product 5- (3) dithiol aryl compound and 2-ethylene-ethyl benzoate in a molar ratio of 1:2.4 into a reaction vessel with a reflux device and a stirring device, adding a mixture of a catalyst triethylamine and dimethylphenylphosphine and a free radical initiator AIBN, heating to 100 ℃, stirring and reacting for 10 hours to obtain an aromatic diester substance containing thioether groups, cooling to room temperature, adding excessive methanol and a proper amount of potassium hydroxide solution with concentration of 10wt%, stirring and refluxing at 60-70 ℃ for 12 hours, and ending the reaction; after the reactant is cooled to room temperature, pouring distilled water, regulating the pH value to be 2-3 by hydrochloric acid for hydrolysis, generating precipitate, filtering, washing for a plurality of times by distilled water, filtering, and drying in a vacuum oven to obtain the aromatic diacid monomer D5 containing thioether groups.
Example 6
A flame-retardant liquid crystal polymer with rigidity and toughness is prepared by esterifying and polycondensing an aromatic diacid monomer D6 containing a thioether group and an aromatic diol monomer A6, and has the following reaction formula:
the specific reaction process is as follows: 13.72g of aromatic diacid containing a thio ether group with a D6 structure, 8.23g of aromatic diol with an A6 structure, 0.1098g of antimony trioxide and 0.0439g of tetrabutyl titanate are added into a reaction bottle with a reflux and stirring device; heating to 200 ℃ in nitrogen atmosphere, starting stirring and reacting for 5 hours, and when the distilled liquid reaches 70-80wt% of theoretical value, no bubbles are generated in the reaction system; then heating to 210 ℃, removing nitrogen, vacuumizing the reaction system, controlling the vacuum degree within 30Pa, performing polycondensation reaction for 6 hours, stopping the reaction when the product viscosity generates the pole climbing phenomenon, and cooling to room temperature to obtain the liquid crystal polymer with the structure of formula I-6.
The method for obtaining the aromatic diacid containing a thio ether group of D6 structure in this example comprises the following steps:
into the reaction flask, 5g of 4- (methoxy) phenol, 32.64g of 1, 8-dibromooctane, 150mL of acetone and 7.5g of potassium carbonate were charged, and after stirring was started and the reaction was completed after 20 hours at 70 ℃. After cooling to room temperature, the mixture was filtered, the filtrate was washed with acetone and filtered, and the filtrate was evaporated under reduced pressure to give a crude product. Ethanol was added to the crude product and pure product 6- (1) was obtained by recrystallization.
Into a reaction flask were charged 12.70g of pure product 6- (1), 125mL of cyclohexene, 125mL of ethanol, and 1.25g of Pd (OH) 2 The temperature was raised to 70℃and the mixture was stirred under reflux for 18h to terminate the reaction. After cooling to room temperature, filtration and evaporation of the filtrate under reduced pressure gave the crude product. To the crude product was added 24mL ethylene glycol monopropyl ether and 4.8mL ethyl acetate, and purified to give pure product 6- (2).
10.83g of 6- (2), 9.03g of 4- (6-bromohexyloxy) benzoic acid and 150mL of methylene chloride were added to the reaction flask, nitrogen was introduced under the action of DCC (4.9 g)/DMAP (0.20 g), stirring was started, and the reaction was completed after 18 hours at normal temperature. The mixture was filtered, the filtrate was washed with 150mL glacial acetic acid and then with 150mL water, and the layers were separated to leave an organic layer. After drying over sodium sulfate, filtration and evaporation under reduced pressure gave the crude product. Ethanol was added to the crude product and pure product 6- (3) was obtained by recrystallization.
To the reaction flask were added 8.76g of the product 6- (3), 13.68g of potassium thioacetate and 40ml of mf, and the reaction was terminated after stirring at room temperature for 5 hours. 40mL of water was added, the organic phase of the product was extracted with 80mL of ethyl acetate, then dried over sodium sulfate, filtered and evaporated under reduced pressure to give the crude product, to which ethanol was added, and pure product 6- (4) was obtained by recrystallization.
5.74g of product 6- (4) are dissolved in 30ml of THF and then 0.57g of NaBH are slowly added to the reaction flask at 0 ℃ 4 And 60mL of water, then washing the mixture with water after reacting for 24 hours at room temperature, then adding 60mL of methylene chloride to extract the organic phase of the product, then adding sodium sulfate to dry, filtering and evaporating under reduced pressure to obtain a crude product, adding 16mL of ethylene glycol monopropyl ether and 3.2mL of ethyl acetate to the crude product, and purifying to obtain a pure product 6- (5) dithiol aryl compound.
Adding pure product 6- (5) dithiol aryl compound and methyl 2-pentenoate according to the mol ratio of 1:2.4 in a reaction vessel with a reflux device and a stirring device, adding a mixture of a catalyst triethylamine and dimethylphenylphosphine and a free radical initiator AIBN, heating to 100 ℃, stirring and reacting for 10 hours to obtain an aromatic diester substance containing thioether groups, cooling to room temperature, adding excessive methanol and a proper amount of potassium hydroxide solution with the concentration of 10wt%, stirring and refluxing at 60-70 ℃ for 12 hours, and ending the reaction; after the reactant is cooled to room temperature, pouring distilled water, regulating the pH value to be 2-3 by hydrochloric acid for hydrolysis, generating precipitate, filtering, washing for a plurality of times by distilled water, filtering, and drying in a vacuum oven to obtain the aromatic diacid monomer D6 containing thioether groups.
Example 7
A flame-retardant liquid crystal polymer with rigidity and toughness is prepared by esterifying and polycondensing an aromatic diacid monomer D7 containing a thioether group and an aromatic diol monomer A7, and has the following reaction formula:
the specific reaction process is as follows: 10.96g of an aromatic diacid containing a thio ether group and having a D7 structure, 3.65g of an aromatic diol having an A7 structure, 0.0731g of stannous octoate and 0.0292g of zinc acetate are added into a reaction bottle with a reflux and stirring device; heating to 195 ℃ in nitrogen atmosphere, starting stirring and reacting for 7 hours, and when the distilled liquid reaches 70-80wt% of theoretical value, no bubbles are generated in the reaction system; then heating to 220 ℃, removing nitrogen, vacuumizing the reaction system, controlling the vacuum degree within 30Pa, performing polycondensation reaction for 5 hours, stopping the reaction when the product viscosity generates the pole climbing phenomenon, and cooling to room temperature to obtain the liquid crystal polymer with the structure of formula I-7.
The method for obtaining the aromatic diacid containing a thio ether group of D7 structure in this example:
19.44g of 1, 4-dibromobutane, 6.84g of bisphenol A, 150mL of acetone and 7.9g of potassium carbonate are added into a reaction bottle with a reflux and stirring device, the temperature is raised to 120-130 ℃, and the reaction is completed after the reflux and stirring reaction is carried out for 20 hours. After cooling to room temperature, washing with acetone, filtering, evaporating under reduced pressure to obtain a crude product, adding ethanol into the crude product, and obtaining a pure product 7- (1) through recrystallization.
14.94g of the product 7- (1), 27.36g of potassium thioacetate and 80 mM of MF were placed in a reaction flask, and the reaction was terminated after stirring at room temperature for 6 hours. 80mL of water was added, the organic phase of the product was extracted with 150mL of ethyl acetate, then dried over sodium sulfate, filtered and evaporated under reduced pressure to give the crude product, to which ethanol was added, and pure product 7- (2) was obtained by recrystallization.
14.64g of the product 7- (2) are dissolved in 60ml of THF and 1.13g of NaBH are slowly added to the reaction flask at 0 ℃ 4 And 40mL of water, then after 26h of reaction at room temperature, the mixture is washed with water, then 150mL of dichloromethane solvent is added to extract the organic phase of the product, then sodium sulfate is added to dry, filtration and evaporation under reduced pressure are carried out to obtain a crude product, 25mL of ethylene glycol monopropyl ether and 5mL of ethyl acetate are added to the crude product, and the pure product 7- (3) dithiol aryl compound is obtained after purification.
Adding pure product 7- (3) dithiol aryl compound and methyl acrylate in a molar ratio of 1:2.4 into a reaction vessel with a reflux device and a stirring device, adding a mixture of triethylamine and dimethylphenylphosphine serving as a catalyst and benzoyl peroxide serving as a free radical initiator, heating to 100 ℃, stirring and reacting for 10 hours to obtain an aromatic diester substance containing thioether groups, cooling to room temperature, adding excessive methanol and a proper amount of potassium hydroxide solution with concentration of 10wt%, stirring and refluxing at 60-70 ℃ for 12 hours, and ending the reaction; after the reactant is cooled to room temperature, pouring distilled water, regulating the pH value to be 2-3 by hydrochloric acid for hydrolysis, generating precipitate, filtering, washing for a plurality of times by distilled water, filtering, and drying in a vacuum oven to obtain the aromatic diacid monomer D7 containing thioether groups.
Example 8
A flame-retardant liquid crystal polymer with rigidity and toughness is prepared by esterifying and polycondensing an aromatic diacid monomer D8 containing a thioether group and an aromatic diol monomer A8, and has the following reaction formula:
wherein Ph is phenyl;
the specific reaction process is as follows: 13.16g of an aromatic diacid containing a thio ether group and having a D8 structure, 5.36g of an aromatic diol having an A8 structure, 0.0926g of stannous octoate and 0.0307g of zinc acetate are added into a reaction bottle with a reflux and stirring device; heating to 195 ℃ in a nitrogen atmosphere, starting stirring and reacting for 4 hours, and when the distilled liquid reaches 70-80wt% of the theoretical value, generating no bubbles in the reaction system; then heating to 220 ℃, removing nitrogen, vacuumizing the reaction system, controlling the vacuum degree within 30Pa, performing polycondensation reaction for 5 hours, stopping the reaction when the product viscosity generates the pole climbing phenomenon, and cooling to room temperature to obtain the liquid crystal polymer with the structure of formula I-8.
The method for obtaining the aromatic diacid containing the thiol group of D8 structure in this example:
13.38g of 4, 4-biphenyl dichloro, 6.36g of 4-mercapto-1-butanol, 100mL of toluene and 5.9g of potassium carbonate are added into a reaction bottle with a reflux and stirring device, the temperature is raised to 130-150 ℃, and the reaction is completed after the reflux and stirring reaction is carried out for 20 hours. After cooling to room temperature, washing with toluene, filtering, evaporating under reduced pressure to obtain a crude product, adding ethanol into the crude product, and recrystallizing to obtain a pure product 8- (1) dithiol aryl compound.
Adding pure product 8- (1) dithiol aryl compound and 2-phenyl-ethyl acrylate according to the mol ratio of 1:2.4 in a reaction vessel with a reflux device and a stirring device, adding a mixture of a catalyst triethylamine and dimethylphenylphosphine and a free radical initiator AIBN, heating to 100 ℃, stirring and reacting for 10 hours to obtain an aromatic diester substance containing thioether groups, cooling to room temperature, adding excessive methanol and a proper amount of potassium hydroxide solution with the concentration of 10wt%, stirring and refluxing at 60-70 ℃ for 12 hours, and ending the reaction; after the reactant is cooled to room temperature, pouring distilled water, regulating the pH value to be 2-3 by hydrochloric acid for hydrolysis, generating precipitate, filtering, washing for a plurality of times by distilled water, filtering, and drying in a vacuum oven to obtain the aromatic diacid monomer D8 containing thioether groups.
Example 9
A flame-retardant liquid crystal polymer with rigidity and toughness is prepared by esterifying and polycondensing an aromatic diacid monomer D9 containing a thioether group and an aromatic diol monomer A5, and has the following reaction formula:
the specific reaction process is as follows: 10g of an aromatic diacid containing a thiol ether group of D9 structure, 4.04g of an aromatic diol of A5 structure, 0.0702g of antimony trioxide and 0.0281g of tetrabutyl titanate are added into a reaction flask with a reflux and stirring device; heating to 190 ℃ in a nitrogen atmosphere, starting stirring and reacting for 4 hours, and when the distilled liquid reaches 70-80wt% of the theoretical value, generating no bubbles in the reaction system; then heating to 225 ℃, removing nitrogen, vacuumizing the reaction system, controlling the vacuum degree within 30Pa, performing polycondensation reaction for 6 hours, stopping the reaction when the product viscosity generates the pole climbing phenomenon, and cooling to room temperature to obtain the liquid crystal polymer with the structure of formula I-9.
The method for obtaining the aromatic diacid containing a thio ether group of D9 structure in this example:
6.89g of 4-bromo-1-butanol, 8.81g of 4- (5-bromopentyloxy) benzoic acid and 150mL of methylene chloride were added to the reaction flask, nitrogen was introduced under the action of DCC (3.9 g)/DMAP (0.16 g), stirring was turned on, and the reaction was completed after 20 hours at normal temperature. The mixture was filtered, the filtrate was washed with 100mL glacial acetic acid and then 100mL water, and the layers were separated to leave an organic layer. After drying over sodium sulfate, filtration and evaporation under reduced pressure gave the crude product. Ethanol was added to the crude product and pure product 9- (1) was obtained by recrystallization.
8.44g of the product 9- (1), 20.52g of potassium thioacetate and 50 mM of MF are added into a reaction flask, and the reaction is completed after stirring for 5 hours at room temperature; 50mL of water was added, the organic phase of the product was extracted with 100mL of ethyl acetate, then dried over sodium sulfate, filtered and evaporated under reduced pressure to give the crude product, to which ethanol was added, and recrystallized to give pure product 9- (2).
4.12g of the product 9- (2) are dissolved in 20ml of THF and then 0.57g of NaBH are slowly added to the reaction flask at 0 ℃ 4 And 50mL of water, then washing the mixture with water after reacting for 24 hours at room temperature, then adding 50mL of dichloromethane to extract the organic phase of the product, then adding sodium sulfate to dry, filtering and evaporating under reduced pressure to obtain a crude product, adding 14mL of ethylene glycol monopropyl ether and 2.5mL of ethyl acetate to the crude product, and purifying to obtain the pure product 9- (3) dithiol aryl compound.
Adding a pure product 9- (3) dithiol aryl compound and methyl methacrylate into a reaction vessel with a reflux device and a stirring device according to the mol ratio of 1:2.4, adding a mixture of a catalyst triethylamine and dimethylphenylphosphine and a free radical initiator benzoyl peroxide, heating to 100 ℃, stirring and reacting for 10 hours to obtain an aromatic diester substance containing thioether groups, cooling to room temperature, adding excessive methanol and a proper amount of potassium hydroxide solution with the concentration of 10wt%, stirring and refluxing at 60-70 ℃ for 12 hours, and ending the reaction; after the reactant is cooled to room temperature, pouring distilled water, regulating the pH value to be 2-3 by hydrochloric acid for hydrolysis, generating precipitate, filtering, washing for a plurality of times by distilled water, filtering, and drying in a vacuum oven to obtain the aromatic diacid monomer D9 containing thioether groups.
Example 10
A flame-retardant liquid crystal polymer with rigidity and toughness is prepared by esterifying and polycondensing an aromatic diacid monomer D10 containing a thioether group and an aromatic diol monomer A5, and has the following reaction formula:
the specific reaction process is as follows: into a reaction flask with reflux and stirring device were added 11.80g of an aromatic diacid containing a thiol group of D10 structure, 5.05g of an aromatic diol of A5 structure, 0.0843g of antimony trioxide and 0.0337g of zinc acetate; heating to 190 ℃ in a nitrogen atmosphere, starting stirring and reacting for 7 hours, and when the distilled liquid reaches 70-80wt% of the theoretical value, generating no bubbles in the reaction system; then heating to 210 ℃, removing nitrogen, vacuumizing the reaction system, controlling the vacuum degree within 30Pa, performing polycondensation reaction for 4 hours, stopping the reaction when the product viscosity generates the pole climbing phenomenon, and cooling to room temperature to obtain the liquid crystal polymer with the structure of formula I-10.
The method for obtaining the aromatic diacid containing a thio ether group of D10 structure in this example:
4.84g of ethyl 4-hydroxy-biphenyl-4-carboxylate, 17.28g of 1, 4-dibromobutane, 150mL of acetone and 4.4g of potassium carbonate are added into a reaction bottle, nitrogen is introduced, stirring is started, and the reaction is completed after 20 hours of reaction at 80 ℃. After cooling to room temperature, the mixture was filtered, the filtrate was washed with acetone and filtered, and the filtrate was evaporated under reduced pressure to give a crude product. Ethanol was added to the crude product and the pure product was obtained by recrystallization. And (3) regulating the pH value to be 2-3 by hydrochloric acid, hydrolyzing, filtering, washing for multiple times by using distilled water, filtering, and drying in a vacuum oven to obtain the product 10- (1).
10.47g of 10- (1), 4.59g of 4-bromo-1-butanol and 150mL of methylene chloride were added to the reaction flask, nitrogen was introduced under the action of DCC (3.76 g)/DMAP (0.15 g), stirring was turned on, and the reaction was completed after 20 hours at normal temperature. The mixture was filtered, the filtrate was washed with 100mL glacial acetic acid and then 100mL water, and the layers were separated to leave an organic layer. After drying over sodium sulfate, filtration and evaporation under reduced pressure gave the crude product. Ethanol was added to the crude product and pure product 10- (2) was obtained by recrystallization.
9.68g of the product 10- (2), 22.80g of potassium thioacetate and 100 mM of MF were placed in a reaction flask, and the reaction was terminated after stirring at room temperature for 5 hours. 100mL of water was added, the organic phase of the product was extracted with 150mL of ethyl acetate, then dried over sodium sulfate, filtered and evaporated under reduced pressure to give the crude product, to which ethanol was added, and recrystallized to give pure product 10- (3).
7.11g of product 10- (3) are dissolved in 40ml of THF and then 0.57g of NaBH are slowly added to the reaction flask at 0 ℃ 4 And 80mL of water, then after 26h of reaction at room temperature, the mixture is washed with water, then 80mL of dichloromethane solvent is added to extract the organic phase of the product, then sodium sulfate is added to dry, filtration and reduced pressure evaporation are carried out to obtain a crude product, 20mL of ethylene glycol monopropyl ether and 4mL of ethyl acetate are added to the crude product, and the pure product 10- (4) dithiol aryl compound is obtained after purification.
Adding pure product 10- (4) dithiol aryl compound and 2-ethyl acrylate according to the mol ratio of 1:2.4 in a reaction vessel with a reflux device and a stirring device, adding a mixture of a catalyst triethylamine and dimethylphenylphosphine and a free radical initiator benzoyl peroxide, heating to 100 ℃, stirring and reacting for 10 hours to obtain an aromatic diester substance containing thioether groups, cooling to room temperature, adding excessive methanol and a proper amount of potassium hydroxide solution with the concentration of 10wt%, stirring and refluxing at 60-70 ℃ for 12 hours, and ending the reaction; after the reactant is cooled to room temperature, pouring distilled water, regulating the pH value to be 2-3 by hydrochloric acid for hydrolysis, generating precipitate, filtering, washing for a plurality of times by distilled water, filtering, and drying in a vacuum oven to obtain the aromatic diacid monomer D10 containing thioether groups.
Example 11
A flame-retardant liquid crystal polymer with rigidity and toughness is prepared by esterifying and polycondensing an aromatic diacid monomer D11 containing a thioether group and an aromatic diol monomer A3, and has the following reaction formula:
the specific reaction process is as follows: 15.16g of an aromatic diacid containing a thio ether group of the D11 structure, 3.72g of an aromatic diol of the A3 structure, 0.0944g of stannous octoate and 0.0378g of zinc acetate are added to a reaction flask with a reflux and stirring device; heating to 195 ℃ in a nitrogen atmosphere, starting stirring and reacting for 4 hours, and when the distilled liquid reaches 70-80wt% of the theoretical value, generating no bubbles in the reaction system; then heating to 230 ℃, removing nitrogen, vacuumizing the reaction system, controlling the vacuum degree within 30Pa, performing polycondensation reaction for 5 hours, stopping the reaction when the product viscosity generates the pole climbing phenomenon, and cooling to room temperature to obtain the liquid crystal polymer with the structure of formula I-8.
The method for obtaining the aromatic diacid containing a thio ether group of D11 structure in this example comprises the following steps:
6.02g of 4- (6-bromohexyloxy) benzoic acid, 5.52g of 4-hydroxy-1-benzoic acid and 150mL of methylene dichloride are added into a reaction bottle, nitrogen is introduced under the action of DCC (4.5 g)/DMAP (0.18 g), stirring is started, 6.68g of 5-bromo-1-pentanol is added after the reaction is carried out for 16 hours at normal temperature, and the reaction is finished after the reaction is continued for 24 hours. The mixture was filtered, the filtrate was washed with 150mL glacial acetic acid and then with 150mL water, and the layers were separated to leave an organic layer. After drying over sodium sulfate, filtration and evaporation under reduced pressure gave the crude product. Ethanol was added to the crude product and pure product 11- (1) was obtained by recrystallization.
11.4g of the product 11- (1), 22.52g of potassium thioacetate and 60 mM of MF were placed in a reaction flask, and the reaction was terminated after stirring at room temperature for 5 hours. 60mL of water was added, the organic phase of the product was extracted with 120mL of ethyl acetate, then dried over sodium sulfate, filtered and evaporated under reduced pressure to give the crude product, to which ethanol was added, and pure product 11- (2) was obtained by recrystallization.
11.2g of the product 11- (2) are dissolved in 60ml of THF and then 0.98g of NaBH are slowly added to the reaction flask at 0 ℃ 4 And 150mL of water, then the mixture is washed with water after being reacted for 26 hours at room temperature, then 150mL of dichloromethane solvent is added to extract the organic phase of the product, then sodium sulfate is added to dry, and the crude product is obtained by filtration and evaporation under reduced pressure, and the reaction is carried out in the presence ofTo the product was added 30mL of ethylene glycol monopropyl ether and 6mL of ethyl acetate, and the pure product 11- (3) dithiol aryl was obtained after purification.
Adding pure product 11- (3) dithiol aryl compound and 2-phenyl-ethyl acrylate according to the mol ratio of 1:2.4 in a reaction vessel with a reflux device and a stirring device, adding a mixture of a catalyst triethylamine and dimethylphenylphosphine and a free radical initiator AIBN, heating to 100 ℃, stirring and reacting for 10 hours to obtain an aromatic diester substance containing thioether groups, cooling to room temperature, adding excessive methanol and a proper amount of potassium hydroxide solution with the concentration of 10wt%, stirring and refluxing at 60-70 ℃ for 12 hours, and ending the reaction; after the reactant is cooled to room temperature, pouring distilled water, regulating the pH value to be 2-3 by hydrochloric acid for hydrolysis, generating precipitate, filtering, washing for a plurality of times by distilled water, filtering, and drying in a vacuum oven to obtain the aromatic diacid monomer D11 containing thioether groups.
Comparative example 1
The material of this comparative example was Japanese Bao Li T130 LCP liquid crystal polymer.
Comparative example 2
The material of this comparative example was DuPont A410 Vectra LCP liquid crystal polymer.
Test bars were prepared by a mini-injection molding machine for testing the relevant properties for the above examples and comparative materials, and the results are shown in Table 1.
Table 1 example and comparative example material related properties
As is clear from the data in Table 1, the liquid crystal polymer obtained by the present invention has both rigidity and toughness by comparison with the comparative examples. As can be seen from melt flow rate data, the introduction of thioether and/or substituent groups on the molecular main chain is beneficial to reducing the acting force of the molecular chain, improving the fluidity of the liquid crystal polymer, and being easy to process and mold, and meanwhile, the introduction of thioether and/or fluorine ensures that the liquid crystal polymer has rigidity and toughness, obtains high flame retardant property and is beneficial to widening the application range of the liquid crystal polymer.
The specific structure of the flame retardant liquid crystal polymer with rigidity and toughness according to the present invention is shown in a series of structures of formula i, which is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art who is familiar with the technical scope of the present invention can apply equivalent substitutions or alterations according to the technical scheme of the present invention and the inventive concept thereof, and all the modifications are covered in the scope of the present invention.

Claims (8)

1. The flame-retardant liquid crystal polymer with rigidity and toughness is characterized by comprising the following chemical structures:
，
wherein R is 0 Has one of the following structures:
、/>、
；
wherein R is 5 And R is 7 Is one of phenyl, n-alkyl with 4-8 carbon atoms or isomeric alkyl radical, R 5 And R is 7 May be the same or different;
R 6 is one of phenyl, biphenyl, naphthyl, diphenyl ether group, diphenyl propyl group and diphenyl ester group;
R 1 is one of hydrogen, methyl and ethyl;
R 2 is one of hydrogen, methyl, ethyl and phenyl;
R 3 is methylene, the number of the methylene is 0-7;
R 4 is one of phenyl, biphenyl, diphenyl ether, aromatic radical containing at least one fluorine atom and aromatic cycloalkyl;
wherein the value range of n is 5-95.
2. The method for preparing a flame retardant liquid crystal polymer with rigidity and toughness as claimed in claim 1, wherein the liquid crystal polymer is obtained by esterification and polycondensation of aromatic diol monomers and aromatic diacid monomers containing thioether groups;
the chemical structure of the aromatic diacid monomer containing the thioether group is as follows:
；
the chemical structure of the aromatic diol is as follows:。
3. the method for preparing a flame retardant liquid crystal polymer with rigidity and toughness according to claim 2, wherein the aromatic diol can be but not limited to the following substances: hydroquinone, 4'- (1, 4-phenylene diisopropyl) diphenol, diphenyl diphenol, 2' -diphenyl dimethanol, 3 '-dimethyl-4, 4' -diphenyl diphenol, 2, 4-difluoro catechol 2, 3-difluorohydroquinone, 4 '-dihydroxydiphenyl ether, 2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1' -bis (4-hydroxyphenyl) cyclohexane.
4. The method for preparing the flame-retardant liquid crystal polymer with rigidity and toughness as claimed in claim 2, wherein the aromatic diacid monomer containing the thioether group is obtained by reacting a dithiol aryl compound and a vinyl acid ester compound under the action of a first catalyst and a free radical initiator to generate an aromatic diester substance containing the thioether group, and then hydrolyzing to obtain the aromatic diacid monomer containing the thioether group;
the dithiol aryl compound is a dithiol compound comprising an ether bond and/or an ester group in its main chain structure, and a phenyl group and/or an alkyl group;
the vinyl acid ester compound has a structural formula as follows:
；
wherein R is 1 Is one of hydrogen, methyl and ethyl;
R 2 is one of hydrogen, methyl, ethyl and phenyl;
R 3 is methylene, the number of the methylene is 0-7;
R 8 is one of methyl and ethyl;
the first catalyst is a mixture of triethylamine and dimethylphenylphosphine;
the free radical initiator is AIBN or benzoyl peroxide.
5. The method for preparing a flame retardant liquid crystal polymer with both rigidity and toughness according to claim 4, wherein the vinyl acid ester compound is one of methyl acrylate, 2-phenyl-ethyl acrylate, methyl methacrylate, 2-ethylene-ethyl benzoate, 2-methyl pentenoate and 2-ethyl acrylate.
6. The method for preparing the flame-retardant liquid crystal polymer with rigidity and toughness according to claim 2, which is characterized by comprising the following steps: heating the aromatic diacid monomer containing the thioether group and the aromatic diol monomer to 180-200 ℃ under the action of a second catalyst and nitrogen atmosphere, carrying out esterification reaction for 4-7h under stirring, continuously heating to 210-230 ℃ after no bubbles are generated in a reaction system, removing nitrogen after reaching the temperature, vacuumizing the reaction system until the vacuum degree is kept within 30Pa, carrying out polycondensation reaction for 3-6h, stopping the reaction when the product generates a pole climbing phenomenon, and cooling to room temperature to obtain the liquid crystal polymer.
7. The method for preparing a flame retardant liquid crystal polymer with both rigidity and toughness according to claim 6, wherein the molar ratio of the aromatic diol monomer to the aromatic diacid monomer containing the thio ether group is 1.1-1.25:1.
8. The preparation method of the flame-retardant liquid crystal polymer with both rigidity and toughness according to claim 6, wherein the second catalyst consists of a main catalyst and a cocatalyst, wherein the addition amount of the main catalyst is 0.5% of the total mass of the reaction monomers, and the addition amount of the cocatalyst is 0.2% of the total mass of the reaction monomers; the main catalyst is one of stannous octoate and antimony trioxide, and the cocatalyst is one of zinc acetate and tetrabutyl titanate.
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