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CN113024785A - Low dielectric heating induced liquid crystal polymer and preparation method thereof - Google Patents

Low dielectric heating induced liquid crystal polymer and preparation method thereof Download PDF

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Publication number
CN113024785A
CN113024785A CN202110161289.5A CN202110161289A CN113024785A CN 113024785 A CN113024785 A CN 113024785A CN 202110161289 A CN202110161289 A CN 202110161289A CN 113024785 A CN113024785 A CN 113024785A
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liquid crystal
diacid
crystal polymer
diether
thermotropic liquid
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王贤文
廖坚良
李培骏
黄文刚
潘宏程
梁军
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Guangdong Youju Advanced New Material Co Ltd
Guilin University of Technology
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Guangdong Youju Advanced New Material Co Ltd
Guilin University of Technology
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    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C09K19/3804—Polymers with mesogenic groups in the main chain
    • C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides

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Abstract

The invention discloses a low dielectric heating induced liquid crystal polymer and a preparation method thereof, wherein the liquid crystal polymer comprises the following repeating units derived from the following monomers in percentage by mol: 40-60 mol% of p-hydroxybenzoic acid; 10-20 mol% of aromatic diethanedioic acid; 5-10 mol% of terephthalic acid; 5-10 mol% of isophthalic acid; 10-20 mol% of bisphenol S; 5-15 mol% of biphenyl diphenol. According to the invention, aromatic diethanedioic acid and bisphenol S are selected, and a non-conjugated molecular structure is introduced into a liquid crystal polymer molecular chain to reduce the electron mobility of a molecular main chain, so that the dielectric constant of the liquid crystal polymer is reduced; the thermotropic liquid crystal polymer with low dielectric constant and high mechanical strength is prepared by controlling the content ratio of each monomer structure, and the requirements of 5G technology development on low dielectric materials can be met.

Description

Low dielectric heating induced liquid crystal polymer and preparation method thereof
Technical Field
The invention relates to the field of high molecular materials, in particular to a low dielectric heating induced liquid crystal polymer and a preparation method thereof.
Background
With the continuous development of 5G technology in recent years, mobile communication speed is faster and faster, the requirement on the dielectric property of materials is higher, and materials with low dielectric constant become a research hotspot in the industry.
Thermotropic Liquid Crystalline Polymer (TLCP) is a rigid polymer that has both liquid fluidity and crystalline anisotropy at temperatures above the melting or glass transition temperature. Due to the rigid chain structure and the ordered arrangement among molecules, the TLCP has excellent comprehensive physical and mechanical properties and is widely applied to the fields of aerospace, electronics and electrical, automobile industry and the like. Currently commercially available TLCPs comprise wholly aromatic polyesters, semi-aromatic polyesters, polyester-amides and other polymers. The traditional wholly aromatic polyester TLCP is mainly synthesized by p-hydroxybenzoic acid (HBA), Biphenol (BP) and Terephthalic Acid (TA)/Isophthalic Acid (IA) monomers with different proportions, has good mechanical properties, but has high dielectric constant, and limits the application thereof. Therefore, the research on the material with low dielectric constant and high mechanical strength has better market prospect.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a thermotropic liquid crystal polymer which has low dielectric constant and high mechanical strength.
Another object of the present invention is to provide a method for preparing the low dielectric thermotropic liquid crystal polymer.
The invention is realized by the following technical scheme:
a low dielectric thermotropic liquid crystalline polymer comprising repeating units derived from the following monomers in mole percent:
40-60 mol% of p-hydroxybenzoic acid;
10-20 mol% of aromatic diethanedioic acid;
5-10 mol% of terephthalic acid;
5-10 mol% of isophthalic acid;
10-20 mol% of bisphenol S;
5-15 mol% of biphenyl diphenol.
The ratio of the sum of the mole numbers of the aromatic diether diacid, the terephthalic acid and the isophthalic acid to the sum of the mole numbers of the bisphenol S and the diphenol is 1: (0.85-1.20).
The structure of the aromatic diether diacid is any one of a formula (I), a formula (II) or a formula (III),
Figure 801481DEST_PATH_IMAGE001
formula (I)
Figure 494631DEST_PATH_IMAGE002
Formula (II)
Figure 149603DEST_PATH_IMAGE003
Formula (III)
Wherein R is1Is selected from
Figure 902795DEST_PATH_IMAGE004
、
Figure 908798DEST_PATH_IMAGE005
、
Figure 405638DEST_PATH_IMAGE006
Any one of a heterocyclic aromatic group or a polycyclic aromatic group; n is a positive integer greater than or equal to 1; the R is2Is selected from
Figure 446275DEST_PATH_IMAGE007
、
Figure 104790DEST_PATH_IMAGE008
、
Figure 99553DEST_PATH_IMAGE009
、
Figure 134505DEST_PATH_IMAGE010
、
Figure 232911DEST_PATH_IMAGE011
、
Figure 186960DEST_PATH_IMAGE012
、
Figure 308500DEST_PATH_IMAGE013
、
Figure 271777DEST_PATH_IMAGE014
Oxygen atom, sulfur atom or a linear or branched aliphatic divalent group of more than 6 carbon atoms, wherein n2Is a positive integer of 1-6; the heterocyclic aromatic group is an aromatic group in which atoms constituting a ring contain at least one hetero atom in addition to carbon atoms; the polycyclic aromatic group means an aromatic group in which two or more benzene rings are connected in a fused ring form.
Preferably, the aromatic diether diacid has a structure of
Figure 460575DEST_PATH_IMAGE001
The ether bond is at para position on benzene ring, so the activity is stronger and the reaction is easy to proceed.
Specifically, the aromatic diether diacid is selected from any one or more of bisphenol A diether diacid, bisphenol S diether diacid, biphenol diether diacid, 6 ' -dihydroxy-2, 2 ' -bipyridyl diether diacid, 2, 6-naphthalene diphenol diether diacid, bis (4,4' -dihydroxy) phenyl acetylene diether diacid, dihydroxy benzophenone diether diacid, dihydroxy diphenyl ether diether diacid, dihydroxy diphenyl sulfide diether diacid or phenol diether diacid. .
The aromatic diethanedioic acid of the invention can be obtained commercially; can also be prepared by the following method:
(1) adding aromatic diphenol, basic carbonate, p-chlorobenzonitrile, N-methyl pyrrolidone and a water diversion agent into a reaction device, heating to 130-160 ℃, refluxing and water diversion, stirring and heating to 170-200 ℃ after water is not drained, reacting for 3-5 hours, finishing the reaction, filtering a product, washing a solid with water, and drying to obtain aromatic diether dicarbonitrile;
(2) adding aromatic diether dicarbonitrile, alkali and an alcohol solvent into a reaction device, heating to 100-150 ℃, refluxing, after the reaction is finished, acidifying with inorganic acid until the pH of the solution is 2-3, filtering, washing with water to be neutral, and drying to obtain the aromatic diether diacid.
The melting point of the thermotropic liquid crystal polymer is 200-380 ℃; preferably, the melting point of the thermotropic liquid crystal polymer is 250-370 ℃; more preferably, the melting point of the thermotropic liquid crystal polymer is 280-360 ℃.
The invention also provides a preparation method of the low-dielectric thermotropic liquid crystal polymer, which comprises the following steps:
(1) adding an acetic anhydride solution into a reaction kettle according to a ratio, adding p-hydroxybenzoic acid, aromatic diether diacid, isophthalic acid, terephthalic acid, bisphenol S, biphenol and a catalyst, heating to 50-160 ℃, acetylating for 1-2 h, heating to 285-335 ℃ at a speed of 1-3 ℃/h, carrying out heat preservation reaction for 7-10 h, discharging at a high temperature, cooling, and then carrying out grain cutting or crushing to obtain a prepolymer;
(2) and (2) putting the prepolymer obtained in the step (1) into a reaction kettle, and carrying out solid-phase polycondensation for 5-48 hours under the condition that the melting point of the prepolymer is 20-30 ℃ lower, so as to obtain the low dielectric heating induced liquid crystal polymer.
Wherein the dosage of the acetic anhydride is 1.1 to 1.5 times of the sum of the mole numbers of hydroxyl in p-hydroxybenzoic acid, biphenol and bisphenol S; the dosage of the catalyst is 0.01-0.1% of the total mole number of the monomers.
Preferably, the dosage of the acetic anhydride is 1.2 to 1.3 times of the sum of the mole numbers of hydroxyl in the p-hydroxybenzoic acid, the biphenol and the bisphenol S.
The catalyst is selected from any one of nitrogen-containing organic matters or acetate; preferably, the catalyst is selected from any one of N-methylimidazole, zinc acetate, potassium acetate, magnesium acetate or calcium acetate.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, aromatic diethanedioic acid and bisphenol S are selected, and a non-conjugated molecular structure is introduced into a liquid crystal polymer molecular chain to reduce the electron mobility of a molecular main chain, so that the dielectric constant of the liquid crystal polymer is reduced; the thermotropic liquid crystal polymer with low dielectric constant and high mechanical strength is prepared by controlling the content ratio of each monomer structure, and the requirements of 5G technology development on low dielectric materials can be met.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
The materials used in the examples and comparative examples of the present invention are described below, but not limited to these materials.
The aromatic diether diacids used in the examples of the invention and the comparative examples were prepared by the following method, using the starting materials commercially available:
(1) adding aromatic diphenol, anhydrous potassium carbonate, parachlorobenzonitrile, N-methylpyrrolidone and a water diversion agent into a reaction device, heating to 130-160 ℃, refluxing and diverting water, stirring and heating to 170-200 ℃ after no water comes out, reacting for 3-5 hours, then finishing the reaction, filtering a product, washing a solid with water, and drying to obtain aromatic diether dicarbonitrile;
(2) adding aromatic diether dicarbonitrile, alkali and an alcohol solvent into a reaction device, heating to 100-150 ℃, refluxing, after the reaction is finished, acidifying with hydrochloric acid until the pH of the solution is 2-3, filtering, washing with water to be neutral, and drying to obtain the aromatic diether diacid.
The aromatic diphenol is bisphenol A, bisphenol S and diphenol, and bisphenol A diethanedioic acid, bisphenol S diethanedioic acid and diphenol diethanedioic acid are respectively prepared.
The other sources of raw materials used in the examples of the invention and comparative examples are as follows:
p-hydroxybenzoic acid: saint chemical, Zhejiang;
terephthalic acid: jiangsu Runhu chemical Co., Ltd;
isophthalic acid: mitsubishi chemical industry;
biphenyl diphenol: ita loyalty (china) group ltd;
bisphenol S: southeast baisheng chemical company;
acetic anhydride: dongguan neutralization chemical industry;
n-methylimidazole: shanghai Demao chemical Co., Ltd.
Example 1:
(1) 367.52g of acetic anhydride solution was put into a reaction vessel equipped with a stirrer, a torque meter, a nitrogen inlet tube, a thermometer and a reflux condenser, 207.19g of p-hydroxybenzoic acid, 210.60g of bisphenol A diethanedioic acid, 24.92g of terephthalic acid, 24.92g of isophthalic acid, 112.62g of bisphenol S and 55.86g of biphenyldiol were added, and they were mixed by stirring, and 0.25g of N-methylimidazole was added to the mixture after stirring. Introducing nitrogen to fully displace the air in the reaction kettle, raising the temperature of the mixture to 150 ℃ within 20 minutes under the flow of the nitrogen, performing reflux acetylation reaction for 1 hour, then raising the temperature to 325 ℃ at the speed of 1 ℃/h, performing heat preservation reaction for 7 hours, discharging at high temperature after the reaction is finished, cooling, crushing, and performing vacuum drying on the crushed material at 130 ℃ for 2 hours to obtain a prepolymer;
(2) and (2) putting the prepolymer obtained in the step (1) into a reaction kettle, and carrying out solid-phase polycondensation reaction for 10 hours at a temperature of 30 ℃ lower than the melting point of the prepolymer in a nitrogen atmosphere to obtain the low dielectric thermally induced liquid crystal polymer.
Example 2:
example 2 is different from example 1 in that 220.5g of bisphenol S type diethanedioic acid is used as the aromatic diethanedioic acid; the preparation method is the same as that of example 1.
Example 3:
example 3 is different from example 1 in that 191.7g of diphenol diether diacid is selected as aromatic diether diacid; the preparation method is the same as that of example 1.
Example 4:
example 4 differs from example 1 in that aromatic diether diacid is selected from bisphenol A diether diacid 140.4g, terephthalic acid 37.39g and isophthalic acid 37.39 g; the preparation method is the same as that of example 1.
Example 5:
example 5 differs from example 1 in that aromatic diether diacid is selected from bisphenol A diether diacid 140.4g, terephthalic acid 24.92g and isophthalic acid 49.84 g; the preparation method is the same as that of example 1.
Example 6:
example 6 differs from example 1 in that aromatic diether diacid is selected from bisphenol A diether diacid 140.4g, terephthalic acid 49.84g and isophthalic acid 24.92 g; the preparation method is the same as that of example 1.
Example 7:
example 7 differs from example 1 in that 150.16g of bisphenol S, 27.93g of biphenol; the preparation method is the same as that of example 1.
Example 8:
example 8 differs from example 1 in that each monomer is 240.34g of p-hydroxybenzoic acid, 176.4g of bisphenol S diether diacid, 24.92g of terephthalic acid, 24.92g of isophthalic acid, 75.08g of bisphenol S, 55.86g of biphenol; the preparation method is the same as that of example 1.
Example 9:
example 9 differs from example 1 in that the monomers were p-hydroxybenzoic acid 182.33g, biphenol-type diethanedioic acid 230.04g, terephthalic acid 24.92g, isophthalic acid 24.92g, bisphenol S135.15 g, biphenol 55.86 g; the preparation method is the same as that of example 1.
Comparative example 1:
207.19g of p-hydroxybenzoic acid, 210.60g of bisphenol A diethanedioic acid, 24.92g of terephthalic acid, 24.92g of isophthalic acid, 112.62g of bisphenol S, 55.86g of biphenol,
comparative example 2:
comparative example 2 differs from example 1 in that the monomers used were only 331.51g of p-hydroxybenzoic acid, 24.92g of terephthalic acid, 24.92g of isophthalic acid, 55.86g of biphenol; the preparation method is the same as that of example 1.
Comparative example 3:
comparative example 3 differs from example 1 in that the monomers used were only 290.07g of p-hydroxybenzoic acid, 210.60g of bisphenol A diether diacid, and S112.62g of bisphenol; the preparation method is the same as that of example 1.
Comparative example 4:
comparative example 4 differs from example 1 in that the monomers used were only 207.19g of p-hydroxybenzoic acid, 210.6g of bisphenol A diethanedioic acid, 24.92g of terephthalic acid, 24.92g of isophthalic acid, 139.66g of biphenol; the preparation method is the same as that of example 1.
Comparative example 5:
comparative example 5 differs from example 1 in that the monomers used were only 207.19g of p-hydroxybenzoic acid, 62.31g of terephthalic acid, 62.31g of isophthalic acid, 112.62g of bisphenol S, 55.86g of biphenol; the preparation method is the same as that of example 1.
Relevant performance test methods or standards:
(1) melting point: DSC test, heating to 400 ℃ at a speed of 10 ℃/min under the nitrogen atmosphere, then cooling to 30 ℃ at a speed of 10 ℃/min, and heating to 400 ℃ at a speed of 10 ℃/min; the polymer melting point temperature was measured by Differential Scanning Calorimetry (DSC);
(2) mechanical properties: the test method for tensile strength is according to standard ISO 527; the test method for flexural strength is referred to standard ISO 178;
(3) dielectric constant: the test method is referred to IEC 60250-.
Table 1: the monomer ratios (in mol percent) in examples 1 to 9 and comparative examples 1 to 5 and the performance test results of the prepared liquid crystal polymers
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7
P-hydroxybenzoic acid 50 50 50 50 50 50 50
Bisphenol A type diethanedioic acid 15 10 10 10 15
Bisphenol S type diethanedioic acid 15
Diphenyl diphenol diether diacid 15
Terephthalic acid (TPA) 5 5 5 7.5 5 10 5
Isophthalic acid 5 5 5 7.5 10 5 5
Bisphenol S 15 15 15 15 15 15 20
Biphenyldiphenol 10 10 10 10 10 10 5
Melting Point C 350.9 358.2 337.1 345.6 341.7 348.0 352.5
Tensile strength/MPa 138.0 143.6 126.2 133.1 130.9 137.2 140.3
Flexural Strength/MPa 137.2 144.0 127.6 134.9 132.2 135.0 140.9
Dielectric constant 2.71 2.86 2.82 2.78 2.76 2.79 2.73
Table 1 is shown below:
example 8 Example 9 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5
P-hydroxybenzoic acid 58 44 70 80 70 50 50
Bisphenol A type diethanedioic acid 5 / 15 15 /
Bisphenol S type diethanedioic acid 12
Diphenyl diphenol diether diacid 18
Terephthalic acid (TPA) 5 5 5 5 / 5 12.5
Isophthalic acid 5 5 5 5 / 5 12.5
Bisphenol S 10 18 5 / 15 / 15
Biphenyldiphenol 10 10 10 10 / 25 10
Melting Point C 357.6 339.9 307.3 291.0 328.6 310.3 293.5
Tensile strength/MPa 142.9 129.1 111.3 98.5 119.3 107.0 97.6
Flexural Strength/MPa 141.2 130.8 114.6 99.8 118.5 103.3 100.2
Dielectric constant 2.85 2.83 3.01 3.46 3.04 2.99 3.14
As can be seen from the above examples and comparative examples, the thermotropic liquid crystalline polymer prepared by the present invention has a low dielectric constant while having excellent tensile strength and bending strength.

Claims (10)

1.一种低介电热致液晶聚合物，其特征在于，按摩尔百分比计，包含衍生自以下单体的重复单元：1. A low-dielectric thermotropic liquid crystal polymer, characterized in that, on a molar percentage basis, it comprises repeating units derived from the following monomers: 对羟基苯甲酸 40~60mol%；p-Hydroxybenzoic acid 40~60mol%; 芳香型二醚二酸 10~20mol%；Aromatic diether diacid 10~20mol%; 对苯二甲酸 5~10mol%；5~10mol% of terephthalic acid; 间苯二甲酸 5~10mol%；Isophthalic acid 5~10mol%; 双酚S 10~20mol%；Bisphenol S 10~20mol%; 联苯二酚 5~15mol%。Biphenol 5~15mol%. 2.根据权利要求1所述的低介电热致液晶聚合物，其特征在于，所述的芳香型二醚二酸、对苯二甲酸、间苯二甲酸的摩尔数之和与双酚S、联苯二酚的摩尔数之和的比值为1：（0.85~1.20）。2 . The low-dielectric thermotropic liquid crystal polymer according to claim 1 , wherein the sum of the moles of the aromatic diether diacid, terephthalic acid and isophthalic acid and bisphenol S , the ratio of the sum of the moles of biphenol is 1: (0.85~1.20). 3.根据权利要求1所述的低介电热致液晶聚合物，其特征在于，所述的芳香型二醚二酸的结构为式（Ⅰ）、式（Ⅱ）或式（Ⅲ）中的任意一种，3 . The low-dielectric thermotropic liquid crystal polymer according to claim 1 , wherein the aromatic diether diacid has the structure of formula (I), formula (II) or formula (III). 4 . any one,
Figure 99331DEST_PATH_IMAGE001
式（Ⅰ）
Figure 99331DEST_PATH_IMAGE001
Formula (I)
Figure 813209DEST_PATH_IMAGE002
式（Ⅱ）
Figure 813209DEST_PATH_IMAGE002
Formula (II)
Figure 874837DEST_PATH_IMAGE003
式（Ⅲ）
Figure 874837DEST_PATH_IMAGE003
Formula (III) 其中，R1选自
Figure 801205DEST_PATH_IMAGE004
、
Figure 412315DEST_PATH_IMAGE005
、
Figure 765936DEST_PATH_IMAGE006
、杂环芳香基团或多环芳香基团中的任意一种；所述n为大于或等于1的正整数；所述R2选自
Figure 314860DEST_PATH_IMAGE007
、
Figure 44919DEST_PATH_IMAGE008
、
Figure 244956DEST_PATH_IMAGE009
、
Figure 769478DEST_PATH_IMAGE010
、
Figure 805698DEST_PATH_IMAGE011
、
Figure 73869DEST_PATH_IMAGE012
、
Figure 128412DEST_PATH_IMAGE013
、
Figure 89415DEST_PATH_IMAGE014
、氧原子、硫原子或高于6个碳原子的直链或支化的脂肪族二价基团中的任意一种，其中，n2为1~6的正整数；所述杂环芳香基团是指构成环的原子除碳原子外，还至少含有一个杂原子的芳香基团；所述多环芳香基团是指两个或两个以上苯环以稠环形式相连的芳香基团。wherein R 1 is selected from
Figure 801205DEST_PATH_IMAGE004
,
Figure 412315DEST_PATH_IMAGE005
,
Figure 765936DEST_PATH_IMAGE006
, any one of heterocyclic aromatic groups or polycyclic aromatic groups; the n is a positive integer greater than or equal to 1; the R 2 is selected from
Figure 314860DEST_PATH_IMAGE007
,
Figure 44919DEST_PATH_IMAGE008
,
Figure 244956DEST_PATH_IMAGE009
,
Figure 769478DEST_PATH_IMAGE010
,
Figure 805698DEST_PATH_IMAGE011
,
Figure 73869DEST_PATH_IMAGE012
,
Figure 128412DEST_PATH_IMAGE013
,
Figure 89415DEST_PATH_IMAGE014
, oxygen atom, sulfur atom or any one of straight-chain or branched aliphatic divalent groups higher than 6 carbon atoms, wherein, n 2 is a positive integer of 1 to 6; the heterocyclic aromatic group A group refers to an aromatic group in which the atoms constituting the ring also contain at least one heteroatom in addition to carbon atoms; the polycyclic aromatic group refers to an aromatic group in which two or more benzene rings are connected in the form of condensed rings. 4.根据权利要求3所述的低介电热致液晶聚合物，其特征在于，所述的芳香型二醚二酸的结构为
Figure 612931DEST_PATH_IMAGE001
。4. The low-dielectric thermotropic liquid crystal polymer according to claim 3, wherein the structure of the aromatic diether diacid is
Figure 612931DEST_PATH_IMAGE001
. 5.根据权利要求3所述的低介电热致液晶聚合物，其特征在于，所述的芳香型二醚二酸选自双酚A型二醚二酸、双酚S型二醚二酸、联苯二酚型二醚二酸、6,6’-二羟基-2,2’-联吡啶型二醚二酸、2,6-萘二酚型二醚二酸、二(4,4'-二羟基)苯基乙炔型二醚二酸、二羟基二苯甲酮二醚二酸、二羟基二苯醚二醚二酸、二羟基二苯硫醚二醚二酸或苯酚型二醚二酸中的任意一种或几种。5 . The low-dielectric thermotropic liquid crystal polymer according to claim 3 , wherein the aromatic diether diacid is selected from the group consisting of bisphenol A type diether diacid and bisphenol S type diether diacid. 6 . , biphenol-type diether diacid, 6,6'-dihydroxy-2,2'-bipyridine-type diether diacid, 2,6-naphthalenediol-type diether diacid, bis(4,4 '-Dihydroxy)phenylacetylene type diether diacid, dihydroxybenzophenone diether diacid, dihydroxydiphenyl ether diether diacid, dihydroxydiphenyl sulfide diether diacid or phenol type diether Any one or more of the diacids. 6.根据权利要求1所述的低介电热致液晶聚合物，其特征在于，所述热致液晶聚合物的熔点为200℃~380℃；优选的，所述热致液晶聚合物的熔点为250℃~370℃；更优选的，所述热致液晶聚合物的熔点为280℃~360℃。6 . The low-dielectric thermotropic liquid crystal polymer according to claim 1 , wherein the melting point of the thermotropic liquid crystal polymer is 200° C. to 380° C.; preferably, the melting point of the thermotropic liquid crystal polymer is 250°C to 370°C; more preferably, the melting point of the thermotropic liquid crystal polymer is 280°C to 360°C. 7.根据权利要求1~6任一项所述的低介电热致液晶聚合物的制备方法，其特征在于，包括以下步骤：7. The preparation method of the low-dielectric thermotropic liquid crystal polymer according to any one of claims 1 to 6, characterized in that, comprising the following steps: （1）按照配比，在反应釜中加入乙酸酐溶液，再加入对羟基苯甲酸、芳香型二醚二酸、间苯二甲酸、对苯二甲酸、双酚S、联苯二酚和催化剂，升温至50~160℃乙酰化1~2h，然后以1~3℃/h速率升温至285~335℃，并保温反应7~10h，高温出料，冷却后，切粒或粉碎，得到预聚物；(1) According to the proportion, add acetic anhydride solution to the reaction kettle, then add p-hydroxybenzoic acid, aromatic diether diacid, isophthalic acid, terephthalic acid, bisphenol S, biquinol and catalyst , heat up to 50~160°C for 1~2h acetylation, then heat up to 285~335°C at a rate of 1~3°C/h, and keep the reaction for 7~10h, discharge at high temperature, after cooling, cut into pellets or pulverize to obtain a polymer; （2）将步骤（1）得到的预聚物投入反应釜，在低于预聚物熔点20~30℃的条件下进行固相缩聚反应 5~48小时，制得低介电热致液晶聚合物；(2) The prepolymer obtained in step (1) is put into the reaction kettle, and the solid-phase polycondensation reaction is carried out for 5 to 48 hours under the condition that the melting point of the prepolymer is 20-30° C. to obtain a low-dielectric thermotropic liquid crystal polymerization. thing; 其中，所述乙酸酐的用量为对羟基苯甲酸、联苯二酚、双酚S中羟基摩尔数之和的1.1~1.5倍；所述催化剂的用量为单体总摩尔数的0.01%~0.1%。Wherein, the consumption of the acetic anhydride is 1.1 to 1.5 times the sum of the moles of hydroxyl groups in p-hydroxybenzoic acid, biphenol and bisphenol S; the consumption of the catalyst is 0.01% to 0.1 of the total moles of the monomers %. 8.根据权利要求7所述的低介电热致液晶聚合物的制备方法，其特征在于，优选的，所述乙酸酐的用量为对羟基苯甲酸、联苯二酚、双酚S中羟基摩尔数之和的1.2~1.3倍。8 . The preparation method of low-dielectric thermotropic liquid crystal polymer according to claim 7 , wherein, preferably, the amount of the acetic anhydride used is the hydroxyl group in p-hydroxybenzoic acid, biquinol, and bisphenol S. 9 . 1.2 to 1.3 times the sum of the number of moles. 9.根据权利要求7所述的低介电热致液晶聚合物的制备方法，其特征在于，所述催化剂选自含氮有机物或乙酸盐中的任意一种。9 . The method for preparing a low-dielectric thermotropic liquid crystal polymer according to claim 7 , wherein the catalyst is selected from any one of nitrogen-containing organic compounds or acetates. 10 . 10.根据权利要求9所述的低介电热致液晶聚合物的制备方法，其特征在于，所述催化剂选自N-甲基咪唑、乙酸锌、乙酸钾、乙酸镁或乙酸钙中的任意一种。10. The method for preparing a low-dielectric thermotropic liquid crystal polymer according to claim 9, wherein the catalyst is selected from any of N-methylimidazole, zinc acetate, potassium acetate, magnesium acetate or calcium acetate A sort of.
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