WO2023045821A1 - 一种液晶聚酯及其制备方法和应用 - Google Patents

一种液晶聚酯及其制备方法和应用 Download PDF

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WO2023045821A1
WO2023045821A1 PCT/CN2022/118967 CN2022118967W WO2023045821A1 WO 2023045821 A1 WO2023045821 A1 WO 2023045821A1 CN 2022118967 W CN2022118967 W CN 2022118967W WO 2023045821 A1 WO2023045821 A1 WO 2023045821A1
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liquid crystal
crystal polyester
repeating unit
mol
substituent
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PCT/CN2022/118967
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English (en)
French (fr)
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马达锋
肖中鹏
姜苏俊
陈平绪
叶南飚
黄险波
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珠海万通特种工程塑料有限公司
金发科技股份有限公司
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Publication of WO2023045821A1 publication Critical patent/WO2023045821A1/zh

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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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/065—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids the hydroxy and carboxylic ester groups being bound to aromatic rings
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6852—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from hydroxy carboxylic acids
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • 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
    • C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
    • 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
    • C08G2250/00—Compositions for preparing crystalline polymers
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones

Definitions

  • the invention relates to the technical field of polymer materials, in particular to a liquid crystal polyester and its preparation method and application.
  • Thermoplastic liquid crystal polymer has excellent low moisture absorption, heat resistance, chemical resistance and electrical properties, and has a wide range of applications in the field of electronic appliances.
  • LCP Thermoplastic liquid crystal polymer
  • the high-frequency signal transmission of 5G communication technology puts forward higher requirements on the dielectric properties of the insulating layer in printed circuit boards at high frequencies.
  • Liquid crystal polymers have excellent dielectric properties at high frequencies. It has received extensive attention, and the preparation of liquid crystal polymers into thin films for printed circuit boards has become a hot topic in recent years.
  • higher requirements are placed on the flexibility of materials.
  • General liquid crystal polymer resin has a very rigid rod-shaped polymer chain structure, which is easy to cause unidirectional orientation of the polymer chain during processing and molding.
  • the anisotropy of this molecular segment makes the liquid crystal polymer There are great difficulties.
  • the orientation destruction is not complete, and the performance difference of the film in the flow direction (MD direction) and perpendicular to the flow direction (TD direction) is too large, which makes the film easy to Tear along the MD direction, even unable to form a film. Therefore, in the process of LCP film preparation, the film-forming resin is the most basic and the most critical part.
  • Patent CN1003510668C mentions the use of amorphous resin to modify the film-forming resin to improve the formability of the film and the stability of the film bubble during film formation, but this method has the compatibility and dispersibility of the amorphous resin and the liquid crystal polymer problem, and the resulting film still has a high tensile modulus.
  • FCCL is one of the most important application fields of LCP film.
  • copper foil and LCP are usually hot-compressed.
  • the surface of the copper foil is generally less rough, which requires the LCP film to have a relatively low tensile modulus, that is, to have better toughness, and the two will produce a more significant anchoring effect during the lamination process , the obtained laminate has better peel strength while maintaining good high-frequency characteristics.
  • the object of the present invention is to provide a liquid crystal polyester with good formability.
  • the film prepared by the liquid crystal polyester has low tensile modulus and high elongation at break, and is more suitable for the preparation of FCCL.
  • Another object of the present invention is to provide the preparation method and application of the above-mentioned liquid crystal polyester.
  • a liquid crystal polyester in terms of molar percentage, said liquid crystal polyester is composed of the following repeating units,
  • a repeating unit a repeating unit with a 1,4-phenylene structure, with a content of 65-85mol%, derived from at least one of p-hydroxybenzoic acid, hydroquinone, and terephthalic acid;
  • B repeating unit repeating unit with 2,6-naphthylene structure, content 14.4-28mol%, derived from 6-hydroxy-2-naphthoic acid, 2,6-naphthalenediol, 2,6-naphthalene dicarboxylic acid at least one;
  • the molar ratio of hydroxyl and carboxyl groups in A repeating unit and B repeating unit is 1.02:1 ⁇ 1:1.02;
  • C repeating unit derived from the following compound, content 0.5-7mol%, wherein the X substituents are -O- and/or -NH-, the hydroxyl group is at the meta or para position of the X substituent, and the carboxyl group is at the meta position of the X substituent or counterpoint
  • the A repeating unit content is 69-80 mol%
  • the B repeating unit content is 18.9-26 mol%
  • the C repeating unit is 1-5 mol%.
  • the A repeating unit content is 72-76 mol%
  • the B repeating unit content is 20.9-25 mol%
  • the C repeating unit is 2.9-4 mol%.
  • the hydroxyl group is at the para-position of the X substituent
  • the carboxyl group is at the para-position of the X substituent
  • -NH- accounts for 0-20 mol% of the total molar percentage of X substituents, more preferably 5-20 mol%.
  • Introducing an appropriate amount of -NH- into the molecular segment can form a slight cross-link, which can effectively increase the intralayer bonding force and prevent the film from peeling off during peeling; There will be more gel points in the film, which is not conducive to the appearance of the film.
  • a certain amount of other repeating units D can be added to the liquid crystal polyester of the present invention. Based on the molar percentage of the total chain segments of liquid crystal polyester, 0-3mol% D repeating unit: derived from one of m-hydroxybenzoic acid, bisphenol A, isophthalic acid, biphenol or resorcinol or more.
  • the melting point of the liquid crystal polyester is between 250°C and 350°C.
  • the preparation method of liquid crystal polyester of the present invention comprises the following steps:
  • Step 1 under the condition of inert gas, add each reaction monomer, and carry out the acylation reaction under the action of an acylating agent, the reaction temperature is 100°C-180°C, and the reaction time is 30 minutes-4 hours;
  • Step 2 After the acylation reaction, keep the pressure in the reactor at normal pressure, and raise the temperature to 200°C to 310°C at a rate of 0.1°C/min to 5°C/min, and discharge acetic acid and unreacted acetic acid from the rectifying column Anhydride molecules, when the amount of acetic acid received reaches more than 90wt% of the theoretical value, reduce the pressure in the reactor to 1-10kPa, maintain this reduced pressure condition and raise the temperature of the reaction system to 330-400°C.
  • the stirring power reaches the set
  • the discharged material is cooled and granulated to obtain liquid crystal polyester.
  • the application of the liquid crystal polyester of the invention is for preparing FCCL films.
  • the present invention introduces a small amount of C repeating units with a bent structure into the polymerization system to increase the entanglement performance of molecular chain segments and increase the formability of the film.
  • the obtained film has moderate tensile modulus (too high tensile modulus is not conducive to subsequent processing, too low affects film performance) and higher elongation at break and higher intralayer peeling due to the entanglement of chain segments performance (higher peel strength).
  • By controlling the type and content of the substituent X in the repeating unit C while enhancing the bonding force between the film and the copper foil, it can also prevent the gel point from occurring during the film forming process and affect the appearance and performance of the film.
  • the monomer raw materials and acylating agent used in the present invention are derived from commercially available products.
  • Melting point of liquid crystal polyester Measured by DSC 200F3 manufactured by NETZSCH Company, the heating rate is 20°C/min, the temperature is raised to 30°C above the melting point, and the melting point is obtained by taking the second heating curve.
  • the film bubble can be continuously and stably formed for more than 1 hour, that is, the formability is excellent; the film bubble can be inflated to the maximum, but the film bubble is unstable, that is, the formability is good; the film bubble cannot be inflated to the maximum diameter. That is, the formability is poor.
  • Film tensile modulus Using ASTM D882-18 method, cut a 10mm ⁇ 15cm sample from the film, and use Shenzhen Sansi universal tensile testing equipment to measure it, and the tensile speed is 10mm/min.
  • Film peeling strength Make a 1.5cm wide peeling test piece from the laminate, fix the surface layer on the flat plate with two face tapes, peel it off at 180° at a speed of 50mm/min, and measure the peeling strength.
  • Example 12 p-Hydroxybenzoic acid, mol% 75 75 75 75 75 6-Hydroxy-2-naphthoic acid, mol% twenty one twenty one twenty one twenty one twenty one twenty one Repeat unit C, mol% 4 4 4 4 4 -NH- accounts for X substituent mole% the 50 20 10 5 -O- accounts for X substituent mole% 100 50 80 90 95 The position of the hydroxyl group with respect to the X substituent meta meta meta meta meta Position of the carboxyl group with respect to the X substituent meta meta meta meta meta meta meta meta meta meta
  • Example 16 Example 18 p-Hydroxybenzoic acid, mol% 59 72 68 67.9 68 66.5 Hydroquinone, mol% 5 the 4 4 3.7 4 Terephthalic acid, mol% 5 the 4 4 4 4 6-Hydroxy-2-naphthoic acid, mol% 26 15 20 20 20 20 2,6-Naphthalenediol, mol% the 5 0.5 0.5 0.5 0.5 2,6-naphthalene dicarboxylic acid, mol% the 5 0.5 0.5 0.5 0.5 0.5 m-Hydroxybenzoic acid, mol% the 0.1 the 1.5 Bisphenol A, mol% the the the the 0.3 the Repeat unit C, mol% 5 3 3 3 3 3 3 -NH- accounts for X substituent mole% the the the the the the -O- accounts for X substituent mole% 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100
  • Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 p-Hydroxybenzoic acid, mol% 50 60 73 80 6-Hydroxy-2-naphthoic acid, mol% 45 28 27 20 Repeat unit C, mol% 5 12 the the -NH- accounts for X substituent mole% the 100 the the -O- accounts for X substituent mole% 100 the the the the The position of the hydroxyl group with respect to the X substituent counterpoint counterpoint the the Position of the carboxyl group with respect to the X substituent counterpoint counterpoint the the
  • Example 8 Example 9
  • Example 10 Example 11
  • Example 12 Melting point, °C 297 296 294 295 297 Film Formability excellent good excellent excellent excellent excellent Film tensile modulus, GPa 3.9 4.1 4.0 3.8 3.9 Film elongation at break, % 22.5 20.3 23.5 23.1 22.9 Film peel strength, kg/cm 1.25 1.22 1.29 1.30 1.27 Film Appearance (Gel Point) excellent good excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent
  • the hydroxyl group is preferably at the para-position of the X substituent, and the carboxyl group is at the para-position of the X substituent.
  • -NH- in the C repeating unit preferably accounts for 0-20 mol% of the total molar percentage of X substituents, more preferably 5-20 mol%.
  • Example 13 Example 14
  • Example 15 Example 16
  • Example 17 Example 18 Melting point, °C 265 283 305 305 303 308 Film Formability excellent excellent excellent excellent excellent excellent excellent excellent Film tensile modulus, GPa 5.2 4.1 4.7 4.6 4.7 4.5 Film elongation at break, % 16.9 20.1 18.1 18.3 18.0 18.6 Film peel strength, kg/cm 1.18 1.21 1.23 1.22 1.23 1.20 Film Appearance (Gel Point) excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent excellent
  • repeating unit C can greatly reduce the tensile modulus and improve the elongation at break and peel strength.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

本发明公开了一种液晶聚酯，按摩尔百分比计，所述的液晶聚酯由包括以下重复单元构成，A重复单元、B重复单元、C重复单元：衍生自以下化合物，含量0.5-7mol％，其中X取代基为-O-和/或-NH-，羟基在X取代基的间位或对位、羧基在X取代基的间位或对位。本发明在保持分子链全芳香环结构的基础上，通过在聚合体系中引入少量具有弯折结构的重复单元，增加分子链段的缠结性能，增加薄膜的成型性。此外得到的薄膜因为链段的缠结，具有适中的拉伸模量、更高的断裂伸长率以及更高的层内剥离性能。

Description

一种液晶聚酯及其制备方法和应用 技术领域
本发明涉及高分子材料技术领域，特别是涉及一种液晶聚酯及其制备方法和应用。
背景技术
热塑性液晶聚合物(LCP)具有优异的低吸湿性、耐热性、耐药品性及电性能，在电子电器领域有着广泛的用途。随着5G相关产业的发展，5G通讯技术高频段的信号传输对印刷电路板中绝缘层在高频下的介电性能提出了更高的要求，液晶聚合物因高频下优异的介电性能而受到了广泛的关注，而将液晶聚合物制备成薄膜应用于印刷电路板则更是近年来的热门课题。此外，随着智能终端设备的小型化，集成化以及可穿戴化发展，对材料的柔性提出了更高的要求。
一般的液晶聚合物树脂具有刚性极强的棒状高分子链结构，在加工成型过程中易引起聚合物链的单向取向，这种分子链段的各向异性使得液晶聚合物在成膜过程中存在极大的困难，在常见的如吹塑成型或者流延成型过程中取向破坏不彻底，流动方向(MD方向)和垂直于流动方向(TD方向)上薄膜的性能差异过大，导致薄膜易沿着MD方向撕裂，甚至无法成膜。因此，在LCP薄膜制备的流程中，成膜树脂是最基础也是最关键的部分。专利CN1003510668C提到使用非晶树脂对成膜树脂进行改性，以提高薄膜的成形性以及成膜时膜泡的稳定性，但是该方法存在着非晶树脂与液晶聚合物相容性以及分散性的问题，且得到的薄膜仍具有较高的拉伸模量。
FCCL是LCP薄膜最重要的应用领域之一，制备FCCL时通常是通过将铜箔及LCP热压贴合。为减少铜箔的传输损耗，铜箔表面通常粗糙程度较低，这需要LCP薄膜有相对较低的拉伸模量，即具有较好的韧性，两者在层压过程中产生更显著锚固效应，得到的层叠体在维持良好的高频特性下具有更好的剥离强度。
发明内容
本发明的目的在于，提供一种成型性能好的液晶聚酯，用该液晶聚酯制得的薄膜拉伸模量低、断裂伸长率高，更适合于FCCL的制备。
本发明的另一目的在于，提供上述液晶聚酯的制备方法和应用。
本发明是通过以下技术方案实现的：
一种液晶聚酯，按摩尔百分比计，所述的液晶聚酯由以下重复单元构成，
A重复单元：具有1,4-亚苯基结构的重复单元，含量65-85mol％，衍生自对羟基苯甲酸、对 苯二酚、对苯二甲酸中的至少一种；
B重复单元：具有2,6-亚萘基结构的重复单元，含量14.4-28mol％，衍生自6-羟基-2-萘甲酸、2,6-萘二酚、2,6-萘二甲酸的至少一种；
其中，A重复单元和B重复单元中羟基与羧基摩尔比为1.02:1～1:1.02；
C重复单元：衍生自以下化合物，含量0.5-7mol％，其中X取代基为-O-和/或-NH-，羟基在X取代基的间位或对位、羧基在X取代基的间位或对位
Figure PCTCN2022118967-appb-000001
优选的，按摩尔百分比计，A重复单元含量69-80mol％，B重复单元含量18.9-26mol％，C重复单元1-5mol％。
更优选的，A重复单元含量72-76mol％，B重复单元含量20.9-25mol％，C重复单元2.9-4mol％。
优选的，所述的C重复单元中，羟基在X取代基的对位、羧基在X取代基的对位。
优选的，所述的C重复单元中，-NH-占X取代基总摩尔百分比的0-20mol％，更优选5-20mol％。在分子链段中引入适量的-NH-能形成轻微的交联，能有效地增加层内结合力，防止在剥离时薄膜发生层内剥离；但是若-NH-含量过多，则在成型过程中会产生较多的凝胶点，不利于薄膜外观。
本发明液晶聚酯可以增加一定量的其他重复单元D。按液晶聚酯总链段摩尔百分比计，可以0-3mol％的D重复单元：衍生自间羟基苯甲酸、双酚A、间苯二甲酸、联苯二酚或间苯二酚中的一种或多种。
考虑到加工难度，所述液晶聚酯的熔点在250～350℃之间。
本发明的液晶聚酯的制备方法，包括以下步骤：
步骤1，在惰性气体条件下，加入各反应单体，在酰化剂的作用下进行酰化反应，反应温度为100℃～180℃，反应时间为30分钟～4小时；
步骤2，酰化反应结束后，保持反应釜内压力为常压，并以0.1℃/min～5℃/min的速率升温至200℃～310℃，从精馏柱排出醋酸及未反应的醋酸酐分子，当醋酸接收量到达理论值的90wt％以上时，将反应釜内压力进行减压至1～10kPa，保持此减压条件并将反应体系升温到330～400℃，当搅拌功率达到设定值时，排出物料冷却造粒得到液晶聚酯。
本发明的液晶聚酯的应用，用于制备FCCL薄膜。
本发明具有如下有益效果：
本发明在保持分子链全芳香环结构的基础上，通过在聚合体系中引入少量具有弯折结构的C重复单元，增加分子链段的缠结性能，增加薄膜的成型性。得到的薄膜因为链段的缠结，具有适中的拉伸模量(拉伸模量过高不利于后续加工，太低影响薄膜性能)及更高的断裂伸长率以及更高的层内剥离性能(剥离强度更高)。通过重复单元C中取代基X的种类和含量控制，在增强薄膜与铜箔结合力的同时也能防止薄膜成型过程中出现凝胶点，影响薄膜外观和性能。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
本发明所用单体原料与酰化剂来源于市售产品。
以下实施例中，液晶聚酯及用该液晶聚酯制得的薄膜性能评价由以下方法进行。
1.液晶聚酯熔点：采用NETZSCH公司制DSC 200F3测得，升温速率20℃/min，升温至熔点以上30℃，取第二次升温的曲线得到熔点。
2.薄膜成型性：膜泡能连续稳定成型1h以上，即为成型性优；膜泡可以吹胀至最大，但膜泡不稳定，即成型性良；膜泡无法吹胀至最大折径，即成型性差。
3.薄膜拉伸模量：采用ASTM D882-18方法，从薄膜上裁取10mm×15cm的样条，使用深圳三思万能拉伸试验设备测得，拉伸速度10mm/min。
4.薄膜断裂伸长率：采用ASTM D882-18方法，从薄膜上裁取10mm×15cm的样条，使用深圳三思万能拉伸试验设备测得，拉伸速度10mm/min。
5.薄膜剥离强度：从层叠体上制作1.5cm宽的剥离试验片将表层用两个面试用胶带固定在平板上，采用180°剥离，以50mm/min的速度剥离，测量剥离时的强度。
6.薄膜外观(凝胶点数)：薄膜透过光看，10米内无凝胶点为优，有0～10个凝胶点为良，10个凝胶点以上为差。
实施例和对比例液晶聚酯的制备方法：在惰性气体条件下，加入各反应单体，在酰化剂的作用下进行酰化反应，反应温度为100℃～180℃，反应时间为30分钟～4小时；酰化反应结束后，保持反应釜内压力为常压，并以0.1℃/min～5℃/min的速率升温至200℃～400℃，从精馏柱排出醋酸及未反应的醋酸酐分子，当醋酸接收量到达理论值的90％以上时，将反应 釜内压力进行减压至1～10kPa，保持此减压条件并将反应体系程序升温到反应最高温度，维持真空度及搅拌直至搅拌功率达到一定的值，排出物料冷却造粒得到液晶聚酯。
表1：实施例1-7液晶聚酯各组分含量(摩尔百分比)
Figure PCTCN2022118967-appb-000002
表2：实施例8-12液晶聚酯各组分含量(摩尔百分比)
  实施例8 实施例9 实施例10 实施例11 实施例12
对羟基苯甲酸，mol％ 75 75 75 75 75
6-羟基-2-萘甲酸，mol％ 21 21 21 21 21
重复单元C，mol％ 4 4 4 4 4
-NH-占X取代基mol％   50 20 10 5
-O-占X取代基mol％ 100 50 80 90 95
羟基对于X取代基的位置 间位 间位 间位 间位 间位
羧基对于X取代基的位置 间位 间位 间位 间位 间位
表3：实施例13-18液晶聚酯各组分含量(摩尔百分比)
  实施例13 实施例14 实施例15 实施例16 实施例17 实施例18
对羟基苯甲酸，mol％ 59 72 68 67.9 68 66.5
对苯二酚，mol％ 5   4 4 3.7 4
对苯二甲酸，mol％ 5   4 4 4 4
6-羟基-2-萘甲酸，mol％ 26 15 20 20 20 20
2,6-萘二酚，mol％   5 0.5 0.5 0.5 0.5
2,6-萘二甲酸，mol％   5 0.5 0.5 0.5 0.5
间羟基苯甲酸，mol％       0.1   1.5
双酚A，mol％         0.3  
重复单元C，mol％ 5 3 3 3 3 3
-NH-占X取代基mol％            
-O-占X取代基mol％ 100 100 100 100 100 100
羟基对于X取代基的位置 对位 对位 对位 对位 对位 对位
羧基对于X取代基的位置 对位 对位 对位 对位 对位 对位
表4：对比例液晶聚酯各组分含量(摩尔百分比)
  对比例1 对比例2 对比例3 对比例4
对羟基苯甲酸，mol％ 50 60 73 80
6-羟基-2-萘甲酸，mol％ 45 28 27 20
重复单元C，mol％ 5 12    
-NH-占X取代基mol％   100    
-O-占X取代基mol％ 100      
羟基对于X取代基的位置 对位 对位    
羧基对于X取代基的位置 对位 对位    
表5：实施例和对比例液晶聚酯测试结果
Figure PCTCN2022118967-appb-000003
由实施例1-7可知，在优选的重复单元下，拉伸模量适中，并且断裂伸长率高、剥离强度更高。
续表5：
  实施例8 实施例9 实施例10 实施例11 实施例12
熔点，℃ 297 296 294 295 297
薄膜成型性 优 良 优 优 优
薄膜拉伸模量，GPa 3.9 4.1 4.0 3.8 3.9
薄膜断裂伸长率，％ 22.5 20.3 23.5 23.1 22.9
薄膜剥离强度，kg/cm 1.25 1.22 1.29 1.30 1.27
薄膜外观(凝胶点数) 优 良 优 优 优
由实施例4/8可知，优选羟基在X取代基的对位、羧基在X取代基的对位。
由实施例4/8-12可知，优选C重复单元中-NH-占X取代基总摩尔百分比的0-20mol％，更优选5-20mol％。
续表5：
  实施例13 实施例14 实施例15 实施例16 实施例17 实施例18
熔点，℃ 265 283 305 305 303 308
薄膜成型性 优 优 优 优 优 优
薄膜拉伸模量，GPa 5.2 4.1 4.7 4.6 4.7 4.5
薄膜断裂伸长率，％ 16.9 20.1 18.1 18.3 18.0 18.6
薄膜剥离强度，kg/cm 1.18 1.21 1.23 1.22 1.23 1.20
薄膜外观(凝胶点数) 优 优 优 优 优 优
续表5：
  对比例1 对比例2 对比例3 对比例4
熔点，℃ 259 253 280 318
薄膜成型性 差 差 优 良
薄膜拉伸模量，GPa - - 13.9 15.2
薄膜断裂伸长率，％ - - 7.9 5.2
薄膜剥离强度，kg/cm - - 0.53 0.42
薄膜外观(凝胶点数) - - 良 良
由对比例1/2可知，当A重复单元含量低于65mol％时，无法成膜。
由对比例3/4可知，重复单元C的引入，能够极大降低拉伸模量，提升断裂伸长率和剥离强度。

Claims (9)

  1. 一种液晶聚酯，其特征在于，按摩尔百分比计，所述的液晶聚酯由包括以下重复单元构成，
    A重复单元：具有1,4-亚苯基结构的重复单元，占总链段65-85mol％，衍生自对羟基苯甲酸、对苯二酚、对苯二甲酸中的至少一种；
    B重复单元：具有2,6-亚萘基结构的重复单元，占总链段14.4-28mol％，衍生自6-羟基-2-萘甲酸、2,6-萘二酚、2,6-萘二甲酸的至少一种；
    其中，A重复单元和B重复单元中羟基总量与羧基总量的摩尔比为1.02:1～1:1.02；
    C重复单元：衍生自以下化合物，占总链段0.5-7mol％，其中X取代基为-O-和/或-NH-，羟基在X取代基的间位或对位、羧基在X取代基的间位或对位
    Figure PCTCN2022118967-appb-100001
  2. 根据权利要求1所述的液晶聚酯，其特征在于，按摩尔百分比计，A重复单元占总链段69-80mol％，B重复单元占总链段18.9-26mol％，C重复单元占总链段1-5mol％。
  3. 根据权利要求2所述的液晶聚酯，其特征在于，A重复单元占总链段72-76mol％，B重复单元占总链段20.9-25mol％，C重复单元占总链段2.9-4mol％。
  4. 根据权利要求3所述的液晶聚酯，其特征在于，所述的C重复单元中，羟基在X取代基的对位、羧基在X取代基的对位。
  5. 根据权利要求1所述的液晶聚酯，其特征在于，所述的C重复单元中，-NH-占X取代基总摩尔百分比的0-20mol％，更优选5-20mol％。
  6. 根据权利要求1所述的液晶聚酯，其特征在于，按液晶聚酯总链段摩尔百分比计，还包括0-3mol％的D重复单元：衍生自间羟基苯甲酸、双酚A、间苯二甲酸、联苯二酚或间苯二酚中的一种或多种。
  7. 根据权利要求书1所述的液晶聚酯，其特征在于，所述的液晶聚酯的熔点在250～350℃之间。
  8. 权利要求1-7任一项所的液晶聚酯的制备方法，其特征在于，包括以下步骤：
    步骤1，在惰性气体条件下，加入各反应单体，在酰化剂的作用下进行酰化反应，反应温度为100℃～180℃，反应时间为30分钟～4小时；
    步骤2，酰化反应结束后，保持反应釜内压力为常压，并以0.1℃/min～5℃/min的速率升温至200℃～310℃，从精馏柱排出醋酸及未反应的醋酸酐分子，当醋酸接收量到达理论值的 90wt％以上时，将反应釜内压力进行减压至1～10kPa，保持此减压条件并将反应体系升温到330～400℃，当搅拌功率达到设定值时，排出物料冷却造粒得到液晶聚酯。
  9. 权利要求1-7任一项所的液晶聚酯的应用，其特征在于，用于制备FCCL。
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