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WO2023186187A1 - 一种液晶聚合物及其制备方法和应用 - Google Patents

一种液晶聚合物及其制备方法和应用 Download PDF

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Publication number
WO2023186187A1
WO2023186187A1 PCT/CN2023/095591 CN2023095591W WO2023186187A1 WO 2023186187 A1 WO2023186187 A1 WO 2023186187A1 CN 2023095591 W CN2023095591 W CN 2023095591W WO 2023186187 A1 WO2023186187 A1 WO 2023186187A1
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repeating unit
liquid crystal
crystal polymer
acid
derived
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PCT/CN2023/095591
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English (en)
French (fr)
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肖中鹏
邢羽雄
徐显骏
陈平绪
叶南飚
黄险波
姜苏俊
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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 WO2023186187A1 publication Critical patent/WO2023186187A1/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
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • 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
    • 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
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/87—Non-metals or inter-compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the invention relates to the technical field of polymer materials, and in particular to a liquid crystal polymer and its preparation method and application.
  • Thermotropic liquid crystal polymer (TLCP) has good properties such as rigid mechanical properties, chemical resistance and dimensional accuracy. As a high-performance special engineering plastic, it is widely used in electronic appliances and small precision thin-walled parts and other fields. In the field of information and communications, very thin components are sometimes required. In particular, personal computers and mobile phones use highly integrated devices, which are gradually developing towards miniaturization and thin-walling.
  • Chinese patent application CN103360730A discloses adding fillers such as titanium oxide, composite metal oxide, and ultramarine to the liquid crystal polymer to form a composition with anti-foaming properties.
  • Chinese patent application CN102140232A uses a composition of liquid crystal polymer, filled flake filler and carbon black of a certain size, and uses a good modification method to prepare a composition with zero bubbling incidence rate.
  • Chinese patent application CN105907058B introduces strontium element into the liquid crystal polymer composition, and the high temperature stability and welding blistering resistance of the composition are unexpectedly and significantly improved.
  • the current conventional method to improve the foaming resistance of TLCP materials is mainly by adding fillers.
  • filling modification methods usually require the use of fixed additive types, and often affect the fluidity of the material and weaken its molding performance, which is a great challenge for the injection molding of small, thin-walled parts.
  • the object of the present invention is to provide a liquid crystal polymer with excellent foaming resistance and good fluidity.
  • a liquid crystal polymer consisting of the following repeating units:
  • the molar content of the repeating unit A is 59-72mol%; the molar content of the repeating unit B is 2-12mol%; the molar content of the repeating unit C is 8-20mol%; the molar content of the repeating unit D is 5-17mol%; the repeating The molar content of unit E is 3-10 mol%; among them, Ar1 in repeating unit A represents p-phenylene; Ar2 in repeating unit B represents naphthylene; Ar3 and Ar4 in repeating units C and D independently represent Any one of phenylene, naphthylene or biphenylene; Ar5 in the repeating unit E represents any one of phenylene, naphthylene or biphenylene, Y and Z are the same or different organic or inorganic groups, but at least one of them contains -NH- or -NR, wherein R is any one of an aryl group or an alkyl group containing
  • One or more hydrogen atoms of Ar1, Ar2, Ar3, Ar4 and Ar5 may each be independently substituted by a halogen atom, an alkyl group or an aryl group.
  • the repeating unit A is derived from at least one of 4-hydroxybenzoic acid, 3-hydroxybenzoic acid or 2-hydroxybenzoic acid; the repeating unit B is derived from 6-hydroxy-2-naphthoic acid, 3-hydroxybenzoic acid.
  • the repeating unit C is derived from terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid or 4,4'- At least one of biphenyl dicarboxylic acid;
  • the repeating unit D is derived from at least one of 4,4'-dihydroxybiphenyl, hydroquinone or 2,6-naphthodiol;
  • the repeating unit E is derived from at least one of 4-acetaminophen, p-aminophenol, 4'-amino-4-biphenol or 6-acetamido-2-naphthol.
  • the repeating unit A is derived from 4-hydroxybenzoic acid; the repeating unit B is derived from 6-hydroxy-2-naphthoic acid; the repeating unit C is derived from terephthalic acid; the repeating unit D Derived from 4,4'-dihydroxybiphenyl; the repeating unit E is derived from 4-acetaminophen.
  • the liquid crystal polymer of the present invention has a melt viscosity change rate of -0.3 to 0.3.
  • the melt viscosity change rate is an effective characterization method that reflects the degree of thermal degradation, segment transesterification or molecular end group reaction of the liquid crystal polymer.
  • the present invention has found through research that the melt viscosity change rate of the liquid crystal polymer of the present invention is - Within the range of 0.3 ⁇ 0.3, it shows good foaming resistance and fluidity.
  • the melt viscosity change rate is less than -0.3, the liquid crystal polymer is prone to foaming; when the melt viscosity change rate is greater than 0.3, the liquid crystal polymer has good foaming resistance, but its fluidity becomes poor.
  • the present invention also provides a preparation method for the above-mentioned liquid crystal polymer, which includes the following steps:
  • Acetylation section Put the monomers, acylating agent, and catalyst corresponding to the repeating unit A, repeating unit B, repeating unit D, and repeating unit E respectively into the first reactor at the same time, and react at a temperature of 100-160°C 0.5-5h, allow the monomer to be fully acetylated;
  • the acylating agent is selected from acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, 2-ethylhexanoic anhydride, dichloroacetic anhydride or difluoroacetic acid Any one of the anhydrides;
  • the catalyst is an onium salt catalyst;
  • the molar ratio of the acylating agent to the total molar amount of phenolic hydroxyl groups in the monomer is (1-1.2):1; the amount of catalyst is 20-2000ppm of the theoretical discharge amount;
  • Step (2) Condensation polymerization section: Transfer the acetylated reactants in step (1) into the second reactor, conduct melt polycondensation of the monomer corresponding to repeating unit C, and heat up to 280°C at a heating rate of 0.3-1.5°C/min. Finally, control the heating rate to keep the heating time in the 280-300°C heating section at 1-3h, and finally continue to use a heating rate of 0.3-1.5°C/min to heat up to T m -10°C ⁇ T m +30°C, T m is The melting point of the target product, acetic acid and its by-products are continuously distilled out during the heating period;
  • Reduced compression polymerization section By performing reduced compression polymerization in the second reactor, the target vacuum degree is 0.1kPa ⁇ 40kPa, the reduced compression polymerization time is controlled within 3 hours, and the temperature of the prepolymer melt during final control is T m +5°C ⁇ T m +30°C, T m is the melting point of the target product; discharge the prepolymer in a molten state, solidify the prepolymer, and cut or crush to obtain prepolymer particles or powder;
  • Solid-state polymerization section Discharge the prepolymer in an inert gas atmosphere, and perform solid-phase polymerization under a vacuum of 0.1 Pa to 50,000 Pa or an inert gas atmosphere.
  • the polymerization temperature is 0 to 340°C, and the reaction time is 0.5 to 40 hours. After reaching a predetermined melt viscosity, the temperature is lowered to prepare a fully aromatic polyester amide.
  • the preparation method of the onium salt catalyst includes the following steps: add the cationic compound and the anionic functional compound into the reactor at a molar ratio of 1: (1.01 ⁇ 1.20), stir and react at a temperature of 80°C for 0-10h, and prepare Onium salt catalyst.
  • the anionic functional compound is selected from any one of acetic acid, propionic acid or butyric acid; preferably, the anionic functional compound is selected from acetic acid.
  • the cationic compound is selected from heterocyclic organic base compounds containing two or more nitrogen atoms; preferably, the cationic compound is selected from any one of imidazole compounds, triazole compounds or dipyridyl compounds;
  • the imidazole compound is selected from 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 4-ethylimidazole, 1,2-dimethylimidazole, Either 1,4-dimethylimidazole or 2,4-dimethylimidazole; more preferably, the cationic compound is selected from 1-methylimidazole.
  • the present invention uses an onium salt as a catalyst. Due to the formation of ionic bonds, the onium salt catalyst has high chemical bond energy, which makes it good in thermal stability. It overcomes the characteristics of traditional imidazole catalysts such as easy volatilization and insufficient thermal stability, and has more efficient catalysis. As a result, a liquid crystal polymer with a required melt viscosity change rate can be prepared.
  • the heating time of 1-3 hours needs to be strictly controlled in the temperature range of 280-300°C, and a slow heating method is used to promote the full participation of aromatic dicarboxylic acid in the polymerization, which avoids Monomer loss causes end-group imbalance in the resin, which in turn causes a decrease in melt viscosity retention. From the perspective of energy consumption economy and effect, the total time of this heating section is controlled to 1-3 hours.
  • the invention also provides a liquid crystal polyester composition, which includes the following components in parts by weight: 50-80 parts of the liquid crystal polymer of the invention; 20-50 parts of reinforcing filler.
  • the reinforcing filler is selected from any one or more of fibrous fillers or non-fibrous fillers.
  • the non-fibrous filler is selected from any one or more of flaky fillers or granular fillers.
  • the preferred average length of the fibrous filler is 50-250 microns, and the aspect ratio is 30:1-600:1.
  • the fibrous filler includes but is not limited to glass fiber, potassium titanate fiber, metal-clad glass fiber, ceramic fiber, wollastonite fiber, metal carbide fiber, metal solidified fiber, asbestos fiber, alumina fiber, silicon carbide Any one or more of fiber, gypsum fiber or boron fiber; preferably glass fiber. When the size of the fibrous filler is within the above range, the liquid crystal polyester composition exhibits good anti-foaming properties.
  • the non-fibrous filler preferably has an average particle size of 0.01-50 microns.
  • the average particle size of the non-fibrous filler is less than 0.01 micron, it will lead to poor melt processability of the liquid crystal polyester composition; when the average particle size of the non-fibrous filler is greater than 50 micron, it will lead to a poor surface of the injection molded product. Exterior.
  • the non-fibrous fillers include, but are not limited to, potassium titanate whiskers, zinc oxide whiskers, aluminum borate whiskers, talc, carbon black, gypsum, asbestos, zeolite, sericite, kaolin, montmorillonite, clay, lithium Montmorillonite, synthetic mica, aluminosilicate, silica, titanium oxide, aluminum oxide, zinc oxide, zirconium oxide, iron oxide, calcium carbonate, magnesium titanate, dolomite, aluminum sulfate, barium sulfate, magnesium sulfate, Any one or more of calcium carbonate, mica, quartz powder, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, glass beads, ceramic beads, boron nitride or silicon carbide.
  • the invention provides a preparation method for the above-mentioned liquid crystal polyester composition, which includes the following steps:
  • a twin-screw extruder is used, and the processing temperature is set to 10-50°C above the melting point.
  • the liquid crystal polymer is added from the main feed port according to the proportion, and the reinforcing filler is added from the side feed port, and is melted after blending through the twin-screw extruder. After stripping out of the die, cooling, and pelletizing, a liquid crystal polyester composition is prepared.
  • liquid crystal polyester composition of the present invention After the liquid crystal polyester composition of the present invention is enhanced and modified by reinforcing fillers, its melt viscosity change rate is in the range of -0.3-0.3, and it still has good fluidity and anti-foaming properties.
  • the liquid crystal polyester composition of the present invention may further include antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, release agents, and colorants containing dyes or pigments within the scope that does not impair the effects of the present invention.
  • the present invention also provides the application of the above-mentioned liquid crystal polymer or liquid crystal polyester composition in the field of electronic and electrical appliances. Specifically, it is especially suitable for preparing small thin-walled electronic devices.
  • the present invention selects a specific monomer combination reaction, controls the monomer composition ratio within a certain range, uses a stable and efficient onium salt catalyst, and at the same time strictly controls the heating rate in the 280-300°C heating section of the polycondensation section to prepare the melt viscosity Liquid crystal polymers with a change rate of -0.3 to 0.3 have good fluidity and anti-foaming properties, and are particularly suitable for use in the field of small thin-walled electronic devices.
  • the liquid crystal polymer of the present invention is prepared by enhancing filler enhancement and modification to obtain a liquid crystal polyester composition. Its melt viscosity change rate is in the range of -0.3-0.3, and it still has good fluidity and anti-foaming properties.
  • 3-Hydroxybenzoic acid 3-HBA, commercially available;
  • 3-Hydroxy-2-naphthoic acid 3,6-HNA, commercially available;
  • Terephthalic acid TA, commercially available
  • Isophthalic acid IA, commercially available
  • Hydroquinone HQ, commercially available
  • Acylating agent acetic anhydride, AA, commercially available;
  • Catalyst Onium salt catalyst, obtained by homemade method: add 1-methylimidazole and acetic acid into a stirred reaction vessel at a molar ratio of 1:1.01, stir and react at 80°C for 5 hours.
  • Reinforcement filler 1 glass fiber, commercially available
  • Reinforcing filler 2 talc powder, commercially available.
  • the polymer is The melt is discharged in a molten state through the discharge port of reactor 2, and is granulated after cooling to obtain a prepolymer.
  • the prepolymer is put into a rotating drum for solid-phase viscosity increase.
  • the viscosity increase temperature is 290°C, and the vacuum degree is below 0.1kPa. After reaching the predetermined melt viscosity, the temperature is lowered to prepare a liquid crystal polymer.
  • the only difference between the preparation method of the liquid crystal polymer in Comparative Example 7 and Example 2 is that in the polycondensation section, the heating rate is controlled to maintain a heating time of 0.5 h in the 280-300°C heating section.
  • the liquid crystal polyester composition is melted, discharged from the die, cooled by a water tank, and hauled to a pelletizer for pelletizing to prepare a liquid crystal polyester composition.
  • Fluidity The length of a rod-shaped sheet injection molded body with dimensions of 5*0.45mm in width*thickness is used to characterize the fluidity of the fully aromatic polyester amide and liquid crystal polyester composition.
  • the average length of the rod-shaped flake injection molded body is used as a parameter to measure the fluidity of the liquid crystal polymer and liquid crystal polyester composition. Under the same injection molding conditions, the longer the length of the rod-shaped flake injection molded body, the better its fluidity.
  • the fully aromatic polyester amide or liquid crystal polyester composition is molded to a thickness of 1.0 mm at 5°C above the melting temperature of the liquid crystal polymer or liquid crystal polyester composition and at an injection speed of 60 mm/s. , a thin sheet with a length and width of 60mm Sample. Put 10 of these samples into an oven at 260°C for 5 minutes, then take out the samples and observe the formation of bubbles on the surface of each sample.
  • the foaming resistance is measured by the foaming rate.
  • the foaming rate the number of foaming blocks/the total number of blocks*100%. The lower the foaming rate, the better the foaming resistance.
  • Table 1 Monomer content and related performance test results of the liquid crystal polymers of Examples 1-7, amounts of each component of the liquid crystal polyester composition and related performance test results
  • Table 2 Monomer content and related performance test results of the liquid crystal polymers of Comparative Examples 1-6, amounts of each component of the liquid crystal polyester composition and related performance test results
  • the present invention selects a specific monomer combination reaction, controls the monomer composition ratio within a certain range, uses a stable and efficient onium salt catalyst, and at the same time raises the temperature at 280-300°C in the polycondensation section.
  • the heating rate is strictly controlled in each section to prepare a liquid crystal polymer with a melt viscosity change rate of -0.3 to 0.3, which has good fluidity and anti-foaming properties; a liquid crystal polyester composition is prepared by adding reinforcing fillers such as glass fiber.
  • the melt viscosity change rate is in the range of -0.3 to 0.3, and it also has good fluidity and anti-foaming properties.
  • the monomer composition ratio of Comparative Examples 1-3 is not within the required range, and a liquid crystal polymer with a melt viscosity change rate in the range of -0.3 to 0.3 cannot be produced; the liquid crystal polymer of Comparative Example 1 has a melt viscosity change rate higher than 0.3. Although it has good anti-foaming performance, its rod-shaped fluid length is obviously small and its melt fluidity is poor.
  • the liquid crystal polymer melt viscosity change rate of Comparative Example 2/3 is lower than -0.3, which is easy to foam and resistant to foaming. Poor foaming performance.
  • Example 6 in order to strictly control the heating rate in the 280-300°C heating section of the polycondensation section, the heating time is less than 1 hour, and a liquid crystal with a melt viscosity change rate in the range of -0.3 to 0.3 cannot be produced. polymer.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Polyamides (AREA)

Abstract

本发明公开了一种液晶聚合物，包括：59-72mol％的重复单元A：-O-Ar1-CO-；2-12mol％的重复单元B：-O-Ar2-CO-；8-20mol％的重复单元C：-CO-Ar3-CO-；5-17mol％的重复单元D：-O-Ar4-O-；3-10mol％的重复单元E：-Y-Ar5-Z-。本发明选用特定的单体组合反应，控制单体组成比例在一定范围内，通过采用稳定高效的鎓盐催化剂，同时在缩聚工段的280-300℃升温段严格控制升温速率，制备得到熔体粘度变化率为-0.3～0.3的液晶聚合物，其具有良好的流动性及抗起泡性能；通过增强填料增强改性制备得到液晶聚酯组合物，其熔体粘度变化率在-0.3-0.3范围内，仍具备良好的流动性和抗起泡性。特别适合在小型薄壁电子器件领域中应用。

Description

一种液晶聚合物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，具体涉及一种液晶聚合物及其制备方法和应用。
背景技术
热致液晶聚合物(TLCP)具有刚性的机械性质、耐化学性和尺寸精度等良好性能，其作为一种高性能的特种工程塑料，广泛应用于电子电器及小型精密薄壁零部件等领域。在信息和通信领域，有时需要非常薄的部件，特别是个人电脑和移动电话使用高度集成的器件，逐渐往小型化、薄壁化的方向发展。
为了安装电子元件，如连接器，目前优选使用环保的无铅焊料。无铅焊料的回流温度相对较高，在对TLCP制件进行焊接时，容易导致产品表面上形成气泡。为了优化材料抗起泡性能，中国专利申请CN103360730A公开通过在液晶聚合物中添加氧化钛或复合金属氧化物、群青等填充物，形成耐起泡性的组合物。中国专利申请CN102140232A采用一种液晶聚合物、填充片状填料和某种尺寸的炭黑的组合物，采用良好的改性方法制备出起泡发生率为零的组合物。中国专利申请CN105907058B通过在液晶聚合物组合物中引入锶元素，其组合物的耐高温稳定性和耐焊接起泡性得到意想不到的显著改善。综上可见，目前改善TLCP材料耐起泡性的常规方法主要是通过添加填充剂。然而，填充改性方法通常需采用固定的添加剂的类型，且往往会影响材料的流动性而削弱其成型性能，这对于小型、薄壁部件的注塑加工具有很大的挑战。
发明内容
为了克服上述现有技术存在的不足，本发明的目的在于提供一种液晶聚合物，具备优异的抗起泡性和良好的流动性。
本发明是通过以下技术方案实现的：
一种液晶聚合物，包括以下重复单元：
重复单元A：-O-Ar1-CO-；
重复单元B：-O-Ar2-CO-；
重复单元C：-CO-Ar3-CO-；
重复单元D：-O-Ar4-O-；
重复单元E：-Y-Ar5-Z-；
基于构成所述全芳香族聚酯酰胺的全部重复单元的总摩尔量，所述重复单元A的摩尔含量为 59-72mol％；所述重复单元B的摩尔含量为2-12mol％；所述重复单元C的摩尔含量为8-20mol％；所述重复单元D的摩尔含量为5-17mol％；所述重复单元E的摩尔含量为3-10mol％；其中，重复单元A中的Ar1表示对亚苯基；重复单元B中的Ar2表示亚萘基；重复单元C、D中的Ar3、Ar4分别独立地表示亚苯基、亚萘基或亚联苯基中的任意一种；重复单元E中的Ar5表示亚苯基、亚萘基或亚联苯基中的任意一种，Y和Z为相同或不同的有机或无机基团，但至少其中之一包含-NH-或-NR，其中R为芳基基团或包含1-6个碳的烷基基团中的任意一种；
所述Ar1、Ar2、Ar3、Ar4和Ar5的一个或多个氢原子可以各自独立地被卤原子、烷基或芳基取代。
优选的，所述重复单元A衍生自4-羟基苯甲酸、3-羟基苯甲酸或2-羟基苯甲酸中的至少一种；所述重复单元B衍生自6-羟基-2-萘甲酸、3-羟基-2-萘甲酸或1-羟基-2萘甲酸中的至少一种；所述重复单元C衍生自对苯二甲酸、间苯二甲酸、2,6萘二甲酸或4,4’-联苯二甲酸中的至少一种；所述重复单元D衍生自4,4’-二羟基联苯、对苯二酚或2,6-萘二酚等其中的至少一种；所述重复单元E衍生自4-乙酰氨基酚、对氨基苯酚、4’-氨基-4-联苯酚或6-乙酰氨基-2-萘酚中的至少一种。
更优选的，所述重复单元A衍生自4-羟基苯甲酸；所述重复单元B衍生自6-羟基-2-萘甲酸；所述重复单元C衍生自对苯二甲酸；所述重复单元D衍生自4,4’-二羟基联苯；所述重复单元E衍生自4-乙酰氨基酚。
本发明的液晶聚合物的熔体粘度变化率为-0.3～0.3。
熔体粘度变化率是一种反映液晶聚合物受热降解、链段酯交换或分子端基反应程度的有效表征手段，本发明经研究发现，本发明的液晶聚合物的熔体粘度变化率在-0.3～0.3范围内，其表现出良好的耐起泡性和流动性。当熔体粘度变化率小于-0.3时，液晶聚合物易于起泡；当熔体粘度变化率大于0.3时，液晶聚合物虽具有较好的耐起泡性，但流动性变差。
本发明所述的熔体粘度变化率，通过以下方法测得：采用毛细管流变仪，测试温度为熔点以上20℃、剪切速率1000s-1，预热后恒温，分别测得恒温0min时的熔融粘度(记为MV0min)和恒温15min时的熔融粘度(记为MV15min)，熔体粘度变化率＝(MV15min-MV0min)/MV15min。
本发明还提供上述液晶聚合物的制备方法，包括以下步骤：
(1)乙酰化工段：将重复单元A、重复单元B、重复单元D和重复单元E分别对应的单体，酰化剂、催化剂同时投入第一反应器中，在100-160℃温度下反应0.5-5h，让单体充分乙酰化；所述酰化剂选自乙酸酐、丙酸酐、丁酸酐、戊酸酐、2-乙基己酸酐、二氯乙酸酐或二氟乙酸 酐中的任意一种；所述催化剂为鎓盐催化剂；
其中，酰化剂与单体中酚羟基总摩尔量的摩尔比为(1-1.2)：1；催化剂的用量为理论出料量的20-2000ppm；
(2)缩聚工段：把步骤(1)乙酰化后的反应物转入第二反应器中，与重复单元C对应的单体进行熔融缩聚，以0.3-1.5℃/min升温速率升温至280℃后，控制升温速率使在280-300℃升温段的升温时间保持在1-3h，最后继续采用0.3-1.5℃/min升温速率升温至Tm-10℃～Tm+30℃，Tm为目标产品的熔点，升温期间不断馏出醋酸及其副产物；
(3)减压缩聚工段：通过对第二反应器进行减压缩聚，目标真空度为0.1kPa～40kPa，减压缩聚时间控制在3小时以内，最终控制排出时预聚物熔体的温度为Tm+5℃～Tm+30℃，Tm为目标产品的熔点；在熔融状态下排出预聚物，固化所述预聚物，进行切割或粉碎，得到的预聚物颗粒或粉末；
(4)固相聚合工段：在惰性气体氛围中排出预聚物，在真空度0.1Pa～50000Pa或者惰性气体氛围下进行固相聚合，聚合温度为0～340℃，反应时间0.5～40小时，达到既定熔融黏度后降温，制备得到全芳香族聚酯酰胺。
所述鎓盐催化剂的制备方法，包括以下步骤：将阳离子化合物和阴离子功能化合物按摩尔比为1：(1.01～1.20)加入反应器中，在温度为80℃下搅拌反应0-10h，制备得到鎓盐催化剂。
所述阴离子功能化合物选自乙酸、丙酸或丁酸中的任意一种；优选的，所述阴离子功能化合物选自乙酸。
所述阳离子化合物选自含有两个或两个以上氮原子的杂环有机碱类化合物；优选的，所述阳离子化合物选自咪唑化合物、三唑化合物或二吡啶基化合物中的任意一种；所述咪唑化合物选自1-甲基咪唑、2-甲基咪唑、4-甲基咪唑、1-乙基咪唑、2-乙基咪唑、4-乙基咪唑、1,2-二甲基咪唑、1,4-二甲基咪唑或2,4-二甲基咪唑中的任意一种；更优选的，所述阳离子化合物选自1-甲基咪唑。
本发明采用鎓盐作为催化剂，鎓盐催化剂由于形成离子键，具备高的化学键能使得其热稳定性良好，克服传统咪唑类等催化剂易挥发、热稳定性的不足的特点，具有更高效的催化效果，能够制备得到要求熔体粘度变化率的液晶聚合物。
本发明的液晶聚合物的制备方法，在步骤(2)缩聚工段，需在280-300℃温度段严格控制1-3h的升温时间，采用慢升温方式以促进芳香二羧酸充分参与聚合，避免单体损失引起树脂中的端基失衡，进而导致熔体粘度保持率下降。从能耗经济性及效果角度充分考虑，该升温段总用时控制在1-3小时。
本发明还提供一种液晶聚酯组合物，按重量份数计，包括以下组分：50-80份本发明所述的液晶聚合物；20-50份增强填料。
所述增强填料选自纤维状填料或非纤维状填料中的任意一种或几种。所述非纤维状填料选自片状填料或颗粒状填料中的任意一种或几种。
所述纤维状填料优选平均长度为50-250微米，长径比为30:1～600:1。所述纤维状填料包括但不仅限于玻璃纤维、钛酸钾纤维、金属包层的玻璃纤维、陶瓷纤维、硅灰石纤维、金属碳化物纤维、金属固化纤维、石棉纤维、氧化铝纤维、碳化硅纤维、石膏纤维或硼纤维中的任意一种或几种；优选为玻璃纤维。当所述纤维状填料尺寸在上述范围内时，液晶聚酯组合物表现出良好的抗起泡性能。
所述非纤维状填料优选平均粒径为0.01-50微米。当非纤维状填料的平均粒径小于0.01微米时，将导致液晶聚酯组合物的熔融加工性变差；当非纤维状填料的平均粒径大于50微米时，将导致不良的注塑成型品表面外观。所述非纤维状填料包括但不仅限于钛酸钾晶须、氧化锌晶须、硼酸铝晶须、滑石粉、炭黑、石膏、石棉、沸石、绢云母、高岭土、蒙脱土、粘土、锂蒙脱土、合成云母、硅铝酸盐、二氧化硅、氧化钛、氧化铝、氧化锌、氧化锆、氧化铁、碳酸钙、钛酸镁、白云石、硫酸铝、硫酸钡、硫酸镁、碳酸钙、云母、石英粉、氢氧化镁、氢氧化钙、氢氧化铝、玻璃珠、陶瓷珠、氮化硼或碳化硅的中的任意一种或几种。
本发明提供上述液晶聚酯组合物的制备方法，包括以下步骤：
采用双螺杆挤出机，加工温度设置在熔点以上10-50℃，按照配比将液晶聚合物从主喂口加入，增强填料从侧喂口加入，通过双螺杆挤出机共混之后熔融，经过模头出条、冷却、切粒，制备得到液晶聚酯组合物。
本发明所述的液晶聚酯组合物，通过增强填料增强改性后，其熔体粘度变化率在-0.3-0.3范围内，仍具备良好的流动性和抗起泡性。
本发明所述的液晶聚酯组合物中，在不损坏本发明的效果的范围内，还可以包括抗氧化剂、热稳定剂、紫外线吸收剂、润滑剂、脱模剂、包含染料或颜料的着色剂、增塑剂、抗静电剂中至少一种的加工助剂；或者还可以包括其他结构的液晶性聚酯或液晶聚酯以外的聚合物，所述的其他聚合物可以为全芳香族或半芳香族热致性液晶聚合物、芳香族或半芳香族聚酰胺、聚醚醚酮、聚醚砜、聚烯烃均聚物或共聚物等的一种或几种。通过这样的配合，可以进一步赋予规定的特性。
本发明还提供上述液晶聚合物或液晶聚酯组合物在电子电器领域的应用。具体的，特别适用于制备小型薄壁电子器件。
本发明具有以下有益效果：
本发明选用特定的单体组合反应，控制单体组成比例在一定范围内，通过采用稳定高效的鎓盐催化剂，同时在缩聚工段的280-300℃升温段严格控制升温速率，制备得到熔体粘度变化率为-0.3～0.3的液晶聚合物，其具有良好的流动性及抗起泡性能，特别适合在小型薄壁电子器件领域中应用。
本发明的液晶聚合物，通过增强填料增强改性制备得到液晶聚酯组合物，其熔体粘度变化率在-0.3-0.3范围内，仍具备良好的流动性和抗起泡性。
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。
对本发明实施例及对比例所用的原材料做如下说明，但不限于这些材料：
4-羟基苯甲酸：HBA，市购；
3-羟基苯甲酸：3-HBA，市购；
6-羟基-2-萘甲酸：2,6-HNA，市购；
3-羟基-2-萘甲酸：3,6-HNA，市购；
对苯二甲酸：TA，市购；
间苯二甲酸：IA，市购；
4,4’-二羟基联苯：BP，市购；
对苯二酚：HQ，市购；
4-乙酰氨基酚：APAP，市购；
4-氨基酚：p-AP，市购；
酰化剂：乙酸酐，AA，市购；
催化剂：鎓盐催化剂，通过自制获得：将1-甲基咪唑与乙酸按照摩尔比为1：1.01加入带搅拌的反应容器，在温度为80℃下搅拌反应5小时制备得到。
增强填料1：玻璃纤维，市购；
增强填料2：滑石粉，市购。
实施例1-5和对比例1-6的液晶聚合物的制备方法：
按照表1/表2配比，向装有搅拌器、单体投料口、回流冷凝器、温度计、氮气导入口的反应容器一中，加入HBA、HNA、BP、APAP、乙酸酐、鎓盐催化剂。投料完成后，用氮气彻底置换反应容器内的气氛，通氮气保护下将反应体系的温度升高至140℃，维持此温度回 流2h进行乙酰化反应。乙酰化反应结束后，将物料转移至配有扭矩传感器的搅拌器、保护气导入口、采出装置和真空装置反应器二中，并加入单体TA，搅拌并以1℃/min的升温速率升温至280℃后，控制升温速率使在280-300℃升温段保持1-3h的升温时间，然后再以1℃/min的升温速率升温至360℃，在此过程中，通过醋酸采出装置将聚合生成的醋酸采出。待物料温度达到360℃后，在30min内将反应器中压力降低至10kPa，待扭矩达到设定值后，通过保护气到入口通入二氧化碳至反应器的压力至0.3MPa，此时将聚合物熔体经反应器二的排出口以熔融态排出，冷却后造粒，得到预聚物。将预聚物投入转鼓进行固相增粘，增粘温度290℃，真空度至0.1kPa以下，达到既定熔融黏度后降温，制备得到液晶聚合物。
对比例7的液晶聚合物的制备方法与实施例2的区别仅在于：缩聚工段中，控制升温速率使在280-300℃升温段保持0.5h的升温时间。
实施例1-5和对比例1-7的液晶聚酯组合物的制备方法：
按照表1/表2配比制备液晶聚酯组合物：
采用双螺杆挤出机，加工温度设置在熔点以上10-50℃，按照表1/表2配比，将液晶聚合物从主喂口加入，增强填料从侧喂口加入，通过双螺杆挤出机共混之后熔融，经过模头出条、水槽冷却、牵引至切粒机进行切粒，制备得到液晶聚酯组合物。
采用下列方法对本发明所述全芳香族聚酯酰胺或液晶聚酯组合物的性能进行评价。
(1)熔融温度：采用差示扫描量热仪测得，从室温起以20℃/min的升温速率条件下升温到熔点+30℃的最高温度，在此温度下停留3min后再以20℃/min的速率降温至室温，测试样品在室温下停留3min后再次以20℃/min的升温速率升温到熔点+30℃的最高温度，得到聚合物的第二次熔融曲线，选取熔融峰值即为熔点。
(2)熔融粘度：采用毛细管流变仪测试，测试温度在熔融温度以上20℃，剪切速率1000S-1，使用内径1mm、长度40mm的口模，预热4min测得数据。
(3)熔体粘度变化率：按第(2)点测量熔融粘度，记为MV0min；再采用该方法测量，预热4min后继续保持15min，测得熔融粘度记为MV15min；计算熔体粘度变化率：
熔体粘度变化率＝(MV15min-MV0min)/MV15min。
(4)流动性：采用尺寸为宽*厚为5*0.45mm的棒状薄片注塑体的长度来表征全芳香族聚酯酰胺及液晶聚酯组合物的流动性，注塑温度在熔点附近，通过30根棒状薄片注塑体的长度平均值作为参数衡量液晶聚合物及液晶聚酯组合物的流动性。在相同注塑条件下，棒状薄片注塑体长度越长，表明其流动性越好。
(5)抗起泡性：在液晶聚合物或液晶聚酯组合物熔融温度以上5℃以及60mm/s的注射速度下，将全芳香族聚酯酰胺或液晶聚酯组合物成型为厚度1.0mm，长宽为60mm的薄片状 试样。将这些试样中的10个试样放入260℃的烘箱中5min，然后将试样取出，观察各试样表面的气泡产生情况。抗起泡性采用起泡率进行衡量，起泡率＝起泡块数/总块数*100％，起泡率越低，抗起泡性越好。
表1：实施例1-7的液晶聚合物的各单体含量及相关性能测试结果、液晶聚酯组合物各组分用量及相关性能测试结果
表2：对比例1-6的液晶聚合物的各单体含量及相关性能测试结果、液晶聚酯组合物各组分用量及相关性能测试结果

由上述实施例和对比例可看出，本发明选用特定的单体组合反应，控制单体组成比例在一定范围内，通过采用稳定高效的鎓盐催化剂，同时在缩聚工段的280-300℃升温段严格控制升温速率，制备得到熔体粘度变化率为-0.3～0.3的液晶聚合物，其具有良好的流动性及抗起泡性能；通过添加玻璃纤维等增强填料制备得到液晶聚酯组合物，熔体粘度变化率在-0.3～0.3范围内，同样具备良好的流动性和抗起泡性能。
对比例1-3的单体组成比例不在要求范围内，无法制得的熔体粘度变化率在-0.3～0.3范围内的液晶聚合物；对比例1的液晶聚合物熔体粘度变化率高于0.3，虽然具有较好的抗起泡性能，但其棒状流体长度明显较小，熔体流动性差；对比例2/3的液晶聚合物熔体粘度变化率低于-0.3，易于起泡，抗起泡性能差。
对比例4与实施例2比较，采用1-甲基咪唑催化剂，无法制得的熔体粘度变化率在-0.3～0.3范围内的液晶聚合物。
对比例5与实施例2/5比较，鎓盐催化剂用量过多，无法制得的熔体粘度变化率在-0.3～0.3范围内的液晶聚合物。
对比例6与实施例2比较，为严格控制在缩聚工段的280-300℃升温段的升温速率，升温用时低于1h，无法制得的熔体粘度变化率在-0.3～0.3范围内的液晶聚合物。

Claims (11)

  1. 一种液晶聚合物，其特征在于，包括以下重复单元：
    重复单元A：-O-Ar1-CO-；
    重复单元B：-O-Ar2-CO-；
    重复单元C：-CO-Ar3-CO-；
    重复单元D：-O-Ar4-O-；
    重复单元E：-Y-Ar5-Z-；
    基于构成所述液晶聚合物的全部重复单元的总摩尔量，所述重复单元A的摩尔含量为59-72mol％；所述重复单元B的摩尔含量为2-12mol％；所述重复单元C的摩尔含量为8-20mol％；所述重复单元D的摩尔含量为5-17mol％；所述重复单元E的摩尔含量为3-10mol％；其中，重复单元A中的Ar1表示亚苯基；重复单元B中的Ar2表示亚萘基；重复单元C、D中的Ar3、Ar4分别独立地表示亚苯基、亚萘基或亚联苯基中的任意一种；重复单元E中的Ar5表示亚苯基、亚萘基或亚联苯基中的任意一种，Y和Z为相同或不同的有机或无机基团，但至少其中之一包含-NH-或-NR，其中R为芳基基团或包含1-6个碳的烷基基团中的任意一种；
    所述Ar1、Ar2、Ar3、Ar4和Ar5的一个或多个氢原子可以各自独立地被卤原子、烷基或芳基取代。
  2. 根据权利要求1所述的液晶聚合物，其特征在于，所述重复单元A衍生自4-羟基苯甲酸、3-羟基苯甲酸或2-羟基苯甲酸中的至少一种；所述重复单元B衍生自6-羟基-2-萘甲酸、3-羟基-2-萘甲酸或1-羟基-2萘甲酸中的至少一种；所述重复单元C衍生自对苯二甲酸、间苯二甲酸、2,6-萘二甲酸或4,4’-联苯二甲酸中的至少一种；所述重复单元D衍生自4,4’-二羟基联苯、对苯二酚或2,6-萘二酚等其中的至少一种；所述重复单元E衍生自4-乙酰氨基酚、对氨基苯酚、4’-氨基-4-联苯酚或6-乙酰氨基-2-萘酚中的至少一种。
  3. 根据权利要求2所述的液晶聚合物，其特征在于，所述重复单元A衍生自4-羟基苯甲酸；所述重复单元B衍生自6-羟基-2-萘甲酸；所述重复单元C衍生自对苯二甲酸；所述重复单元D衍生自4,4’-二羟基联苯；所述重复单元E衍生自4-乙酰氨基酚。
  4. 根据权利要求1所述的液晶聚合物，其特征在于，所述液晶聚合物的熔体粘度变化率为-0.3～0.3。
  5. 根据权利要求1-4任一项所述的液晶聚合物的制备方法，其特征在于，包括以下步骤：
    (1)乙酰化工段：将重复单元A、重复单元B、重复单元D和重复单元E分别对应的单体，酰化剂、催化剂同时投入第一反应器中，在100-160℃温度下反应0.5-5h，让单体充分乙酰化；所述酰化剂选自乙酸酐、丙酸酐、丁酸酐、戊酸酐、2-乙基己酸酐、二氯乙酸酐或二氟乙酸 酐中的任意一种；所述催化剂为鎓盐催化剂；
    其中，酰化剂与单体中酚羟基总摩尔量的摩尔比为(1-1.2)：1；催化剂的用量为理论出料量的20-2000ppm；
    (2)缩聚工段：把步骤(1)乙酰化后的反应物转入第二反应器中，与重复单元C对应的单体进行熔融缩聚，以0.3-1.5℃/min升温速率升温至280℃后，控制升温速率使在280-300℃升温段的升温时间保持在1-3h，最后继续采用0.3-1.5℃/min升温速率升温至Tm-10℃～Tm+30℃，Tm为目标产品的熔点，升温期间不断馏出醋酸及其副产物；
    (3)减压缩聚工段：通过对第二反应器进行减压缩聚，目标真空度为0.1kPa～40kPa，减压缩聚时间控制在3小时以内，最终控制排出时预聚物熔体的温度为Tm+5℃～Tm+30℃，Tm为目标产品的熔点；在熔融状态下排出预聚物，固化所述预聚物，进行切割或粉碎，得到的预聚物颗粒或粉末；
    (4)固相聚合工段：在惰性气体氛围中排出预聚物，在真空度0.1Pa～50000Pa或者惰性气体氛围下进行固相聚合，聚合温度为0～340℃，反应时间0.5～40小时，达到既定熔融黏度后降温，制备得到液晶聚合物。
  6. 根据权利要求5所述的液晶聚合物的制备方法，其特征在于，所述鎓盐催化剂的制备方法，包括以下步骤：将阳离子化合物和阴离子功能化合物按摩尔比为1：(1.01～1.20)加入反应器中，在温度为80℃下搅拌反应0-10h，制备得到鎓盐催化剂；所述阴离子功能化合物选自乙酸、丙酸或丁酸中的任意一种；所述阳离子化合物选自含有两个或两个以上氮原子的杂环有机碱类化合物；优选的，所述阳离子化合物选自咪唑化合物、三唑化合物或二吡啶基化合物中的任意一种；所述咪唑化合物选自1-甲基咪唑、2-甲基咪唑、4-甲基咪唑、1-乙基咪唑、2-乙基咪唑、4-乙基咪唑、1,2-二甲基咪唑、1,4-二甲基咪唑或2,4-二甲基咪唑中的任意一种。
  7. 根据权利要求6所述的液晶聚合物的制备方法，其特征在于，所述阴离子功能化合物选自乙酸；所述阳离子化合物选自1-甲基咪唑。
  8. 一种液晶聚酯组合物，其特征在于，按重量份数计，包括以下组分：50-80份权利要求1-4任一项所述的液晶聚合物；20-50份增强填料。
  9. 根据权利要求8所述的液晶聚合物，其特征在于，所述液晶聚酯组合物的熔体粘度变化率为-0.3～0.3。
  10. 根据权利要求1-4任一项所述的液晶聚合物或权利要求8-9任一项所述的液晶聚酯组合物在电子电器领域的应用。
  11. 根据权利要求9所述的液晶聚合物或液晶聚酯组合物在电子电器领域的应用，其特征在于，用于制备小型薄壁电子器件。
PCT/CN2023/095591 2022-04-01 2023-05-22 一种液晶聚合物及其制备方法和应用 WO2023186187A1 (zh)

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