CN117510804A - Liquid crystal polyester suitable for manufacturing thin-wall electronic product and preparation method thereof - Google Patents
Liquid crystal polyester suitable for manufacturing thin-wall electronic product and preparation method thereof Download PDFInfo
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- CN117510804A CN117510804A CN202210901372.6A CN202210901372A CN117510804A CN 117510804 A CN117510804 A CN 117510804A CN 202210901372 A CN202210901372 A CN 202210901372A CN 117510804 A CN117510804 A CN 117510804A
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- 229920000728 polyester Polymers 0.000 title claims abstract description 65
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 36
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 14
- -1 aliphatic acid anhydride Chemical class 0.000 claims abstract description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 12
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims abstract description 3
- 239000002981 blocking agent Substances 0.000 claims abstract 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 52
- 239000000463 material Substances 0.000 claims description 38
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 33
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 26
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- 238000006116 polymerization reaction Methods 0.000 claims description 24
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 claims description 21
- 238000006640 acetylation reaction Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 15
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 10
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 2
- DUCKXCGALKOSJF-UHFFFAOYSA-N pentanoyl pentanoate Chemical compound CCCCC(=O)OC(=O)CCCC DUCKXCGALKOSJF-UHFFFAOYSA-N 0.000 claims description 2
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 238000007789 sealing Methods 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 14
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 10
- 238000007599 discharging Methods 0.000 description 10
- 238000006068 polycondensation reaction Methods 0.000 description 10
- 239000004246 zinc acetate Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000004321 preservation Methods 0.000 description 8
- 229920000106 Liquid crystal polymer Polymers 0.000 description 6
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 5
- 229940031826 phenolate Drugs 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZMRQTIAUOLVKOX-UHFFFAOYSA-L calcium;diphenoxide Chemical compound [Ca+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 ZMRQTIAUOLVKOX-UHFFFAOYSA-L 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- KRPXAHXWPZLBKL-UHFFFAOYSA-L magnesium;diphenoxide Chemical compound [Mg+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 KRPXAHXWPZLBKL-UHFFFAOYSA-L 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- ZGJADVGJIVEEGF-UHFFFAOYSA-M potassium;phenoxide Chemical compound [K+].[O-]C1=CC=CC=C1 ZGJADVGJIVEEGF-UHFFFAOYSA-M 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- 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
- C08G63/78—Preparation processes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a liquid crystal polyester suitable for manufacturing thin-wall electronic products and a preparation method thereof, wherein the liquid crystal polyester is prepared by reacting aromatic hydroxycarboxylic acid, a blocking agent and aliphatic acid anhydride, the blocking agent is at least one of aromatic dicarboxylic acid, aliphatic carboxylic acid and aromatic diphenol, the molar ratio of the aromatic hydroxycarboxylic acid to the blocking agent is (95:5) - (99.9:0.1), and the ratio of the total molar amount of hydroxyl provided by the aromatic hydroxycarboxylic acid and the blocking agent to the total molar amount of carboxyl provided by the aromatic hydroxycarboxylic acid and the blocking agent is 1 (1.001-1.05) or 1.001-1.05): 1. The invention realizes the end sealing of the molecular chain from the molecular structure by relatively slightly excessive hydroxyl or carboxyl in the reaction system, not only effectively improves the fluidity of the liquid crystal polyester, but also has excellent mechanical strength, can ensure the stability of the molecular weight of the liquid crystal polyester, and has remarkable application value for realizing the industrialized manufacture of the thinned electronic product.
Description
Technical Field
The invention relates to a liquid crystal polyester suitable for manufacturing thin-wall electronic products and a preparation method thereof, belonging to the technical field of liquid crystal polyester materials.
Background
The liquid crystal polyester (liquid crystal polymer, LCP) is a novel high-performance special engineering plastic developed in the early 80 s, and belongs to the category of aromatic thermoplastic polyesters. The molecular structure of LCP is a rigid chain segment, forms a liquid crystal state in a molten state, has high strength and high rigidity, is generally known for various purposes such as high strength, high modulus, excellent melt processing and molding characteristics, inherent flame retardance, low water absorption, chemical corrosion resistance, good irradiation resistance and high temperature, and has been widely used in the fields of aviation, aerospace, sports goods, automobile industry, ocean engineering, petroleum industry and the like in recent years, in particular for thin-wall electronic parts. However, when used in thin-wall electronic products, the liquid crystal polyester has higher requirements on fluidity and strength. Therefore, how to improve the fluidity of the liquid crystal polyester while ensuring the excellent mechanical properties of the liquid crystal polyester has become a major research focus in the art.
Chinese patent application CN 201911322541.5 provides a high-fluidity wholly aromatic liquid crystalline polyester and a preparation method thereof, wherein the liquid crystalline polyester is prepared by firstly performing an acetylation reaction on a monomer, aliphatic acid anhydride and a capping agent, then performing melt polymerization to obtain a prepolymer, and then crushing and tackifying the prepolymer; although the patent application can effectively control the molecular weight of the liquid crystal polyester by introducing the end-capping agent, so that the synthesized liquid crystal polyester has the advantages of high fluidity, good stability and favorability for post-processing and forming, the end-capping agent used in the patent application is metal phenolate, and particularly one or more of sodium phenolate, potassium phenolate, calcium phenolate or magnesium phenolate disclosed in the specification of the application has the following defects: 1) The metal phenolate type end-capping agent is easy to decompose at high temperature to generate byproducts in the later stage of melt polycondensation, so that the product quality of the liquid crystal polyester can be influenced; 2) The high-purity metal phenolate raw material is difficult to obtain, the price of the metal phenolate with common purity is also very high, the production cost is increased, and trace moisture and impurities in the metal phenolate are unfavorable for polycondensation reaction; therefore, the technology of the patent application cannot well meet the industrial production requirement, so that the development of the liquid crystal polyester which has excellent mechanical properties, good fluidity, easy discharging in production and capability of controlling the stability of molecular weight among batches is very necessary, and has the key points of low-cost and easily obtained raw materials, low cost and no influence on the quality of the final product caused by byproducts generated in polymerization reaction and the preparation method of the liquid crystal polyester have very high necessity and obvious practical value and important significance for industrialization of thin-wall electronic products.
Disclosure of Invention
In view of the foregoing problems and needs in the art, it is an object of the present invention to provide a liquid crystal polyester suitable for manufacturing thin-walled electronic articles and a method for preparing the same.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a liquid crystal polyester suitable for manufacturing thin-wall electronic products is prepared by reacting aromatic hydroxycarboxylic acid, end-capping agent and aliphatic acid anhydride, wherein the end-capping agent is at least one of aromatic dicarboxylic acid, aliphatic carboxylic acid and aromatic diphenol, the molar ratio of the aromatic hydroxycarboxylic acid to the end-capping agent is (95:5) - (99.9:0.1), and the ratio of the total molar amount of hydroxyl groups provided by the aromatic hydroxycarboxylic acid and the end-capping agent to the total molar amount of carboxyl groups provided by the aromatic hydroxycarboxylic acid and the end-capping agent is 1 (1.001-1.05) or 1.001-1.05): 1.
In a preferred embodiment, the end-capping agent is at least one selected from terephthalic acid, isophthalic acid, 2, 6-naphthalene dicarboxylic acid, phthalic acid, 1,3, 5-benzene tricarboxylic acid, hydroquinone, 4-dihydroxybiphenyl, and 2, 6-naphthalene diphenol.
Further preferably, the end capping agent is selected from any one of terephthalic acid, isophthalic acid, phthalic acid and hydroquinone.
In a preferred embodiment, the molar ratio of the aromatic hydroxycarboxylic acid to the capping agent is (97:3) to (99.5:0.5).
In a preferred embodiment, the ratio of the total molar amount of hydroxyl groups provided by the aromatic hydroxycarboxylic acid and the capping agent to the total molar amount of carboxyl groups provided is 1 (1.005-1.03) or 1.005-1.03): 1.
In a preferred embodiment, the aromatic hydroxycarboxylic acid is a composition comprising p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid.
In a preferred embodiment, the molar ratio of p-hydroxybenzoic acid to 2-hydroxy-6-naphthoic acid in the aromatic hydroxycarboxylic acid is (65:35) to (85:15).
In a further preferred embodiment, the molar ratio of p-hydroxybenzoic acid to 2-hydroxy-6-naphthoic acid in the aromatic hydroxycarboxylic acid is from (70:30) to (80:20).
Preferably, the aliphatic acid anhydride is at least one selected from acetic anhydride, propionic anhydride, butyric anhydride and valeric anhydride, and more preferably acetic anhydride.
Preferably, the aliphatic anhydride is used in an amount of 1.01 to 1.5 times, most preferably 1.03 to 1.3 times, the total molar amount of hydroxyl groups provided by the aromatic hydroxycarboxylic acid and the capping agent.
The preparation method of the liquid crystal polyester suitable for manufacturing the thin-wall electronic product comprises the following steps:
a) Adding the aromatic hydroxycarboxylic acid, the end-capping agent, the aliphatic acid anhydride and the catalyst in the proportion into a reactor, and heating to 120-180 ℃ at a heating rate of 1-10 ℃/min (preferably 3-6 ℃/min) to enable acetylation reaction to occur;
b) After the acetylation reaction is completed, the temperature is raised to 280-360 ℃ at a heating rate of 20-40 ℃/h (preferably 25-30 ℃/h), and the temperature is preferably 310-330 ℃ for 10-60 minutes (preferably 20-40 minutes) to enable melt polymerization to occur;
c) Then reducing the pressure, and when the stirring torque value is stable or reaches a preset value, introducing nitrogen to enable the system to be in a normal pressure state, and terminating the polymerization reaction;
d) The obtained polymer is pressurized and discharged from the polymerization reactor in the form of material strips, and the material strips are granulated by water bracing, so as to obtain the liquid crystal polyester granules.
In a preferred embodiment, the catalyst comprises a metal compound (e.g., titanium dioxide, antimony trioxide), an alkali metal or alkaline earth metal salt of a carboxylic acid (e.g., potassium acetate, zinc acetate),salts of mineral acids (e.g. K 2 SO 4 ) Lewis acids (e.g. BF 3 ) Gaseous acid catalysts (e.g., HCl); more preferably an alkali metal salt, still more preferably zinc acetate, in an amount of 1 to 1000ppm (preferably 30 to 300 ppm) based on the total amount of all monomers.
Compared with the prior art, the invention has the following beneficial effects:
experiments prove that the ratio of the total molar quantity of hydroxyl groups to the total molar quantity of carboxyl groups provided in a reaction system is unbalanced by adding the component of the end-capping agent containing hydroxyl groups or carboxyl groups, so that the total molar quantity of hydroxyl groups or the total molar quantity of carboxyl groups is relatively slightly excessive, the end capping of molecular chains on a molecular structure is realized, the molecular weight of the liquid crystal polyester is effectively controlled, the viscosity of the liquid crystal polyester is reduced, the flowability of the liquid crystal polyester is effectively improved, and the liquid crystal polyester has excellent mechanical strength, so that the liquid crystal polyester has excellent processability and is very suitable for manufacturing thinned electronic products; in addition, the invention can effectively control the molecular weight of the liquid crystal polyester, thus ensuring the stability of the molecular weight of the liquid crystal polyester in different discharging time and different batches in the same batch and improving the quality stability of the final liquid crystal polyester product; therefore, compared with the prior art, the invention has obvious progress and application value.
Detailed Description
The technical scheme of the invention is further and fully described in the following by combining examples and comparative examples. It should be understood that the following examples are illustrative of the present invention and are not intended to limit the scope of the present invention.
The experimental procedures, which do not address the specific conditions in the examples below, are generally carried out under conventional conditions or under conditions recommended by the manufacturer.
Example 1
921.6g (6.7 mol) of parahydroxybenzoic acid (HBA) and 463.9g (2.5 mol) of 2-hydroxy-6-naphthoic acid (HNA) were first mixed and then introduced into a reactor equipped with a nitrogen inlet, a torquemeter, a condenser and a stirring device, and 980g (9.6 mol) of acetic anhydride, 9.1g (0.05 mol) of terephthalic acid (TPA) and 712.7mg of zinc acetate were then introduced into the reactor;
after nitrogen is introduced for 10 minutes in a stirring state, the temperature of the material is raised from room temperature to 150 ℃ for 30 minutes, so that the material is subjected to acetylation reaction at 150 ℃ in a heat preservation way;
when the acetylation reaction is finished (about 2 hours of reaction), slowly heating to 320 ℃ for 6 hours, carrying out melt polycondensation reaction at 320 ℃ for 30 minutes while evaporating out byproduct acetic acid;
then the pressure of the system is reduced to 5 mmHg after 60 minutes, when the stirring torque value is stable or reaches a preset value, nitrogen is introduced to make the system in a normal pressure state, and the polymerization reaction is terminated;
pressurizing and discharging the obtained polymer from the polymerization reactor in a material strip mode, and granulating the material strip through a water brace to obtain the liquid crystal polyester particles.
Example 2
921.6g (6.7 mol) of parahydroxybenzoic acid (HBA) and 463.9g (2.5 mol) of 2-hydroxy-6-naphthoic acid (HNA) were first mixed and then introduced into a reactor equipped with a nitrogen inlet, a torquemeter, a condenser and a stirring device, and 980g (9.6 mol) of acetic anhydride, 12.1g (0.07 mol) of terephthalic acid (TPA) and 712.7mg of zinc acetate were then introduced into the reactor;
after nitrogen is introduced for 10 minutes in a stirring state, the temperature of the material is raised from room temperature to 150 ℃ for 30 minutes, so that the material is subjected to acetylation reaction at 150 ℃ in a heat preservation way;
when the acetylation reaction is finished (about 2 hours of reaction), slowly heating to 320 ℃ for 6 hours, carrying out melt polycondensation reaction at 320 ℃ for 30 minutes while evaporating out byproduct acetic acid;
then the pressure of the system is reduced to 5 mmHg after 60 minutes, when the stirring torque value is stable or reaches a preset value, nitrogen is introduced to make the system in a normal pressure state, and the polymerization reaction is terminated;
pressurizing and discharging the obtained polymer from the polymerization reactor in a material strip mode, and granulating the material strip through a water brace to obtain the liquid crystal polyester particles.
Example 3
921.6g (6.7 mol) of parahydroxybenzoic acid (HBA) and 463.9g (2.5 mol) of 2-hydroxy-6-naphthoic acid (HNA) were first mixed and then introduced into a reactor equipped with a nitrogen inlet, a torquemeter, a condenser and a stirring device, and 980g (9.6 mol) of acetic anhydride, 18.2g (0.11 mol) of terephthalic acid (TPA) and 715.8mg of zinc acetate were then introduced into the reactor;
after nitrogen is introduced for 10 minutes in a stirring state, the temperature of the material is raised from room temperature to 150 ℃ for 30 minutes, so that the material is subjected to acetylation reaction at 150 ℃ in a heat preservation way;
when the acetylation reaction is finished (about 2 hours of reaction), slowly heating to 320 ℃ for 6 hours, carrying out melt polycondensation reaction at 320 ℃ for 30 minutes while evaporating out byproduct acetic acid;
then the pressure of the system is reduced to 5 mmHg after 60 minutes, when the stirring torque value is stable or reaches a preset value, nitrogen is introduced to make the system in a normal pressure state, and the polymerization reaction is terminated;
pressurizing and discharging the obtained polymer from the polymerization reactor in a material strip mode, and granulating the material strip through a water brace to obtain the liquid crystal polyester particles.
Example 4
921.6g (6.7 mol) of parahydroxybenzoic acid (HBA) and 463.9g (2.5 mol) of 2-hydroxy-6-naphthoic acid (HNA) were first mixed and then introduced into a reactor having a nitrogen inlet, a torquemeter, a condenser and a stirring device, and 980g (9.6 mol) of acetic anhydride, 12.1g (0.07 mol) of isophthalic acid and 712.7mg of zinc acetate were then introduced into the reactor;
after nitrogen is introduced for 10 minutes in a stirring state, the temperature of the material is raised from room temperature to 150 ℃ for 30 minutes, so that the material is subjected to acetylation reaction at 150 ℃ in a heat preservation way;
when the acetylation reaction is finished (about 2 hours of reaction), slowly heating to 320 ℃ for 6 hours, carrying out melt polycondensation reaction at 320 ℃ for 30 minutes while evaporating out byproduct acetic acid;
then the pressure of the system is reduced to 5 mmHg after 60 minutes, when the stirring torque value is stable or reaches a preset value, nitrogen is introduced to make the system in a normal pressure state, and the polymerization reaction is terminated;
pressurizing and discharging the obtained polymer from the polymerization reactor in a material strip mode, and granulating the material strip through a water brace to obtain the liquid crystal polyester particles.
Example 5
921.6g (6.7 mol) of parahydroxybenzoic acid (HBA) and 463.9g (2.5 mol) of 2-hydroxy-6-naphthoic acid (HNA) were first mixed and then introduced into a reactor having a nitrogen inlet, a torquemeter, a condenser and a stirring device, and 980g (9.6 mol) of acetic anhydride, 12.1g (0.07 mol) of phthalic acid and 712.7mg of zinc acetate were then introduced into the reactor;
after nitrogen is introduced for 10 minutes in a stirring state, the temperature of the material is raised from room temperature to 150 ℃ for 30 minutes, so that the material is subjected to acetylation reaction at 150 ℃ in a heat preservation way;
when the acetylation reaction is finished (about 2 hours of reaction), slowly heating to 320 ℃ for 6 hours, carrying out melt polycondensation reaction at 320 ℃ for 30 minutes while evaporating out byproduct acetic acid;
then the pressure of the system is reduced to 5 mmHg after 60 minutes, when the stirring torque value is stable or reaches a preset value, nitrogen is introduced to make the system in a normal pressure state, and the polymerization reaction is terminated;
pressurizing and discharging the obtained polymer from the polymerization reactor in a material strip mode, and granulating the material strip through a water brace to obtain the liquid crystal polyester particles.
Example 6
921.6g (6.7 mol) of parahydroxybenzoic acid (HBA) and 463.9g (2.5 mol) of 2-hydroxy-6-naphthoic acid (HNA) were first mixed and then introduced into a reactor having a nitrogen inlet, a torquemeter, a condenser and a stirring device, and 997g (9.8 mol) of acetic anhydride, 8.0g (0.07 mol) of hydroquinone and 717.3mg of zinc acetate were then introduced into the reactor;
after nitrogen is introduced for 10 minutes in a stirring state, the temperature of the material is raised from room temperature to 150 ℃ for 30 minutes, so that the material is subjected to acetylation reaction at 150 ℃ in a heat preservation way;
when the acetylation reaction is finished (about 2 hours of reaction), slowly heating to 320 ℃ for 6 hours, carrying out melt polycondensation reaction at 320 ℃ for 30 minutes while evaporating out byproduct acetic acid;
then the pressure of the system is reduced to 5 mmHg after 60 minutes, when the stirring torque value is stable or reaches a preset value, nitrogen is introduced to make the system in a normal pressure state, and the polymerization reaction is terminated;
pressurizing and discharging the obtained polymer from the polymerization reactor in a material strip mode, and granulating the material strip through a water brace to obtain the liquid crystal polyester particles.
Comparative example 1
921.6g (6.7 mol) of parahydroxybenzoic acid (HBA) and 463.9g (2.5 mol) of 2-hydroxy-6-naphthoic acid (HNA) were first mixed and then introduced into a reactor having a nitrogen inlet, a torquemeter, a condenser and a stirring device, and 980g (9.6 mol) of acetic anhydride and 709.6mg of zinc acetate were then introduced into the reactor;
after nitrogen is introduced for 10 minutes in a stirring state, the temperature of the material is raised from room temperature to 150 ℃ for 30 minutes, so that the material is subjected to acetylation reaction at 150 ℃ in a heat preservation way;
when the acetylation reaction is finished (about 2 hours of reaction), slowly heating to 320 ℃ for 6 hours, carrying out melt polycondensation reaction at 320 ℃ for 30 minutes while evaporating out byproduct acetic acid;
then the pressure of the system is reduced to 5 mmHg after 60 minutes, when the stirring torque value is stable or reaches a preset value, nitrogen is introduced to make the system in a normal pressure state, and the polymerization reaction is terminated;
pressurizing and discharging the obtained polymer from the polymerization reactor in a material strip mode, and granulating the material strip through a water brace to obtain the contrast liquid crystal polyester particles.
Comparative example 2
921.6g (6.7 mol) of parahydroxybenzoic acid (HBA) and 463.9g (2.5 mol) of 2-hydroxy-6-naphthoic acid (HNA) were first mixed and then introduced into a reactor equipped with a nitrogen inlet, a torquemeter, a condenser and a stirring device, and 980g (9.6 mol) of acetic anhydride, 22.8g (0.14 mol) of terephthalic acid (TPA) and 715.8mg of zinc acetate were then introduced into the reactor;
after nitrogen is introduced for 10 minutes in a stirring state, the temperature of the material is raised from room temperature to 150 ℃ for 30 minutes, so that the material is subjected to acetylation reaction at 150 ℃ in a heat preservation way;
when the acetylation reaction is finished (about 2 hours of reaction), slowly heating to 320 ℃ for 6 hours, carrying out melt polycondensation reaction at 320 ℃ for 30 minutes while evaporating out byproduct acetic acid;
then the pressure of the system is reduced to 5 mmHg after 60 minutes, when the stirring torque value is stable or reaches a preset value, nitrogen is introduced to make the system in a normal pressure state, and the polymerization reaction is terminated;
pressurizing and discharging the obtained polymer from the polymerization reactor in a material strip mode, and granulating the material strip through a water brace to obtain the contrast liquid crystal polyester particles.
In order to verify the progress of the liquid crystal polyesters prepared in examples 1 to 6 of the present invention, the liquid crystal polyesters prepared in examples 1 to 6 and comparative examples 1 to 2 were respectively injection molded into respective standard bars by an injection molding machine, and each liquid crystal polyester sample was subjected to performance evaluation by the following detection method:
1. < method for measuring melting temperature >
Melting point Tm of the liquid crystal polyester was measured using a differential scanning calorimeter (DSC, american TA company), and the LCP sample to be measured was warmed from room temperature to 340℃at a rate of 20℃per minute, and incubated at 340℃for 5 minutes; then cooling the sample to room temperature at a rate of 10 ℃/min, and heating to 340 ℃ at a rate of 10 ℃/min; the final absorption peak is the melting temperature of the LCP sample, namely Tm.
2. < method for measuring melt viscosity >
The measurement was carried out by using a Dynasco LCR7000 capillary rheometer using a die having an inner diameter of 1mm and a length of 40mm, and the measurement was carried out at Tm+20deg.C and a shear rate of 1000S -1 The viscosity under the conditions is melt viscosity.
3. < method for measuring inherent viscosity >
Liquid crystal polyester is prepared into a solution with the concentration of 0.1 weight percent by taking pentafluorophenol as a solvent, the measurement temperature is 60 ℃, and the solution is measured by using a Ubbelohde viscometer with the inner diameter of 0.7mm and then calculated by an inherent viscosity formula.
4. < method for measuring flowability >
After the LCP sample is dried for 4 hours at 150 ℃, an injection molding machine with an S-shaped sample is used for molding, the temperature of a charging barrel is selected to be the Tm+5 ℃ of liquid crystal polyester, and an S-shaped sample strip with the width of 10mm and the thickness of 1.0mm is obtained, and the flow property of the liquid crystal polyester resin is measured according to the length of the sample strip.
5. < method for measuring tensile Property >
Tensile properties were tested according to GB/T1040 standard using the American INSTRON 3400 series Universal materials tester.
The results of the respective tests of the liquid crystal polyesters obtained in examples 1 to 6 and comparative examples 1 to 2 are shown in Table 1.
TABLE 1 results of Performance test of liquid Crystal polyesters obtained in examples 1 to 6 and comparative examples 1 to 2
| Test index | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Comparative example 1 | Comparative example 2 |
| Tensile Strength (MPa) | 111 | 109 | 95 | 103 | 101 | 103 | 115 | 63 |
| Tensile modulus (GPa) | 10.1 | 9.9 | 8.7 | 9.7 | 9.6 | 9.5 | 10.5 | 5.6 |
| Melting point (. Degree. C.) | 281.3 | 281.7 | 281.9 | 281.6 | 281.4 | 281.7 | 281.6 | 281.2 |
| Melt viscosity (Pa.S) | 23.8 | 22.9 | 21.6 | 22.8 | 23 | 23 | 26.2 | 15.7 |
| Inherent viscosity (dl/g) | 4.67 | 4.53 | 4.32 | 4.57 | 4.55 | 4.56 | 5.08 | 3.1 |
| Fluidity (mm) | 690 | 760 | 950 | 757 | 763 | 762 | 530 | ＞1000 |
The results shown in Table 1 can be seen: compared with comparative example 1 (the difference between the comparative example and examples 1-6 is that no end-capping agent is added in the comparative example, the balance between the total molar quantity of hydroxyl groups and the total molar quantity of carboxyl groups provided in the reaction system is 1:1, and the other conditions are the same), the viscosity of the liquid crystal polyesters prepared in examples 1-6 of the invention is reduced, the fluidity is obviously improved, the length of a spline obtained by injection molding can be increased by 79% at most, and the average can be increased by 47%, but the mechanical property can still be kept excellent; the invention shows that the hydroxyl and carboxyl in the reaction system are unbalanced by keeping the total molar quantity of hydroxyl or the total molar quantity of carboxyl in the reaction system in a slight excess, so that the end capping of molecular chains on the molecular structure is realized, the viscosity of the liquid crystal polyester is reduced, the molecular weight of the liquid crystal polyester is effectively controlled, and the fluidity of the liquid crystal polyester is effectively improved. In addition, as can be seen from comparative examples 2, 4, 5 and 6, under the condition of the same conditions, when the same proportion of aromatic dicarboxylic acid or aromatic diphenol is added into the reaction system, the almost same flow property can be achieved, but in contrast, terephthalic acid is used as the end-capping agent, so that better mechanical property can be obtained; meanwhile, as can be seen from comparative examples 1 to 3 and comparative example 2, under the same conditions, the tensile strength of the obtained liquid crystal polyester decreases with the increase of the amount of the end capping agent added in the reaction system, which indicates that the amount of the end capping agent has a positive and negative influence on the fluidity and mechanical strength of the obtained liquid crystal polyester, and a satisfactory comprehensive effect can be obtained by selecting a proper balance point, thereby indicating that the technical scheme of the invention is not expected and obvious.
Finally, it is pointed out here that: the above is only a part of the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adaptations of the present invention based on the foregoing are within the scope of the present invention.
Claims (10)
1. A liquid crystalline polyester suitable for the manufacture of thin-walled electronic articles, characterized by: the aromatic hydroxy carboxylic acid is obtained by reacting aromatic hydroxy carboxylic acid, a blocking agent and aliphatic acid anhydride, wherein the blocking agent is at least one of aromatic dicarboxylic acid, aliphatic carboxylic acid and aromatic diphenol, the molar ratio of the aromatic hydroxy carboxylic acid to the blocking agent is (95:5) - (99.9:0.1), and the ratio of the total molar amount of hydroxyl provided by the aromatic hydroxy carboxylic acid and the blocking agent to the total molar amount of carboxyl provided by the aromatic hydroxy carboxylic acid and the blocking agent is 1 (1.001-1.05) or 1.001-1.05): 1.
2. The liquid crystalline polyester of claim 1, wherein: the end capping agent is at least one selected from terephthalic acid, isophthalic acid, 2, 6-naphthalene dicarboxylic acid, phthalic acid, 1,3, 5-benzene tricarboxylic acid, hydroquinone, 4-dihydroxybiphenyl and 2, 6-naphthalene diphenol.
3. The liquid crystalline polyester of claim 2, wherein: the end capping agent is selected from any one of terephthalic acid, isophthalic acid, phthalic acid and hydroquinone.
4. The liquid crystalline polyester of claim 1, wherein: the molar ratio of the aromatic hydroxycarboxylic acid to the capping agent is (97:3) to (99.5:0.5).
5. The liquid crystalline polyester of claim 1, wherein: the ratio of the total molar quantity of hydroxyl groups provided by the aromatic hydroxycarboxylic acid and the end capping agent to the total molar quantity of carboxyl groups provided is 1 (1.005-1.03) or 1.005-1.03): 1.
6. The liquid crystalline polyester of claim 1, wherein: the aromatic hydroxycarboxylic acid is a composition formed by parahydroxybenzoic acid and 2-hydroxy-6-naphthoic acid.
7. The liquid crystalline polyester of claim 6, wherein: in the aromatic hydroxycarboxylic acid, the molar ratio of the parahydroxybenzoic acid to the 2-hydroxy-6-naphthoic acid is (65:35) to (85:15).
8. The liquid crystalline polyester of claim 1, wherein: the aliphatic acid anhydride is at least one selected from acetic anhydride, propionic anhydride, butyric anhydride and valeric anhydride.
9. The liquid crystalline polyester of claim 1, wherein: the use amount of the aliphatic acid anhydride is 1.01 to 1.5 times of the total molar amount of the hydroxyl groups provided by the aromatic hydroxycarboxylic acid and the end capping agent.
10. A method of preparing a liquid crystalline polyester suitable for the manufacture of thin-walled articles according to any of claims 1 to 9, characterized by the steps of:
a) Adding the aromatic hydroxycarboxylic acid, the end-capping agent, the aliphatic acid anhydride and the catalyst in the proportion into a reactor, and heating to 120-180 ℃ at the heating rate of 1-10 ℃/min to cause acetylation reaction;
b) After the acetylation reaction is finished, the temperature is raised to 280-360 ℃ at a heating rate of 20-40 ℃/hour, so that melt polymerization is carried out for 10-60 minutes;
c) Then reducing the pressure, and when the stirring torque value is stable or reaches a preset value, introducing nitrogen to enable the system to be in a normal pressure state, and terminating the polymerization reaction;
d) The obtained polymer is pressurized and discharged from the polymerization reactor in the form of material strips, and the material strips are granulated by water bracing, so as to obtain the liquid crystal polyester granules.
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