CN117887050A - Preparation method and application of liquid crystal polymer - Google Patents
Preparation method and application of liquid crystal polymer Download PDFInfo
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- CN117887050A CN117887050A CN202410106528.0A CN202410106528A CN117887050A CN 117887050 A CN117887050 A CN 117887050A CN 202410106528 A CN202410106528 A CN 202410106528A CN 117887050 A CN117887050 A CN 117887050A
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- liquid crystal
- crystal polymer
- fiber
- inorganic filler
- biphenol
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- 229920000106 Liquid crystal polymer Polymers 0.000 title claims abstract description 99
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 51
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 46
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 34
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000011261 inert gas Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000011256 inorganic filler Substances 0.000 claims abstract description 15
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- -1 2, 6-dicarboxyl biphenyl alkene Chemical class 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 11
- 239000007790 solid phase Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 21
- SGRVMTDADJLWDP-UHFFFAOYSA-N 2-phenylbenzene-1,3-dicarboxylic acid Chemical group OC(=O)C1=CC=CC(C(O)=O)=C1C1=CC=CC=C1 SGRVMTDADJLWDP-UHFFFAOYSA-N 0.000 claims description 16
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 15
- 239000000835 fiber Substances 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 239000003365 glass fiber Substances 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 229910052582 BN Inorganic materials 0.000 claims description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 4
- 229910010272 inorganic material Inorganic materials 0.000 claims description 3
- 239000011147 inorganic material Substances 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 241000276425 Xiphophorus maculatus Species 0.000 claims description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000000378 calcium silicate Substances 0.000 claims description 2
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000005187 foaming Methods 0.000 abstract description 25
- 238000001125 extrusion Methods 0.000 abstract description 5
- 238000005469 granulation Methods 0.000 abstract description 3
- 230000003179 granulation Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 21
- 238000002844 melting Methods 0.000 description 18
- 230000008018 melting Effects 0.000 description 18
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 14
- 238000012545 processing Methods 0.000 description 12
- 229910000856 hastalloy Inorganic materials 0.000 description 10
- 239000000178 monomer Substances 0.000 description 9
- 239000004305 biphenyl Substances 0.000 description 8
- 235000010290 biphenyl Nutrition 0.000 description 8
- 238000001746 injection moulding Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000007599 discharging Methods 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 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 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
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- 239000001632 sodium acetate Substances 0.000 description 1
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Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
A preparation method and application of a liquid crystal polymer relate to the technical field of high polymer materials. The invention aims to solve the problem of how to avoid foaming of liquid crystal polymers. The method comprises the following steps: mixing four raw materials of parahydroxybenzoic acid, biphenol, 2, 6-dicarboxyl biphenyl alkene and terephthalic acid with an acylating agent and a catalyst to obtain a mixture; carrying out prepolymerization reaction on the mixture to obtain prepolymer; and (3) carrying out solid-phase polycondensation reaction on the prepolymer obtained in the step (S2) in an inert gas atmosphere to obtain the liquid crystal polymer. 100 parts of liquid crystal polymer and 30-35 parts of inorganic filler are added into a double screw extruder, and the liquid crystal polymer composition is obtained through melt plasticization, extrusion, cooling and granulation. The invention can obtain a preparation method and application of the liquid crystal polymer.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a preparation method and application of a liquid crystal polymer.
Background
The liquid crystal polymer is a novel high-performance special engineering plastic, has excellent heat resistance, dimensional stability, fluidity and mechanical property, and is widely applied to the high and new technical fields of electronic appliances, aerospace, national defense and military industry, photoelectric communication and the like. In recent years, with the continuous improvement of environmental awareness and environmental requirements of products, lead-free welding technology is becoming a popular research content in the technical field of surface mounting due to the characteristics of no toxicity, little pollution and the like. Under the push of the trend of densification and miniaturization of electronic components, the lead-free reflow soldering process has put higher demands on the foaming resistance of the used materials at high peak temperatures.
At present, in order to meet the foaming resistance of the liquid crystal polymer under lead-free reflow soldering, the following measures are adopted: the liquid crystal polymer or the composition thereof is sufficiently degassed from the vent holes at the time of melt extrusion to reduce the residence time in the molding equipment, but the range of conditions under which the method can be controlled is very narrow, and is insufficient for suppressing the occurrence of foaming in the molded article. Furthermore, the melting point of the resin is increased, the chain segment movement capability of the resin at the leadless reflow soldering processing temperature is reduced, and the diffusion of residual small molecules is inhibited, so that the purpose of bubbling resistance is achieved. However, this method causes an increase in processing temperature to satisfy melt fluidity during injection molding of the material, and further causes degradation of the resin, resulting in deterioration of mechanical properties.
Therefore, the foaming problem of the liquid crystal polymer is fundamentally solved, and the foaming problem is a common technical problem to be solved by technicians in the industry.
Disclosure of Invention
The invention aims to solve the problem of avoiding foaming of a liquid crystal polymer, and provides a preparation method and application of the liquid crystal polymer.
The preparation method of the liquid crystal polymer comprises the following steps:
Step S1: mixing four raw materials of parahydroxybenzoic acid, biphenol, 2, 6-dicarboxyl biphenyl alkene and terephthalic acid with an acylating agent and a catalyst to obtain a mixture;
The molar ratio of the p-hydroxybenzoic acid, the biphenol, the 2, 6-dicarboxyl biphenyl alkene and the terephthalic acid is (60-75): (12.5-20): (0.5-2): (12-18);
step S2: carrying out a prepolymerization reaction on the mixture obtained in the step S1 to obtain a prepolymer;
step S3: and (3) carrying out solid-phase polycondensation reaction on the prepolymer obtained in the step (S2) in an inert gas atmosphere to obtain the liquid crystal polymer.
In the application of the liquid crystal polymer prepared by the preparation method of the liquid crystal polymer, 100 parts of the liquid crystal polymer and 30-35 parts of the inorganic filler are added into a double-screw extruder according to parts by weight, and the liquid crystal polymer composition is obtained through melt plasticization, extrusion, cooling and granulation.
The invention has the beneficial effects that:
(1) According to the invention, a biphenyl structure is introduced into a molecular chain through a monomer 2, 6-dicarboxyl biphenyl, and the biphenyl structure contains a cyclobutene structural unit with larger tension and a 12-pi electron planar structure with anti-aromaticity, so that the bond energy of an aryl carbon-carbon bond is much lower than that of a corresponding carbon-carbon bond in a biphenyl derivative (about 220 KJ/mol); the introduction of the biphenyl alkene structure can reduce the rigid intermolecular acting force to a certain extent, and the melting point is reduced macroscopically. In addition, the four monomers of the invention are mutually synergistic, so that the liquid crystal polymer has good foaming resistance, mechanical property and fluidity while endowing the liquid crystal polymer with a lower melting point.
(2) The melting point of the liquid crystal polymer prepared by the invention is below 350 ℃, the better melt fluidity can be obtained without increasing the processing temperature, the processing is convenient, the liquid crystal polymer has better foaming resistance in the processing process, and the foaming rate is 0; the alloy also has good mechanical properties, and the tensile strength is higher than 110MPa; meanwhile, the liquid crystal polymer composition obtained by adding the filler into the liquid crystal polymer has good fluidity and low warping degree besides the good performance of the liquid crystal polymer, and the injection molding product manufactured by adopting the liquid crystal polymer composition can be widely applied to the fields of automobiles, photovoltaics, energy storage and the like.
The invention can obtain a preparation method and application of the liquid crystal polymer.
Detailed Description
The first embodiment is as follows: the preparation method of the liquid crystal polymer comprises the following steps:
Step S1: mixing four raw materials of parahydroxybenzoic acid, biphenol, 2, 6-dicarboxyl biphenyl alkene and terephthalic acid with an acylating agent and a catalyst to obtain a mixture;
The molar ratio of the p-hydroxybenzoic acid, the biphenol, the 2, 6-dicarboxyl biphenyl alkene and the terephthalic acid is (60-75): (12.5-20): (0.5-2): (12-18);
step S2: carrying out a prepolymerization reaction on the mixture obtained in the step S1 to obtain a prepolymer;
step S3: and (3) carrying out solid-phase polycondensation reaction on the prepolymer obtained in the step (S2) in an inert gas atmosphere to obtain the liquid crystal polymer.
The beneficial effect of this embodiment is:
(1) In the embodiment, the biphenyl structure is introduced into a molecular chain through a monomer 2, 6-dicarboxyl biphenyl, and the biphenyl structure contains a cyclobutene structural unit with larger tension and a 12-pi electron plane structure with anti-aromaticity, so that the bond energy of an aryl carbon-carbon bond is much lower than that of a corresponding carbon-carbon bond in a biphenyl derivative (about 220 KJ/mol); the introduction of the biphenyl alkene structure can reduce the rigid intermolecular acting force to a certain extent, and the melting point is reduced macroscopically. In addition, the four monomers in the embodiment are mutually synergistic, so that the liquid crystal polymer has good foaming resistance, mechanical property and fluidity while endowing the liquid crystal polymer with a lower melting point.
(2) The liquid crystal polymer prepared by the embodiment has a melting point below 350 ℃, can obtain better melt fluidity without increasing the processing temperature, is convenient to process, has better foaming resistance in the processing process, and has a foaming rate of 0; the alloy also has good mechanical properties, and the tensile strength is higher than 110MPa; meanwhile, the liquid crystal polymer composition obtained by adding the filler into the liquid crystal polymer has good fluidity and low warping degree besides the good performance of the liquid crystal polymer, and the injection molding product manufactured by adopting the liquid crystal polymer composition can be widely applied to the fields of automobiles, photovoltaics, energy storage and the like.
The second embodiment is as follows: the present embodiment differs from the specific embodiment in that: the total number of moles of 2, 6-dicarboxybiphenyl and terephthalic acid in step S1 is equal to the number of moles of biphenol.
The other steps are the same as in the first embodiment.
And a third specific embodiment: the present embodiment differs from the first or second embodiment in that: the acylating agent in the step S1 is one or two of acetic anhydride and maleic anhydride.
Other steps are the same as those of the first or second embodiment.
The specific embodiment IV is as follows: one difference between this embodiment and the first to third embodiments is that: the catalyst in the step S1 is dibutyl tin oxide.
Other steps are the same as those of the first to third embodiments.
Fifth embodiment: one to four differences between the present embodiment and the specific embodiment are: the addition amount of the acylating reagent (the mass is calculated according to the total mole number of the hydroxyl groups in actual addition) is 1.05 to 1.7 times of the total mole number of the hydroxyl groups in four raw materials of parahydroxybenzoic acid, biphenol, 2, 6-dicarboxyl biphenyl alkene and terephthalic acid; the addition amount of the catalyst is 50-120% of the total mass of four raw materials of parahydroxybenzoic acid, biphenol, 2, 6-dicarboxyl biphenyl alkene and terephthalic acid.
Other steps are the same as those of the first to fourth embodiments.
Specific embodiment six: the present embodiment differs from the first to fifth embodiments in that: the prepolymerization in step S2 is carried out as follows: heating the mixture to 130-150 ℃, preserving heat for 4-8 h at 130-150 ℃, heating to 300-320 ℃ after the heat preservation is finished, and preserving heat for 2-4 h continuously; after the heat preservation is finished, crushing, sieving, and finally drying for 2-3 hours at 110-130 ℃ to obtain the prepolymer.
Other steps are the same as those of the first to fifth embodiments.
Seventh embodiment: one difference between the present embodiment and the first to sixth embodiments is that: the solid phase polycondensation reaction in step S3 is performed as follows: and heating the prepolymer to 260-320 ℃ in an inert gas atmosphere, and preserving heat for 12-24 hours at the temperature of 260-320 ℃ to obtain the liquid crystal polymer.
Other steps are the same as those of embodiments one to six.
Eighth embodiment: in the application of the liquid crystal polymer prepared by the preparation method of the liquid crystal polymer, 100 parts of the liquid crystal polymer and 30-35 parts of the inorganic filler are added into a double-screw extruder according to parts by weight, and the liquid crystal polymer composition is obtained through melt plasticization, extrusion, cooling and granulation.
Detailed description nine: one of the differences between this embodiment and the first to eighth embodiments is: the inorganic filler is one or more of fibrous inorganic filler, powdery inorganic material and plate-shaped inorganic filler.
Other steps are the same as those of embodiments one to eight.
Detailed description ten: the present embodiment differs from the first to ninth embodiments in that: the fibrous inorganic filler is one or more of glass fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, magnesium sulfate fiber, aluminum borate fiber and stainless steel, aluminum, titanium and copper metal fiber;
The powdery inorganic material is one or more of carbon black, graphite, silicon dioxide, quartz powder, glass beads, calcium silicate, aluminum silicate, kaolin, antimony trioxide, aluminum oxide, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, silicon carbide, silicon nitride, boron nitride and metal powder;
The platy inorganic filler is one or more of mica powder, glass flake, talcum powder and metal foil.
Other steps are the same as those of embodiments one to nine.
The following examples are used to verify the benefits of the present invention:
example 1: the preparation method of the liquid crystal polymer comprises the following steps:
Step S1: mixing four raw materials of parahydroxybenzoic acid, biphenol, 2, 6-dicarboxybiphenyl and terephthalic acid with an acylating agent acetic anhydride accounting for 1.05 times of the total mole number of hydroxyl groups in the four raw materials and a catalyst dibutyl tin oxide accounting for 50% of the total mass of the four raw materials according to the raw material ratio of 1# in table 1 to obtain a mixture;
Step S2: putting the mixture obtained in the step S1 into a hastelloy kettle, heating to 130 ℃, preserving heat at 130 ℃ for 4 hours, heating to 300 ℃ after the heat preservation is finished, and preserving heat for 2 hours continuously; after the heat preservation is finished, 0.1MPa inert gas is filled into a hastelloy kettle, reaction products are discharged through discharging valves with the diameter of 2mm and the number of holes of 8, crushed and sieved by a 20-mesh sieve, and finally the prepolymer is obtained by drying for 2 hours at the temperature of 110 ℃;
Step S3: and (2) heating the prepolymer obtained in the step (S2) to 260 ℃ in an inert gas atmosphere, and carrying out solid-phase polycondensation reaction for 24 hours at the temperature of 260 ℃ to obtain the liquid crystal polymer, wherein the melting point of the liquid crystal polymer is not higher than 350 ℃.
The molecular structural formula of the parahydroxybenzoic acid is as follows:
the molecular structural formula of the biphenol is as follows:
the molecular structural formula of the 2, 6-dicarboxyl biphenyl alkene is as follows:
The molecular structural formula of terephthalic acid is:
Example 2: the preparation method of the liquid crystal polymer comprises the following steps:
Step S1: mixing four raw materials of p-hydroxybenzoic acid, biphenol, 2, 6-dicarboxybiphenyl and terephthalic acid with an acylating agent maleic anhydride accounting for 1.3 times of the total mole number of hydroxyl groups in the four raw materials and a catalyst dibutyl tin oxide accounting for 70% of the total mass of the four raw materials according to the raw material ratio of the number 2 in table 1 to obtain a mixture;
Step S2: putting the mixture obtained in the step S1 into a hastelloy kettle, heating to 140 ℃, preserving heat at 140 ℃ for 5 hours, heating to 305 ℃ after the heat preservation is finished, and continuing to preserve heat for 3 hours; after the heat preservation is finished, 0.4MPa inert gas is filled into the hastelloy kettle, reaction products are discharged through discharging valves with the diameter of 2mm and the number of holes of 10, crushed and sieved by a 20-mesh sieve, and finally the prepolymer is obtained by drying for 2 hours at 120 ℃;
Step S3: and (3) heating the prepolymer obtained in the step (S2) to 280 ℃ in an inert gas atmosphere, and carrying out solid phase polycondensation reaction for 20 hours at the temperature of 280 ℃ to obtain the liquid crystal polymer.
Example 3: the preparation method of the liquid crystal polymer comprises the following steps:
step S1: mixing four raw materials of p-hydroxybenzoic acid, biphenol, 2, 6-dicarboxybiphenyl and terephthalic acid with an acylating agent maleic anhydride accounting for 1.4 times of the total mole number of hydroxyl groups in the four raw materials and a catalyst dibutyl tin oxide accounting for 80% of the total mass of the four raw materials according to the raw material ratio of 3# in table 1 to obtain a mixture;
Step S2: putting the mixture obtained in the step S1 into a hastelloy kettle, heating to 140 ℃, preserving heat at 140 ℃ for 6 hours, heating to 310 ℃ after the heat preservation is finished, and preserving heat for 2 hours continuously; after the heat preservation is finished, 0.5MPa inert gas is filled into the hastelloy kettle, reaction products are discharged through discharging valves with the diameter of 4mm and the hole number of 8, crushed and sieved by a 30-mesh sieve, and finally the prepolymer is obtained by drying at 110 ℃ for 3 hours;
Step S3: and (2) heating the prepolymer obtained in the step (S2) to 300 ℃ in an inert gas atmosphere, and carrying out solid phase polycondensation reaction for 18 hours at the temperature of 300 ℃ to obtain the liquid crystal polymer.
Example 4: the preparation method of the liquid crystal polymer comprises the following steps:
step S1: mixing four raw materials of p-hydroxybenzoic acid, biphenol, 2, 6-dicarboxybiphenyl and terephthalic acid with an acylating agent acetic anhydride accounting for 1.6 times of the total mole number of hydroxyl groups in the four raw materials and a catalyst dibutyl tin oxide accounting for 100% of the total mass of the four raw materials according to the raw material ratio of 4# in table 1 to obtain a mixture;
Step S2: putting the mixture obtained in the step S1 into a hastelloy kettle, heating to 140 ℃, preserving heat at 140 ℃ for 6 hours, heating to 310 ℃ after the heat preservation is finished, and preserving heat for 4 hours continuously; after the heat preservation is finished, 0.8MPa inert gas is filled into the hastelloy kettle, reaction products are discharged through discharging valves with the diameter of 2mm and the number of holes of 10, crushed and sieved by a 20-mesh sieve, and finally, the prepolymer is obtained by drying for 2 hours at 130 ℃;
Step S3: and (2) heating the prepolymer obtained in the step (S2) to 310 ℃ in an inert gas atmosphere, and carrying out solid phase polycondensation reaction for 15h at the temperature of 310 ℃ to obtain the liquid crystal polymer.
Example 5: the preparation method of the liquid crystal polymer comprises the following steps:
step S1: mixing four raw materials of p-hydroxybenzoic acid, biphenol, 2, 6-dicarboxybiphenyl and terephthalic acid with an acylating agent acetic anhydride accounting for 1.7 times of the total mole number of hydroxyl groups in the four raw materials and a catalyst dibutyl tin oxide accounting for 120% of the total mass of the four raw materials according to the raw material ratio of 5# in table 1 to obtain a mixture;
Step S2: putting the mixture obtained in the step S1 into a hastelloy kettle, heating to 150 ℃, preserving heat at 150 ℃ for 4 hours, heating to 320 ℃ after the heat preservation is finished, and preserving heat for 2 hours continuously; after the heat preservation is finished, filling inert gas with the pressure of 1.0MPa into a hastelloy kettle, discharging reaction products through discharging valves with the diameter of 4mm and the hole number of 8, crushing, sieving with a 30-mesh sieve, and finally drying for 3 hours at the temperature of 110 ℃ to obtain prepolymer;
step S3: and (2) heating the prepolymer obtained in the step (S2) to 320 ℃ in an inert gas atmosphere, and carrying out solid phase polycondensation reaction for 12 hours at the temperature of 320 ℃ to obtain the liquid crystal polymer.
Comparative example 1:
The comparative example differs from example 4 only in that the polymerization reaction was carried out using the 6# raw material formulation in Table 1, i.e., the molar content of 2, 6-dicarboxybiphenyl involved in the reaction was 0.2mol%, the molar content of terephthalic acid was 14.8mol%, and the other experimental conditions were the same as in example 4.
Comparative example 2:
The comparative example differs from example 4 only in that the polymerization reaction was carried out using the raw material formulation of # 7 in Table 1, i.e., the molar content of 2, 6-dicarboxybiphenyl involved in the reaction was 2.5mol%, the molar content of terephthalic acid was 12.5mol%, and the other experimental conditions were the same as in example 4.
Comparative example 3:
The comparative example differs from example 4 only in that the polymerization was carried out using the raw material formulation of # 8 in Table 1, i.e., the reaction monomer did not contain 2, 6-dicarboxybiphenyl, the molar content of terephthalic acid was 15mol%, and the other experimental conditions were the same as in example 4.
Comparative example 4:
The comparative example differs from example 4 only in that the polymerization was carried out using the raw material formulation of # 9 in Table 1, i.e., 6-hydroxy-2-naphthoic acid was used instead of equimolar amounts of parahydroxybenzoic acid, and other experimental conditions were the same as in example 4.
Comparative example 5:
The comparative example differs from example 4 only in that the polymerization was carried out using the 10# raw material formulation of table 1, i.e., hydroquinone was used instead of the equimolar content of biphenol, and the other experimental conditions were the same as in example 4.
Comparative example 6:
The comparative example differs from example 4 only in that the polymerization was carried out using the 11# raw material formulation in table 1, i.e., isophthalic acid was used instead of terephthalic acid in equimolar amounts, with the other being the same as example 4.
Comparative example 7:
This comparative example differs from example 4 only in that sodium acetate was used as catalyst in the polymerization process, and the other is the same as example 4.
Table 1 shows the proportions of the monomer materials in the materials of examples 1 to 5 and comparative examples 1 to 7;
TABLE 1
The relevant performance test methods for the liquid crystal polymers or their compositions in examples 1 to 5 and comparative examples 1 to 7 are as follows:
(1) Melting point: after the endothermic peak temperature (Tm 1) observed when the liquid crystal polymer was measured at a temperature rise rate of 20 ℃/min from room temperature was observed using a differential scanning calorimeter DSC-500C, the liquid crystal polymer was kept at a temperature of (Tm1+30) ℃for 2 minutes, cooled to room temperature at a temperature drop rate of 20 ℃/min, and then the temperature of the endothermic peak observed at a temperature rise rate of 20 ℃/min was measured.
(2) Melt viscosity: the melt viscosity of the liquid crystalline polymer was determined according to GB/T25278-2010 at a shear rate of 1000s -1 using a capillary rheometer.
(3) Tensile strength: the determination is carried out according to ISO 527-2.
(4) Foaming ratio: extruding the liquid crystal polymer or the composition thereof into a sheet sample with the thickness of 1.0mm and the length and width of 50mm at the temperature of 5 ℃ above the melting point of the liquid crystal polymer and the injection speed of 60 mm/s; wherein, sample injection molding respectively at the end of the polymerization and the discharge for 10min, 10 samples are obtained by injection molding each time, 10 samples are put into a baking oven at 270 ℃ to be baked for 5min, then the samples are taken out, and the bubble generation condition on the surfaces of the samples is observed. Foaming ratio = number of foaming blocks/10, the lower the foaming ratio, the better the foaming resistance of the liquid crystal polymer or its composition.
(5) Fluidity: the liquid-crystalline polymer composition was injection-molded on an injection molding machine into a specimen having a diameter of 5X 1.0mm in cross-sectional dimension, and the flow length was measured by spiral flow characterization under the conditions of a molding temperature of 340℃and a molding speed of 30mm/s and a molding pressure of 30 bar.
(6) Warp degree: injecting the liquid crystal polymer composition into a disc-shaped sample with a diameter of 64mm and a thickness of 0.5mm on an injection molding machine; then, the obtained specimen was placed on a flat plate, the outer periphery of the disk was taken as a reference plane, and the portion farthest from the flat plate was taken as a gate portion, and the height from the reference plane to the gate portion was measured using a micrometer, and the displacement was checked. The displacement value obtained is used as the warpage of the molded product.
Table 2 shows the properties of the liquid crystal polymers of examples 1 to 5 and comparative examples 1 to 7;
TABLE 2
As can be seen from the performance test results in Table 2, the liquid crystal polymer prepared by the method has good mechanical properties, has a lower melting point, is more beneficial to processing, and has good foaming resistance in the processing process.
Meanwhile, it was found from comparison of comparative examples 1,3 and 4 that when the reaction monomer does not contain 2, 6-dicarboxybiphenyl or the molar content thereof is less than 0.5%, the melting point of the liquid crystal polymer is high, and a higher processing temperature is required in order to satisfy melt flowability during processing, resulting in decomposition of the liquid crystal polymer into a part of small molecular substances, and formation of expanded bubbles accumulated on the surface of the liquid crystal polymer test piece upon melt extrusion. As a result of comparison between comparative example 2 and example 4, it was found that when the amount of 2, 6-dicarboxybiphenyl added to the reaction monomer exceeds 2.0%, the melting point of the liquid crystal polymer is lowered, but the mechanical properties and the bubbling resistance are significantly deteriorated. According to analysis, mainly because the introduction of the biphenyl alkene structure can reduce the acting force among rigid molecular chains to a certain extent, the melting point is reduced macroscopically, but meanwhile, because the biphenyl alkene structure has certain anti-aromaticity, the thermodynamic stability of the liquid crystal polymer is greatly reduced due to the excessive addition, and the normal processing temperature range is decomposed, so that the foaming is obvious and the mechanical property is reduced. Therefore, the amount of 2, 6-dicarboxybiphenyl added is preferably controlled to be in the range of 0.5 to 2mol% for the present invention.
As can be seen from the comparison of the comparative example 7 and the example 4, the selection of the catalyst is also particularly important for the reaction system of the invention, and the adoption of the traditional catalyst has more side reactions, so that the polymerization product is adhered to the wall of the reaction kettle and can not be discharged smoothly.
In addition, it can be seen from Table 2 that the technical problems of the present invention can be solved only by the synergistic effect of the four monomer materials of the present invention, but the foaming resistance, melting point and mechanical properties of the liquid crystal polymer cannot be maintained consistently with excellent properties by lacking or replacing any one of them (comparative examples 4 to 6).
Example 6:
A liquid crystal polymer composition comprising 100 parts by weight of the liquid crystal polymer of example 4, 30 parts by weight of glass fiber having a diameter of 10 μm and a length of 3 mm; adding the liquid crystal polymer into the extruder from a main feeding port of the double-screw extruder in proportion, controlling the rotating speed of the screw to 200rpm, and adding the glass fiber into the extruder from a side feeding port of the double-screw extruder; melting, plasticizing, extruding, cooling and granulating under the rotation of a screw rod to obtain a liquid crystal polymer composition; the tensile strength of the composition was 140MPa, the foaming rate was 0, the flow length was 550mm, and the warpage was 0.26mm, as tested.
Example 7:
A liquid crystal polymer composition comprising 100 parts by weight of the liquid crystal polymer of example 4, 20 parts by weight of glass fiber having a diameter of 10 μm and a length of 3mm, and 15 parts by weight of talc; adding the liquid crystal polymer into the extruder from a main feeding port of the double-screw extruder in proportion, controlling the rotating speed of the screw to 200rpm, and adding the glass fiber into the extruder from a side feeding port of the double-screw extruder; melting and plasticizing, extruding, cooling and granulating under the rotation of a screw rod to obtain a liquid crystal polymer composition; the composition was tested to have a tensile strength of 127MPa, a foaming rate of 0, a flow length of 600mm and a warpage of 0.22mm.
Example 8:
A liquid crystal polymer composition comprising 100 parts by weight of the liquid crystal polymer of example 4, 20 parts by weight of glass fiber having a diameter of 10 μm and a length of 3mm, and 25 parts by weight of talc; adding the liquid crystal polymer into the extruder from a main feeding port of the double-screw extruder in proportion, controlling the rotating speed of the screw to 200rpm, and adding the glass fiber into the extruder from a side feeding port of the double-screw extruder; melting and plasticizing, extruding, cooling and granulating under the rotation of a screw rod to obtain a liquid crystal polymer composition; the composition was tested to have a tensile strength of 124MPa, a foaming rate of 0, a flow length of 660mm and a warpage of 0.16mm.
In summary, the composition product obtained by modifying the liquid crystal polymer of the invention is endowed with good fluidity and low warp deformation on the basis of ensuring good mechanical property and foaming resistance by adding different fillers according to different application purposes, and the injection molding product manufactured by adopting the composition product can be widely applied to the fields of automobiles, photovoltaics, energy storage and the like.
Claims (10)
1. The preparation method of the liquid crystal polymer is characterized by comprising the following steps:
Step S1: mixing four raw materials of parahydroxybenzoic acid, biphenol, 2, 6-dicarboxyl biphenyl alkene and terephthalic acid with an acylating agent and a catalyst to obtain a mixture;
The molar ratio of the p-hydroxybenzoic acid, the biphenol, the 2, 6-dicarboxyl biphenyl alkene and the terephthalic acid is (60-75): (12.5-20): (0.5-2): (12-18);
step S2: carrying out a prepolymerization reaction on the mixture obtained in the step S1 to obtain a prepolymer;
step S3: and (3) carrying out solid-phase polycondensation reaction on the prepolymer obtained in the step (S2) in an inert gas atmosphere to obtain the liquid crystal polymer.
2. The method for producing a liquid crystal polymer according to claim 1, wherein the total mole number of 2, 6-dicarboxybiphenyl and terephthalic acid in step S1 is equal to the mole number of biphenol.
3. The method for preparing a liquid crystal polymer according to claim 1, wherein the acylating agent in the step S1 is one or both of acetic anhydride and maleic anhydride.
4. The method for preparing a liquid crystal polymer according to claim 1, wherein the catalyst in the step S1 is dibutyl tin oxide.
5. The method for preparing a liquid crystal polymer according to claim 3 or 4, wherein the addition amount of the acylating agent is 1.05 to 1.7 times the total mole number of hydroxyl groups in four raw materials of parahydroxybenzoic acid, biphenol, 2, 6-dicarboxybiphenyl and terephthalic acid; the addition amount of the catalyst is 50-120% of the total mass of four raw materials of parahydroxybenzoic acid, biphenol, 2, 6-dicarboxyl biphenyl alkene and terephthalic acid.
6. The method for preparing a liquid crystal polymer according to claim 1, wherein the pre-polymerization in step S2 is performed as follows: heating the mixture to 130-150 ℃, preserving heat for 4-8 h at 130-150 ℃, heating to 300-320 ℃ after the heat preservation is finished, and preserving heat for 2-4 h continuously; after the heat preservation is finished, crushing, sieving, and finally drying for 2-3 hours at 110-130 ℃ to obtain the prepolymer.
7. The method for producing a liquid crystal polymer according to claim 1, wherein the solid phase polycondensation in step S3 is carried out as follows: and heating the prepolymer to 260-320 ℃ in an inert gas atmosphere, and preserving heat for 12-24 hours at the temperature of 260-320 ℃ to obtain the liquid crystal polymer.
8. Use of a liquid crystalline polymer prepared by the process according to any one of claims 1 to 7, wherein 100 parts by weight of the liquid crystalline polymer and 30 to 35 parts by weight of the inorganic filler are added to a twin screw extruder, and melt plasticizing, extruding, cooling and granulating are carried out to obtain a liquid crystalline polymer composition.
9. The use of the liquid crystal polymer according to claim 8, wherein the inorganic filler is one or more of fibrous inorganic filler, powdery inorganic filler and plate-like inorganic filler.
10. The use of the liquid crystal polymer prepared by the method according to claim 8, wherein the fibrous inorganic filler is one or more of glass fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, magnesium sulfate fiber, aluminum borate fiber, and stainless steel, aluminum, titanium, and copper metal fiber;
The powdery inorganic material is one or more of carbon black, graphite, silicon dioxide, quartz powder, glass beads, calcium silicate, aluminum silicate, kaolin, antimony trioxide, aluminum oxide, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, silicon carbide, silicon nitride, boron nitride and metal powder;
The platy inorganic filler is one or more of mica powder, glass flake, talcum powder and metal foil.
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