CN103342804A - Thermotropic liquid crystal polymer material and synthesis method thereof - Google Patents
Thermotropic liquid crystal polymer material and synthesis method thereof Download PDFInfo
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- 239000004974 Thermotropic liquid crystal Substances 0.000 title claims abstract description 28
- 239000002861 polymer material Substances 0.000 title claims abstract description 17
- 229920000106 Liquid crystal polymer Polymers 0.000 title abstract description 10
- 238000001308 synthesis method Methods 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 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
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 34
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims abstract description 18
- 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 abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 8
- 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 6
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 230000021736 acetylation Effects 0.000 claims abstract description 4
- 238000006640 acetylation reaction Methods 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 46
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 39
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 20
- 238000010189 synthetic method Methods 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 239000006227 byproduct Substances 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-Lutidine Substances CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000005352 clarification Methods 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical compound OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 abstract 2
- 239000012965 benzophenone Substances 0.000 abstract 2
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 150000003504 terephthalic acids Chemical class 0.000 description 5
- 150000005211 2-naphthoic acids Chemical class 0.000 description 4
- 238000012545 processing Methods 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a thermotropic liquid crystal polymer material and a synthesis method thereof. The thermotropic liquid crystal polymer material provided by the invention is prepared through copolymerizing a group of monomers, wherein each monomer comprises p-hydroxybenzoic acid, 6-hydroxyl-2-naphthoic acid, p-dihydroxybenzene and terephthalic acid, and all the monomers are respectively in the following mole percentage range: 50-70%, 10-20%, 7.5-20% and 7.5-20%. Each monomer also comprises 4,4'-dicarboxylic benzophenone which is in the mole percentage of 0.1%. The preparation method of the thermotropic liquid crystal polymer material provided by the invention comprises the following steps of: (1) monomer acetylation; (2) pre-polymerization; and (3) final polymerization. A pre-polymerization and final polymerization two-step method is adopted in the polymerization reaction process, so that the reaction conditions can be better controlled, the reaction time can be shortened, and the production efficiency can be increased. The 4,4'-dicarboxylic benzophenone is added in the polymerization reaction, so that the melting point of a liquid crystal polymer product can be effectively reduced, and the machinability of the material is kept strong.
Description
Technical field:
The present invention relates to a kind of thermotropic liquid crystal high polymer material and synthetic method thereof, belong to the organic chemical synthesis technical field, also belong to the liquid crystal high polymer material technical field simultaneously.
Background technology:
Liquid crystal polymer (LCP) is the high-performance polymer that the class developed the seventies in 20th century has excellent properties, and it can exist with mesomorphic phase under certain condition, and molecule has the feature of rigidity and spontaneous orientation.Be mainly used in making specialty synthetic fibre and special engineering plastics.The LCP goods have high strength, high-modulus, and dimensional stability, flame retardant resistance, good insulating, high temperature resistant, radiation hardness, chemical resistance corrosion, linear expansivity is low and excellent properties such as good processing flowability are arranged.Have wide application at high-technology fields such as electronic apparatus, aerospace, optical-fibre communications, automotive industry, machinofacture and chemical industry, be described as super engineering plastics.
Though Chinese patent CN200410054025 related to the present invention; CN200410054024; CN03150765; CN200910047546; CN200410054025 wherein; CN200410054024 adopts solid state polymerization; solid state polymerization requires high to conversion unit; while processing condition harshness; be not suitable for large-scale production; CN03150765; CN200910047546 does not add 4 in reaction system; 4 '-benzophenonedicarboxylic acid; cause that product easily solidifies when reaction finishes; the discharging difficulty; while CN03150765; CN200910047546 adopts the single stage method polymerization, long reaction time, and production efficiency is low during suitability for industrialized production.
Summary of the invention:
The objective of the invention is provides a kind of thermotropic liquid crystal high polymer material at the problem of above-mentioned existence, can effectively reduce the fusing point of liquid crystal polymer product, improves processing characteristics.Another object of the present invention provides the synthetic method of this thermotropic liquid crystal high polymer material, can control reaction conditions better, shortens the reaction times, enhances productivity, and is fit to suitability for industrialized production.
Thermotropic liquid crystal high polymer material, made by one group of monomer copolymerization, described monomer comprises P-hydroxybenzoic acid, 6-hydroxyl-2-naphthoic acid, Resorcinol and terephthalic acid, and the shared molar percentage scope of each monomer is 50-70%, 10-20%, 7.5-20%, 7.5-20%.
Described thermotropic liquid crystal high polymer material, described monomer also comprises 4,4 '-benzophenonedicarboxylic acid, 4, the shared molar percentage 0.1% of 4 '-benzophenonedicarboxylic acid.
The preparation method of above-mentioned thermotropic liquid crystal high polymer material, this method comprises the steps:
(1) monomer acetylize: P-hydroxybenzoic acid, 6-hydroxyl-2-naphthoic acid and Resorcinol are respectively that acetylation reagent carries out acetylization reaction with the aceticanhydride under catalyst action;
(2) pre-polymerization: in prepolymerization kettle, with P-hydroxybenzoic acid, 6-hydroxyl-2-naphthoic acid with the Resorcinol acetylize obtains product and other monomers carry out preliminary polymerization, remove by product acetic acid with nitrogen during preliminary polymerization;
(3) eventually poly-: the reaction solution that step (2) is obtained is pressed into terminal polymerization kettle with nitrogen to carry out further polymerization and obtains product, removes byproduct acetic acid with vacuum system during poly-reaction eventually.
The preparation method of described thermotropic liquid crystal high polymer material also comprises during preliminary polymerization in the step (2) adding 4, the step of 4 '-benzophenonedicarboxylic acid.
The synthetic method of described thermotropic liquid crystal high polymer, the mol ratio of P-hydroxybenzoic acid and 6-hydroxyl-2-naphthoic acid and aceticanhydride is 1:1.2 in the step (1), the mol ratio of Resorcinol and aceticanhydride is 1:2.4, the mass ratio of P-hydroxybenzoic acid, 6-hydroxyl-2-naphthoic acid and Resorcinol and catalyzer is 1:1000, temperature of reaction is the reflux temperature of reaction system, join after being cooled to 50 ℃ after reaction finishes and separate out product in the frozen water, suction filtration, the oven dry of washing final vacuum.
The synthetic method of described thermotropic liquid crystal high polymer, the catalyzer described in the step (1) are selected a kind of in peroxophosphoric acid, thionamic acid, trifluoromethanesulfonic acid, p-methyl benzenesulfonic acid, pyridine, 4-lutidine, the 1-methylpyrrole for use.
The synthetic method of described a kind of thermotropic liquid crystal high polymer, the catalyzer described in the step (1) is selected p-methyl benzenesulfonic acid or pyridine for use.
The synthetic method of described thermotropic liquid crystal high polymer; pre-polymerization described in the step (2) refers to add P-hydroxybenzoic acid in the polymeric kettle that has logical nitrogen and condenser; 6-hydroxyl-2-naphthoic acid and Resorcinol acetylize obtain product and other monomers carry out preliminary polymerization under the effect of catalyzer; being warmed up to 120 ℃ earlier stopped 30 minutes; begin temperature reaction then; logical nitrogen removes by product acetic acid in the time of temperature reaction; the more high nitrogen flow of temperature is more big; stopped reaction when reaction solution is transferred to clarification and begun to change muddiness into again by white; prepolymerization reaction finishes, and is pressed into terminal polymerization kettle with nitrogen then.
The synthetic method of described thermotropic liquid crystal high polymer, the reaction solution that step (3) described end is poly-to refer to step (2) is pressed into and has further polymerization under the effect of catalyzer behind the terminal polymerization kettle that moment of torsion shows, begin further intensification after being pressed into, begin to vacuumize when heating up and remove acetic acid, temperature more condition of high vacuum degree is more big, and vacuum tightness reaches 70 handkerchiefs when being warmed up to 360-380 ℃, observes to react when no obvious acetic acid is extracted out and finishes, extrude material with nitrogen, cooling and dicing.
The synthetic method of described a kind of thermotropic liquid crystal high polymer, used catalyzer is zinc acetate in the pre-collecting process, consumption be ten thousand of monomeric charge total mass/.
Beneficial effect:
1. polyreaction of the present invention adopts pre-polymerization and eventually poly-two-step approach can control reaction conditions better, shortens the reaction times, enhances productivity.
2. the present invention adopts to add 4 in polyreaction through a large amount of evidences, and 4 '-benzophenonedicarboxylic acid can effectively reduce the fusing point of liquid crystal polymer product, makes that the workability of material is strong.
Embodiment:
Embodiment 1:
In aceticanhydride, be that catalyzer carries out acetylization reaction with the pyridine respectively with 50 moles of P-hydroxybenzoic acid, 20 moles of 6-hydroxyl-2-naphthoic acids and 15 moles of Resorcinol, the sampling analysis terminal point, be cooled to 50 ℃ after the end and join and separate out product in the frozen water, 60 ℃ of vacuum-dryings are standby to constant weight;
With the acetylize product of above-mentioned oven dry and 14.9 moles of terephthalic acids, 0.1 mole 4; 4 '-benzophenonedicarboxylic acid and zinc acetate join and are warmed up to 120 ℃ of dehydrations 30 minutes in the reactor of being with logical nitrogen and condenser; begin then to heat; logical nitrogen removes byproduct acetic acid simultaneously; the more high nitrogen flow of temperature is more big; nitrogen flow and temperature relation such as table 1; observe reaction system and transfer pure stopped reaction when beginning to change muddiness into clearly again to by white; prepolymerization reaction finishes, and is pressed into terminal polymerization kettle with nitrogen.
The relation of table 1 nitrogen flow and temperature of reaction
| Temperature | 120 | 130 | 140 | 150 | 160 | 170 | 180 | 190 | 200 | 210 |
| Nitrogen flow (ml/min) | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
After above-mentioned reaction solution is pressed into terminal polymerization kettle, further polyreaction begins to heat up, opening vacuum pump simultaneously begins to vacuumize and removes byproduct acetic acid, temperature of reaction and vacuum tightness relation are as table 2, when the reaction and display moment of torsion is about 0.27A, observe simultaneously to react when no obvious acetic acid flows out and finish, add nitrogen and remove vacuum, inflated with nitrogen extrudes reaction melt, cooling and dicing to about 0.4Mpa pressure.The product fusing point is 225 ℃ through detecting.
The relation of table 2 vacuum tightness and temperature of reaction
| Temperature | 220 | 230 | 250 | 270 | 290 | 310 | 330 | 350 | 370 | 390 |
| Vacuum (handkerchief) | 350 | 300 | 250 | 210 | 180 | 150 | 100 | 90 | 80 | 70 |
Embodiment 2:
The difference of present embodiment and embodiment 1 is; the consumption of each monomer is: 10 moles of 70 moles of P-hydroxybenzoic acid, 6-hydroxyl-10 moles of 2-naphthoic acids, 10 moles of Resorcinol and terephthalic acids; adopt p-methyl benzenesulfonic acid as catalyzer in the monomer acetylation, the finished product fusing point is 332 ℃ through detecting.Do not add 4 in the present embodiment, 4 '-benzophenonedicarboxylic acid, the fusing point of the finished product is apparently higher than adding 4, the fusing point of the finished product during 4 '-benzophenonedicarboxylic acid.
Embodiment 3:
The difference of present embodiment and embodiment 1 is, the consumption of each monomer is: 14.9 moles of 55 moles of P-hydroxybenzoic acid, 6-hydroxyl-15 moles of 2-naphthoic acids, 15 moles of Resorcinol and terephthalic acids, 4,0.1 mole of 4 '-benzophenonedicarboxylic acid, the finished product fusing point is 221 ℃ through detecting.
Embodiment 4:
The difference of present embodiment and embodiment 1 is, the consumption of each monomer is: 14.9 moles of 60 moles of P-hydroxybenzoic acid, 6-hydroxyl-10 moles of 2-naphthoic acids, 15 moles of Resorcinol and terephthalic acids, 4,0.1 mole of 4 '-benzophenonedicarboxylic acid, the finished product fusing point is 231 ℃ through detecting.
Embodiment 5:
The difference of present embodiment and embodiment 1 is, the consumption of each monomer is: 12.4 moles of 65 moles of P-hydroxybenzoic acid, 6-hydroxyl-10 moles of 2-naphthoic acids, 12.5 moles of Resorcinol and terephthalic acids, 4,0.1 mole of 4 '-benzophenonedicarboxylic acid, the finished product fusing point is 232 ℃ through detecting.
Below only be most preferred embodiment of the present invention, method of the present invention includes but not limited to above-described embodiment, and unaccomplished matter of the present invention belongs to those skilled in the art's common practise.
Claims (10)
1. thermotropic liquid crystal high polymer material, made by one group of monomer copolymerization, it is characterized in that: described monomer comprises P-hydroxybenzoic acid, 6-hydroxyl-2-naphthoic acid, Resorcinol and terephthalic acid, and the shared molar percentage scope of each monomer is 50-70%, 10-20%, 7.5-20%, 7.5-20%.
2. thermotropic liquid crystal high polymer material according to claim 1, it is characterized in that: described monomer also comprises 4,4 '-benzophenonedicarboxylic acid, 4, the shared molar percentage 0.1% of 4 '-benzophenonedicarboxylic acid.
3. the preparation method of an above-mentioned thermotropic liquid crystal high polymer material, it is characterized in that: this method comprises the steps:
(1) monomer acetylize: P-hydroxybenzoic acid, 6-hydroxyl-2-naphthoic acid and Resorcinol are respectively that acetylation reagent carries out acetylization reaction with the aceticanhydride under catalyst action;
(2) pre-polymerization: in prepolymerization kettle, with P-hydroxybenzoic acid, 6-hydroxyl-2-naphthoic acid with the Resorcinol acetylize obtains product and other monomers carry out preliminary polymerization, remove by product acetic acid with nitrogen during preliminary polymerization;
(3) eventually poly-: the reaction solution that step (2) is obtained is pressed into terminal polymerization kettle with nitrogen to carry out further polymerization and obtains product, removes byproduct acetic acid with vacuum system during poly-reaction eventually.
4. the preparation method of thermotropic liquid crystal high polymer material according to claim 3 is characterized in that: also comprise during preliminary polymerization in the step (2) adding 4, the step of 4 '-benzophenonedicarboxylic acid.
5. according to the synthetic method of claim 3 or 4 described thermotropic liquid crystal high polymers, it is characterized in that: the mol ratio of P-hydroxybenzoic acid and 6-hydroxyl-2-naphthoic acid and aceticanhydride is 1:1.2 in the step (1), the mol ratio of Resorcinol and aceticanhydride is 1:2.4, the mass ratio of P-hydroxybenzoic acid, 6-hydroxyl-2-naphthoic acid and Resorcinol and catalyzer is 1:1000, temperature of reaction is the reflux temperature of reaction system, join after being cooled to 50 ℃ after reaction finishes and separate out product in the frozen water, suction filtration, the oven dry of washing final vacuum.
6. according to the synthetic method of claim 3 or 4 described thermotropic liquid crystal high polymers, it is characterized in that: the catalyzer described in the step (1) is selected a kind of in peroxophosphoric acid, thionamic acid, trifluoromethanesulfonic acid, p-methyl benzenesulfonic acid, pyridine, 4-lutidine, the 1-methylpyrrole for use.
7. according to the synthetic method of claim 3 or 4 described a kind of thermotropic liquid crystal high polymers, it is characterized in that: the catalyzer described in the step (1) is selected p-methyl benzenesulfonic acid or pyridine for use.
8. according to the synthetic method of claim 3 or 4 described thermotropic liquid crystal high polymers; it is characterized in that: the pre-polymerization described in the step (2) refers to add P-hydroxybenzoic acid in the polymeric kettle that has logical nitrogen and condenser; 6-hydroxyl-2-naphthoic acid and Resorcinol acetylize obtain product and other monomers carry out preliminary polymerization under the effect of catalyzer; being warmed up to 120 ℃ earlier stopped 30 minutes; begin temperature reaction then; logical nitrogen removes by product acetic acid in the time of temperature reaction; the more high nitrogen flow of temperature is more big; stopped reaction when reaction solution is transferred to clarification and begun to change muddiness into again by white; prepolymerization reaction finishes, and is pressed into terminal polymerization kettle with nitrogen then.
9. according to the synthetic method of claim 3 or 4 described thermotropic liquid crystal high polymers, it is characterized in that: the reaction solution that step (3) described end is poly-to refer to step (2) is pressed into and has further polymerization under the effect of catalyzer behind the terminal polymerization kettle that moment of torsion shows, begin further intensification after being pressed into, begin to vacuumize when heating up and remove acetic acid, temperature more condition of high vacuum degree is more big, vacuum tightness reaches 70 handkerchiefs when being warmed up to 360-380 ℃, observe to react when no obvious acetic acid is extracted out and finish, extrude material with nitrogen, cooling and dicing.
10. according to the synthetic method of claim 3 or 4 described a kind of thermotropic liquid crystal high polymers, it is characterized in that: used catalyzer is zinc acetate in the pre-collecting process, consumption be ten thousand of monomeric charge total mass/.
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| CN103613748A (en) * | 2013-10-23 | 2014-03-05 | 泰莱斯（南通）医药化工有限公司 | Wholly-aromatic thermotropic liquid crystal copolyester and preparation method thereof |
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| CN103804667A (en) * | 2014-03-05 | 2014-05-21 | 南通海迪化工有限公司 | Method for improving molecular weight of thermotropic liquid crystal polymer |
| CN106591997A (en) * | 2016-12-23 | 2017-04-26 | 宁波慧谷特种纤维科技有限公司 | Method for increasing heat treatment efficiency of thermotropic liquid crystal aromatic polyester fiber |
| CN106750198A (en) * | 2016-12-12 | 2017-05-31 | 中山大学 | A kind of thermotropic liquid crystalline polyester of monomer ratio stabilization with and preparation method and application |
| CN110527071A (en) * | 2019-08-01 | 2019-12-03 | 南京清研高分子新材料有限公司 | A kind of liquid crystal high polymer material and its synthetic method |
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| CN114292389A (en) * | 2021-12-28 | 2022-04-08 | 广东省科学院化工研究所 | Liquid crystal polymer and preparation method and application thereof |
| CN116606426A (en) * | 2023-07-20 | 2023-08-18 | 宁波聚嘉新材料科技有限公司 | Thermotropic liquid crystal polyarylester, film, preparation method of thermotropic liquid crystal polyarylester and film, and millimeter wave radar |
| CN118755071A (en) * | 2024-09-06 | 2024-10-11 | 中节能万润股份有限公司 | A method for preparing thermotropic liquid crystal polymer |
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