CN101649044A - Wholly aromatic liquid crystal polymer and preparation method thereof - Google Patents
Wholly aromatic liquid crystal polymer and preparation method thereof Download PDFInfo
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- CN101649044A CN101649044A CN200910192087A CN200910192087A CN101649044A CN 101649044 A CN101649044 A CN 101649044A CN 200910192087 A CN200910192087 A CN 200910192087A CN 200910192087 A CN200910192087 A CN 200910192087A CN 101649044 A CN101649044 A CN 101649044A
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Abstract
The invention discloses a wholly aromatic liquid crystal polymer and a preparation method thereof. The wholly aromatic liquid crystal polymer is obtained by the condensation polymerization reaction offour monomers: para-hydroxybenzoic acid, triptycene quinhydrone, terephthalic acid and m-phthalic acid. By introducing a triptycene unit with a space steric effect, the melting temperature of homopolymerizing para-hydroxybenzoic acid is reduced, a nematic liquid crystal polymer with excellent melting processing performance is obtained and the performance of fiber members is good; the triptycene unit is introduced into a rigid chain so as to have double functions of space steric hindrance and a benzene ring substitutional group, thereby increasing the molecule width of the polymer and reducingthe action force among the molecules and a melting point; however, the extension direction of the rigid chain is not changed and therefore, a copolymer still keeps good liquid crystal performance andgood mechanical performance. The thermal melting temperature of the liquid crystal polymer is from 280 DEG C to 370 DEG C and mostly from 290 DEG C to 350 DEG C. The liquid crystal polymer can be widely used for electronic electric appliances and parts and components of other precise equipment.
Description
Technical field:
The invention belongs to novel all aromatic TLCP and manufacture method thereof, relate to the liquid crystalline polymers that contains the triptycene structural unit with excellent melt processable.
Background technology:
Because the fusing point of P-hydroxybenzoic acid homopolymer is on decomposition temperature, insoluble not melting can not be processed, and commercialization and use are subjected to great restriction.A lot of companies and scientific research institutions adopt copolymerization technique to improve its melting behaviour and make liquid crystalline polymers, and this liquid crystalline polymers is called as super engineering plastics, and its performance is that other engineering plastics can't be compared with it.For example, Carborundum company (US3637595 and US3975487) and SUMITOMO CHEMICAL all adopt P-hydroxybenzoic acid (pHBA), quinhydrones (HQ), terephthalic acid (TA)/m-phthalic acid (IPA) and '-biphenyl diphenol (BP) copolymerization high-temperature resistant liquid crystal polymer material, and Celanese Corp. (US4161470) adopts heatproof liquid crystalline polymers in pHBA and 6-hydroxyl-two kinds of monomer preparations of 2-naphthoic acid (HNA), all obtained the liquid crystalline polymers of melt-processible, and commercially produced already and sell.At present, reducing the indispensable principal monomer of P-hydroxybenzoic acid homopolymer fusing point unit is BP and HNA, as mentioned above the Siveras series of the Vectra series of the Ekonol series of the Xydar series of the Carborundum of company, Sumitomo, Celanese and Toray etc.Particularly the introducing of HNA structural unit is the most effective to reducing fusing point, the naphthalene crank structure has destroyed the linearity of stiff chain, reduced rigidity, thereby reduction fusing point, but the stiff chain direction of extension does not become, so still keep liquid crystal liquid crystal property and mechanical property preferably, thereby make Vectra series become the outstanding person in the liquid crystalline polymers.Although Vectra industrialization more than 20 year, the price of liquid crystalline polymers are still high, a very important reason is exactly the monopolization of fewer companies such as Celanese to HNA synthetic technology and polymerizable mesogenic technology, causes starving.In order to reduce cost, production firm has started to develop new monomer, as 4,4 '-biphenyl dicarboxylic acid, 4, the used monomers of serial liquid crystalline polymers such as 4 '-dihydroxy diphenyl ether etc. and polymeric amide, polycarbonate, urethane, polyethers, but owing to reasons such as price and production technique, Commercial Prospect is still uncertain.
Summary of the invention:
The objective of the invention is to overcome the deficiency that prior art exists, a kind of Wholly aromatic liquid crystal polymer with excellent liquid crystal liquid crystal property and mechanical property is provided.
To achieve these goals, the present invention adopts following technical scheme:
Wholly aromatic liquid crystal polymer of the present invention is obtained through polycondensation by P-hydroxybenzoic acid, triptycene quinhydrones, terephthalic acid and four kinds of monomers of m-phthalic acid.The residue that four kinds of repeating units occur in main polymer chain is respectively:
Wholly aromatic liquid crystal polymer is not limited to above repeating unit, and also substituting group can be arranged on the aromatic nucleus, and substituent quantity and position also can random variation.
The molecular fraction of above-mentioned P-hydroxybenzoic acid, triptycene quinhydrones, terephthalic acid and m-phthalic acid is respectively 30-80%, 35-10%, 21-4% and 21-4%, the mole number sum of terephthalic acid and m-phthalic acid equals the mole number of triptycene quinhydrones, and mole number terephthalic acid/isophthalic acid=3/2-2/3, four mole number sums are 100%.
Preferred molar ratio is: the molecular fraction of P-hydroxybenzoic acid, triptycene quinhydrones, terephthalic acid and m-phthalic acid is respectively 50-75%, 25-12.5%, 15-5% and 15-5%, the mole number sum of terephthalic acid and m-phthalic acid equals the mole number of triptycene quinhydrones, and mole number terephthalic acid/isophthalic acid=3/2-2/3, four mole number sums are 100%.
The polymerization process of Wholly aromatic liquid crystal polymer can adopt suspension polymerization, solution polymerization, interfacial polymerization or melt polymerization, the preferred molten polycondensation, and be aided with solid phase polycondensation and prepare the high-molecular weight product.Concrete grammar comprises the steps: each monomer is mixed in proportion, add diacetyl oxide as acylating agent, and acetate or the fragrant hydrochlorate of Zn, K, Mg, Ca or Co are catalyzer, 140-150 ℃ acetylize 2-6 hour, be warming up to 270-350 ℃ with 10-40 ℃/h speed then, and insulation reaction 10 minutes to 4 hours; Be evacuated to below the 0.3mmHg heat-insulation pressure keeping reaction 15-60 minute; N
2Exist and 10-40 ℃ of following solid state polycondensation 1-24 of prepolymer fusing point hour.
Compared with prior art, the present invention has following beneficial effect: the present invention has the triptycene unit of space steric effect by introducing, reduce the melt temperature of equal poly, obtained to have the nematic liquid crystal polymer of excellent melt-processable, and its fiber part performance is good.Monomer triptycene quinhydrones is the three-dimensional rigid structure unit with big space steric effect, and raw material is easy to get, and synthetic method is fairly simple, only needs can obtain through the addition and the oxidation of benzoquinones and anthracene.The triptycene unit is introduced in the stiff chain and can be played sterically hindered and dual function benzene ring substitution group, make the polymer molecule width increase, Intermolecular Forces reduces, thereby fusing point is reduced, but the direction of extension of stiff chain does not change, so multipolymer still keeps good liquid crystal liquid crystal property and mechanical property.The thermic melt temperature of liquid crystalline polymers of the present invention is 280-370 ℃, how between 290-350 ℃, can be widely used in the component of electronic apparatus and other precision equipment.
Embodiment:
Fusing point is measured by the anti-DSC 200F3 that speeds of Germany, is warming up to each diversity district with 20 ℃/min, is cooled to room temperature with 10 ℃/min speed then, heats up with 10 ℃/min speed again.Liquid crystal property is observed by the hot platform polarizing microscope of German Leica DM2500P.The logarithmic viscosity number of liquid crystalline polymers is 3.5-8dL/g, is to be solvent (concentration is the solution of 0.1wt%) with the Pentafluorophenol, by formula I.V.=[ln (η
r)]/C calculates gained, wherein η
rBe relative viscosity.
Following examples are in order to explanation and further understand the method for carrying out the synthetic and solid phase polycondensation of liquid crystal prepolymer according to the present invention, but do not limit the present invention in any form.
Embodiment 1-4
Is being furnished with N
2In the 500ml there-necked flask of gas inlet, thorn shape splitter, prolong, still head, receptor and agitator, add reactant P-hydroxybenzoic acid, triptycene quinhydrones, terephthalic acid, m-phthalic acid and diacetyl oxide (molar weight of diacetyl oxide is two times of four monomer hydroxyl total amounts) and 0.1% weight catalyzer potassium acetate successively.145 ℃ of back flow reaction 3 hours, 25 ℃/h is warming up to 340 ℃ then, and insulation reaction 30 minutes.Slowly be evacuated to 0.25mmHg, last heat-insulation pressure keeping reaction 30 minutes.Prepolymer is taken out in cooling, and Universalpulverizer is pulverized, 120 ℃ of vacuum-drying 2 hours.N
2Flow down (50ml/min), in 280 ℃ of solid state polycondensations 15 hours.Multipolymer is formed and performance is listed in table 1.
Table 1 multipolymer is formed and performance
Claims (6)
1, a kind of Wholly aromatic liquid crystal polymer is characterized in that being obtained through polycondensation by P-hydroxybenzoic acid, triptycene quinhydrones, terephthalic acid and four kinds of monomers of m-phthalic acid.
2, Wholly aromatic liquid crystal polymer as claimed in claim 1, the molecular fraction that it is characterized in that described P-hydroxybenzoic acid, triptycene quinhydrones, terephthalic acid and m-phthalic acid is respectively 30-80%, 35-10%, 21-4% and 21-4%, the mole number sum of terephthalic acid and m-phthalic acid equals the mole number of triptycene quinhydrones, and mole number terephthalic acid/isophthalic acid=3/2-2/3, four mole number sums are 100%.
3, Wholly aromatic liquid crystal polymer as claimed in claim 2, the molecular fraction that it is characterized in that described P-hydroxybenzoic acid, triptycene quinhydrones, terephthalic acid and m-phthalic acid is respectively 50-75%, 25-12.5%, 15-5% and 15-5%, the mole number sum of terephthalic acid and m-phthalic acid equals the mole number of triptycene quinhydrones, and mole number terephthalic acid/isophthalic acid=3/2-2/3, four mole number sums are 100%.
4, the preparation method of the described Wholly aromatic liquid crystal polymer of claim 1, it is characterized in that comprising the steps: each monomer is mixed in proportion, add diacetyl oxide as acylating agent, and acetate or the fragrant hydrochlorate of Zn, K, Mg, Ca or Co are catalyzer, 140-150 ℃ acetylize 2-6 hour, be warming up to 270-350 ℃ with 10-40 ℃/h speed then, and insulation reaction 10 minutes to 4 hours; Be evacuated to below the 0.3mmHg heat-insulation pressure keeping reaction 15-60 minute; N
2Exist and 10-40 ℃ of following solid state polycondensation 1-24 of prepolymer fusing point hour.
5, preparation method as claimed in claim 1, the molar weight that it is characterized in that described diacetyl oxide are 1.1-3 times of four monomer hydroxyl total amounts.
6, preparation method as claimed in claim 1, the weight that it is characterized in that described catalyzer is the 0.01-1.2% of four total monomer weights.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012759A (en) * | 2011-09-23 | 2013-04-03 | 金发科技股份有限公司 | Liquid crystal polyester and its preparation method and use |
| CN103570927A (en) * | 2012-07-06 | 2014-02-12 | 金发科技股份有限公司 | Thermotropic liquid crystal polyester and preparation method thereof |
| CN104344605A (en) * | 2013-07-29 | 2015-02-11 | 三菱电机株式会社 | Heat pump device |
| 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 |
| CN111727390A (en) * | 2018-02-14 | 2020-09-29 | 富士胶片株式会社 | Polymerizable liquid crystal composition, optically anisotropic film, optical film, polarizing plate, and image display device |
| CN112608462A (en) * | 2020-12-23 | 2021-04-06 | 苏州润佳工程塑料股份有限公司 | LCP (liquid Crystal Polymer) high polymer material suitable for 5G product |
| CN113527647A (en) * | 2021-08-04 | 2021-10-22 | 中国科学院长春应用化学研究所 | Liquid crystal polymer, preparation method thereof and liquid crystal polymer film |
| CN117024719A (en) * | 2023-10-07 | 2023-11-10 | 宁波聚嘉新材料科技有限公司 | Liquid crystal polymer, fiber, preparation method of liquid crystal polymer and fiber, and fiber concrete |
-
2009
- 2009-09-04 CN CN2009101920876A patent/CN101649044B/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012759A (en) * | 2011-09-23 | 2013-04-03 | 金发科技股份有限公司 | Liquid crystal polyester and its preparation method and use |
| CN103012759B (en) * | 2011-09-23 | 2014-07-02 | 金发科技股份有限公司 | Liquid crystal polyester and its preparation method and use |
| CN103570927A (en) * | 2012-07-06 | 2014-02-12 | 金发科技股份有限公司 | Thermotropic liquid crystal polyester and preparation method thereof |
| CN104344605A (en) * | 2013-07-29 | 2015-02-11 | 三菱电机株式会社 | Heat pump device |
| 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 |
| CN106750198B (en) * | 2016-12-12 | 2019-05-07 | 中山大学 | A kind of thermotropic liquid crystalline polyester that monomer ratio is stable with and the preparation method and application thereof |
| CN111727390A (en) * | 2018-02-14 | 2020-09-29 | 富士胶片株式会社 | Polymerizable liquid crystal composition, optically anisotropic film, optical film, polarizing plate, and image display device |
| CN111727390B (en) * | 2018-02-14 | 2021-11-02 | 富士胶片株式会社 | Polymerizable liquid crystal composition, optical film, polarizing plate, and image display device |
| CN112608462A (en) * | 2020-12-23 | 2021-04-06 | 苏州润佳工程塑料股份有限公司 | LCP (liquid Crystal Polymer) high polymer material suitable for 5G product |
| CN113527647A (en) * | 2021-08-04 | 2021-10-22 | 中国科学院长春应用化学研究所 | Liquid crystal polymer, preparation method thereof and liquid crystal polymer film |
| CN117024719A (en) * | 2023-10-07 | 2023-11-10 | 宁波聚嘉新材料科技有限公司 | Liquid crystal polymer, fiber, preparation method of liquid crystal polymer and fiber, and fiber concrete |
| CN117024719B (en) * | 2023-10-07 | 2024-01-30 | 宁波聚嘉新材料科技有限公司 | Liquid crystal polymer, fiber, preparation method of liquid crystal polymer and fiber, and fiber concrete |
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