CN106592002A - Liquid crystal polyester fiber and preparation method thereof - Google Patents
Liquid crystal polyester fiber and preparation method thereof Download PDFInfo
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- CN106592002A CN106592002A CN201510665368.4A CN201510665368A CN106592002A CN 106592002 A CN106592002 A CN 106592002A CN 201510665368 A CN201510665368 A CN 201510665368A CN 106592002 A CN106592002 A CN 106592002A
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Abstract
The invention discloses a liquid crystal polyester fiber and a preparation method thereof. The preparation method comprises the steps that in a polymerization kettle, a phenol monomer bisphenol A and acetic anhydride or polyphosphoric acid are subjected to an acylation reaction to generate bisphenol A diacetic ester or bisphenol A polyphosphoric ester; the bisphenol A diacetic ester or bisphenol A polyphosphoric ester, terephthalic acid and isophthalic acid are subjected to a melting ester exchange reaction, and then bisphenol A-carboxylic aromatic copolyester is prepared through a condensation polymerization reaction; a low-modulus fiber is prepared by taking acetic acid or polyphosphoric acid as a solvent through a dry-jet wet-spinning liquid crystal spinning technology and then put into a heating box to be subjected to heat treatment, and then the liquid crystal polyester fiber is obtained. The liquid crystal polyester fiber obtained through the method has the good strength and tensile property. The preparation method is a one-step method, dry-jet wet-spinning is adopted, operation is easy, polyphosphoric acid or acetic anhydride is especially adopted as an acylating agent and a spinning solvent, the raw materials are convenient to obtain and have no corrosivity to equipment, liquid crystal polyester has the good spinnability, and the fiber obtained through spinning achieves the excellent comprehensive properties.
Description
Technical field
The present invention relates to textile engineering technical field, in particular it relates to a kind of liquid crystalline polyester fiber and preparation method thereof.
Background technology
Liquid crystal polymer (Liquid Crystalline Polymer, abbreviation LCP) is in the one kind between liquid and crystal
Between state macromolecular compound, be the class novel high polymer material for developing rapidly nearest decades.With other macromolecule phases
Than liquid crystal polymer has molecularly oriented sequence and position specific to liquid crystal；With small molecule liquid crystal compound phase ratio, liquid crystal height
Molecule has high molecular characteristic again.The combination of macromolecule and liquid crystal phase sequence impart the distinct individual character of liquid crystal polymer and
Characteristic.Can be divided into according to the condition of Formation of liquid crystals：Lyotropic liquid crystal polymers (Lyotropic Liquid Crystalline Polymer)
With TLCP (Thermotropic Liquid Crystalline Polymer, abbreviation TLCP, with liquid crystal polyester as generation
Table).TLCP refers to temperature range of the macromolecule between certain temperature range, i.e. fusing point and clearing point,
Liquid crystal state is formed, in mesomorphic polymer, the rigid element of strand is arranged according to a certain direction, shows space
The average orientation of strand is different in order, but each microcell, can be molded, extrusion molding etc..
Viscosity of the LCP in its liquid crystal state phase silicon carbide is relatively low and height-oriented, thus LCP materials have it is a series of
Excellent performance, such as high intensity, high-moduluss, the thermostability of protrusion, minimum linear expansion coefficient, excellent flame resistance, electricity
The saturating microwave of insulating properties, chemical resistance, weather-resistant and energy, and excellent moulding processability etc., in recent years more
It is described as in the world " new material of 21 century " or " Super Engineering material ".
TLCP is a kind of high performance material, with the excellent properties such as high temperature resistant, dimensional stability be strong.Conduct
Special material is applied in fields such as Aero-Space, military affairs, electronics, communications.Liquid crystal polyarylate can Jing melt-spinnings into extraordinary fine
Dimension.Not only intensity, modulus can match in excellence or beauty the fiber with aramid fiber, and with unique wet-hot aging performance, vibration fade performance with
And excellent acid and alkali-resistance, abrasion resistance properties.
External existing TLCP manufacturer and product mainly have an Xydar of new Japan's petrochemical industry, Polyplastics and
The Vectra of Ticona company of the U.S., the Ueno series of products of Japanese u'eno, the Rodrun of outstanding Ni Qika companies of Japan, day
The Siveras trades mark of Ben Dongli, the Zenite of du pont company is serial, the K trades mark that in addition also Beyer Co., Ltd produces
LCP materials, Ultrax trade mark LCP materials of BASF AG's production etc..It is domestic for some years recently, it is Beijing University, clear
The colleges and universities such as China, Fudan University and some institutes are also studied, and are had phase to LCP, particularly thermotropic LCP materials
When many research papers and report.Disclose a kind of poly- mixed with low-molecular-weight thermotropic liquid crystal in Chinese patent CN102071493A
The high viscosity thermotropic liquid crystal polyarylate spinning process of aromatic ester, is to adopt melt spinning, belongs to two-step method spinning；Chinese patent
Disclose a kind of embedding using siloxanes or siloxanes in application 86106830 and patent Chinese patent application 200680046533
The copolymer-modified polyarylate of section, such silicone block copolymer forms clad in spinning process, special so as to give fiber
Some premium properties.In general, although the country expands research to liquid crystal polymer material, more it is tracked
Research in terms of research and processing, also has many technical problems not adequately addressed in industrialization practice, and such as thermotropic liquid crystal is high
Molecule aggregation reacts wayward, Thermotropic Liquid Crystalline Copolyesters (TLCP, TLCP) the materials processing temperature of synthesis
Degree window narrows etc., substantially also do not form effective production capacity, particularly there is the product of certain competitiveness.Current liquid crystal
The visible report of Direct-spinning of PET Fiber is all melt spinning method, needs to carry out solid-phase tack producing to liquid crystal polyester before spinning, belongs to two-step method
Technique.And for thermotropic liquid crystal polyester belongs to backbone chain type liquid crystal macromolecule, rigid mesomorphic unit is located among main chain, Gu
Some rigid chain segments make it have higher fusing point, even above its decomposition temperature.Certainly for macrostate, decompose completely
The time is also required to, but even if the liquid crystal polyester melt spinning of this class obtains fiber also due to part has been decomposed so that point
Son amount distribution is extremely irregular, therefore fibre strength is low, and modulus is low.And during liquid crystal polyester melt spinning, fiber meeting
Fibre is frozen within the scope of very narrow temperature, the problem that fibre orientation is uneven is caused.
The content of the invention
In order to overcome the deficiencies in the prior art, the technical problem to be solved to be to provide a kind of liquid crystal polyester of high-moduluss
Fiber and preparation method thereof.The inventive method is simple to operate, and raw material sources are convenient；Liquid crystal copolyester in preparation process has
Good spinnability, be polymerized spinning one-step shaping, it is not necessary to solid-phase tack producing again after liquid crystal polyester pelletize, the technique journey such as remelted
Sequence, it is to avoid phenomenon of decomposing in liquid crystal polyester melting process, and saved energy consumption.The liquid crystal polyester that the present invention is obtained is fine
Dimension has outstanding combination property.
In the present invention, polymer solution is mesomorphic state, directly Jing deaerations and filtration can enter response type twin-screw compounder,
Again fiber is obtained using dry-jet wet-spinning fiber spinning from crystalline state.Concrete technical scheme is described below.
The present invention provides a kind of preparation method of liquid crystalline polyester fiber, comprises the steps：
(1) it is phenolic monomers first from bisphenol-A, it is carried out into acyl with acetic anhydride or polyphosphoric acids under catalyst action
Change to react and generate bisphenol-A diacetate esters or bisphenol-A condensed phosphate, react and remove after terminating acid, addition p-phthalic acid/
M-phthalic acid carries out ester exchange reaction, carries out polycondensation again afterwards and bisphenol-A-right/carboxylic acid aromatic copolyesters are obtained；
(2) gained bisphenol-A-right/carboxylic acid aromatic copolyesters are delivered to into filament spinning component carries out fiber spinning from crystalline state, and temperature is 295～
310 DEG C, winding speed is 90～110m/min；Terminate at a temperature of 95～105 DEG C vacuum drying 0.5～
2h, obtains low modulus liquid crystalline polyester fiber；
(3) low modulus liquid crystalline polyester fiber enters the heater box of inert gas shielding, and heat is carried out at a temperature of 400～800 DEG C
Process, obtain high-moduluss liquid crystalline polyester fiber.
Bisphenol-A is acylated temperature at 130～160 DEG C in above-mentioned steps (1), and reaction raw materials inventory mol ratio is generally bisphenol-A
It is 1 with the mol ratio of acetic anhydride or polyphosphoric acids：2～1：3, need to be continually fed into nitrogen in course of reaction；Polycondensation reaction temperature
Spend for 250～330 DEG C, polycondensation reaction is completed under vacuum conditions, required vacuum is in 20～80Pa.
The catalyst of acylation and ester exchange reaction in above-mentioned steps (1) is lithium acetate, zinc acetate, antimony glycol, titanium system
Catalyst, Methylimidazole. one of which or several；The catalyst concn that acylated and ester exchange reaction is added is 200～450ppm.
In above-mentioned steps (1), also need to add stabilizer in polycondensation phase, the stabilizer is trimethyl phosphate or tricresyl phosphate
Ethyl ester, consumption obtains the theoretical yield meter of polyester based on polycondensation reaction, and consumption is 10～100ppm, preferably 30～60ppm.
Above-mentioned steps (2) spinning process is dry-jet wet-spinning, adopts acetic acid or polyphosphoric acids for solvent.
It is acylating agent according to acetic anhydride in above-mentioned steps (1), device is needed using the special substance equipment of resistance to acetic acid,
General equipment material is then can use using polyphosphoric acids, therefore capital input can be reduced, reduce the loss to equipment.
Liquid crystalline polyester fiber is carried out again in heater box used by heat treatment in above-mentioned steps (3) be with mazy fibre bundle
The structure of arrangement mode.
Assay device in above steps is using the reactor, spinning manifold that electrical heating heating agent is whole assay device, adds
Hot tank and material pipeline provide heating and are incubated required heat, and the low temperature heating agent after heat release is lowered the temperature sends electrical heating back to
Device, heated device heating Posterior circle is used, and delivery pump adopts electrical heating.
The present invention further provides the liquid crystalline polyester fiber obtained by above-mentioned preparation method.
The beneficial effects of the present invention is：
(1) liquid crystal copolyester in preparation process of the present invention has good spinnability,；Polymerization spinning one-step shaping, it is not necessary to liquid
Solid-phase tack producing again after brilliant polyester pelletize, the process such as remelted, can be prevented effectively from liquid crystal polyester melting process and decompose
Phenomenon, and can energy efficient；
(2) preparation method is one-step method, and efficiency high, simple to operate, raw material sources are convenient；With good economic benefits and work
Industry application prospect；
(3) invention especially employs polyphosphoric acids for acylating agent and dry-jet wet-spinning solvent, the corrosion very little to equipment；
(4) the obtained fiber of the present invention has higher intensity and tensile property.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments be merely to illustrate the present invention and
It is not used in restriction the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
At a temperature of 130～160 DEG C, with acetic anhydride by bisphenol-A acetylation, bisphenol-A is 1 with the mol ratio of acetic anhydride：2.2,
Need to be continually fed into nitrogen in course of reaction；Excessive acetic acid is sloughed after acylation reaction, the acetic acid of removing is dilute using sodium hydroxide
Solution is neutralized；
It is afterwards 1 according to the mol ratio of carboxyl functional group and hydroxy functional group：1 adds right/M-phthalic acid,；The second of addition
Glycol antimony catalyst concentration is 250～350ppm；
Polycondensation reaction temperature is 250～330 DEG C, and is completed under vacuum conditions, and required vacuum is in 20～80Pa；
Gained aromatic copolyesters are delivered to into filament spinning component carries out fiber spinning from crystalline state, and acetic acid is solvent, and temperature is 295～310 DEG C,
Winding, 90～110m/min of winding speed, after 95～105 DEG C be vacuum dried 0.5～1.5h, obtain low mould
Amount liquid crystalline polyester fiber.
Under nitrogen protection, and under some tension heat treatment is carried out again to above-mentioned fiber at a high temperature of 400～800 DEG C or so,
Further improve the intensity and modulus of fiber.
Embodiment 2
At a temperature of 130～160 DEG C, bisphenol-A is acylated with polyphosphoric acids, bisphenol-A is 1 with the mol ratio of polyphosphoric acids：
2.5, need to be continually fed into nitrogen in course of reaction；Excessive acid is sloughed after acylation reaction, the acid of removing is dilute using sodium hydroxide
Solution is neutralized；
It is afterwards 1 according to the mol ratio of carboxyl functional group and hydroxy functional group：1 adds right/M-phthalic acid,；The vinegar of addition
Sour lithium catalyst concentration is 350～450ppm；
Polycondensation reaction temperature is 250～330 DEG C, and is completed under vacuum conditions, and required vacuum is in 20～80Pa；
Gained aromatic copolyesters are delivered to into filament spinning component carries out fiber spinning from crystalline state, and polyphosphoric acids are solvent, and temperature is 295～310
DEG C, winding, 90～110m/min of winding speed, after 95～105 DEG C be vacuum dried 1.5～2h, obtain low
Modulus liquid crystalline polyester fiber.
Under nitrogen protection, and under some tension heat treatment is carried out again to above-mentioned fiber at a high temperature of 400～800 DEG C or so,
Further improve the intensity and modulus of fiber.
Embodiment 3
At a temperature of 130～160 DEG C, bisphenol-A is acylated with polyphosphoric acids, bisphenol-A is 1 with the mol ratio of polyphosphoric acids：
2.5, need to be continually fed into nitrogen in course of reaction；Excessive acid is sloughed after acylation reaction, the acid of removing is dilute using sodium hydroxide
Solution is neutralized；
It is afterwards 1 according to the mol ratio of carboxyl functional group and hydroxy functional group：1 adds right/M-phthalic acid and p-phthalic acid；
The methylimidazole catalyst concentration of addition is 350～450ppm；
Polycondensation reaction temperature is 250～330 DEG C, and is completed under vacuum conditions, and required vacuum is in 20～80Pa；
Gained aromatic copolyesters are delivered to into filament spinning component carries out fiber spinning from crystalline state, and polyphosphoric acids are solvent, and temperature is 295～310
DEG C, winding, 90～110m/min of winding speed, then at 95～105 DEG C of 1.5～2h of vacuum drying, is finally obtained
Low modulus liquid crystalline polyester fiber.
Under nitrogen protection, and under some tension heat treatment is carried out again to above-mentioned fiber at a high temperature of 400～800 DEG C or so,
Further improve the intensity and modulus of fiber.
The primary quality measure of each embodiment gained liquid crystalline polyester fiber is shown in Table 1.
Table 1
| Project | Line density | Intensity | Modulus | Fiber logarithmic viscosity number |
| Embodiment 1 | 2.29dtex | 1.29GPa | 62.7GPa | 6.91dl/g |
| Embodiment 2 | 1.85dtex | 1.49GPa | 76.3GPa | 7.36dl/g |
| Embodiment 3 | 2.06dtex | 1.42GPa | 73.1GPa | 7.28dl/g |
Test basis：GB/T 14343-2008《Chemical fiber filament line density test method》
GB/T 14344-2008《Chemical fiber filament Erichsen test method》
Although the present invention discloses preferred embodiment as above, so it is not limited to present disclosure, any to be familiar with this
Those skilled in the art, without departing from the present invention main spirits and context in, when can make it is various change with retouching, therefore invent
Protection domain should be defined by the basic right claimed range applied for a patent.
Claims (7)
1. a kind of preparation method of liquid crystalline polyester fiber, it is characterised in that comprise the steps：
(1) it is phenolic monomers first from bisphenol-A, it is carried out into acyl with acetic anhydride or polyphosphoric acids under catalyst action
Change to react and generate bisphenol-A diacetate esters or bisphenol-A condensed phosphate, react and remove after terminating acid, addition p-phthalic acid/
M-phthalic acid carries out ester exchange reaction, and afterwards again Jing polycondensations are obtained bisphenol-A-right/carboxylic acid aromatic copolyesters；
(2) fiber spinning from crystalline state is carried out by gained bisphenol-A-right/a carboxylic acid aromatic copolyesters is delivered to filament spinning component, temperature is
295～310 DEG C, winding speed is 90～110m/min；Terminate at a temperature of 95～105 DEG C vacuum drying 0.5～
2h, obtains low modulus liquid crystalline polyester fiber；
(3) above-mentioned low modulus liquid crystalline polyester fiber enters the heater box of inert gas shielding, enters at a temperature of 400～800 DEG C
Row heat treatment, obtains high-moduluss liquid crystalline polyester fiber.
2. preparation method according to claim 1, it is characterised in that：In step (1), the temperature of acylation reaction is 130～160
DEG C, bisphenol-A is 1 with the mol ratio of acetic anhydride or polyphosphoric acids：2～1：3；The reaction temperature of polycondensation is 250～330 DEG C,
Vacuum is in 20～80Pa.
3. preparation method according to claim 1, it is characterised in that：In step (1), the catalyst be lithium acetate,
Zinc acetate, antimony glycol, Titanium series catalyst or Methylimidazole. any one or a few；The catalyst concn is
200～450ppm.
4. preparation method according to claim 1, it is characterised in that in step (1), in polycondensation phase stabilizer is added,
The stabilizer is trimethyl phosphate or triethyl phosphate, and consumption obtains the theoretical yield meter of polyester, consumption based on polycondensation reaction
For 10～100ppm.
5. preparation method according to claim 1, it is characterised in that in step (2), the method for fiber spinning from crystalline state is dry spray
Wet spinning, adopts acetic acid or polyphosphoric acids for solvent.
6. preparation method according to claim 1, it is characterised in that：In step (3), there is labyrinth in the heater box
The structure of the fibre bundle arrangement mode of formula.
7. the liquid crystalline polyester fiber that the preparation method according to one of claim 1-6 is obtained.
Priority Applications (1)
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| CN201510665368.4A CN106592002A (en) | 2015-10-14 | 2015-10-14 | Liquid crystal polyester fiber and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510665368.4A CN106592002A (en) | 2015-10-14 | 2015-10-14 | Liquid crystal polyester fiber and preparation method thereof |
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| CN106592002A true CN106592002A (en) | 2017-04-26 |
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| CN201510665368.4A Pending CN106592002A (en) | 2015-10-14 | 2015-10-14 | Liquid crystal polyester fiber and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107523894A (en) * | 2017-08-31 | 2017-12-29 | 宋宏婷 | A kind of liquid crystalline polyester fiber and preparation method thereof |
| CN111364109A (en) * | 2020-01-20 | 2020-07-03 | 宁波海格拉新材料科技有限公司 | Fiber heat treatment reaction device, heat treatment system and heat treatment method |
| CN116180269A (en) * | 2023-04-03 | 2023-05-30 | 广东普利特材料科技有限公司 | Preparation method of wholly aromatic liquid crystal polyester and fiber thereof beneficial to PPO resin compounding |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4374239A (en) * | 1980-03-03 | 1983-02-15 | Union Carbide Corporation | Process for preparing polyarylates |
| CN102443873A (en) * | 2011-08-18 | 2012-05-09 | 四川省纺织科学研究院 | Aromatic copolyester liquid crystal fiber and preparation method thereof |
-
2015
- 2015-10-14 CN CN201510665368.4A patent/CN106592002A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4374239A (en) * | 1980-03-03 | 1983-02-15 | Union Carbide Corporation | Process for preparing polyarylates |
| CN102443873A (en) * | 2011-08-18 | 2012-05-09 | 四川省纺织科学研究院 | Aromatic copolyester liquid crystal fiber and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 严兵等: ""聚酯液晶高分子的制备研究"", 《精细与专用化学品》 * |
| 王睦铿: "高强度热致液晶聚芳酯纤维Vectran", 《化工新型材料》 * |
| 钦维民等: ""高性能聚芳酯纤维的研制和表征"", 《合成纤维》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107523894A (en) * | 2017-08-31 | 2017-12-29 | 宋宏婷 | A kind of liquid crystalline polyester fiber and preparation method thereof |
| CN111364109A (en) * | 2020-01-20 | 2020-07-03 | 宁波海格拉新材料科技有限公司 | Fiber heat treatment reaction device, heat treatment system and heat treatment method |
| CN111364109B (en) * | 2020-01-20 | 2023-10-10 | 宁波海格拉新材料科技有限公司 | Fiber heat treatment reaction device, heat treatment system and heat treatment method |
| CN116180269A (en) * | 2023-04-03 | 2023-05-30 | 广东普利特材料科技有限公司 | Preparation method of wholly aromatic liquid crystal polyester and fiber thereof beneficial to PPO resin compounding |
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