CN106757476A - A kind of thermotropic liquid crystal polyarylate fiber and preparation method thereof - Google Patents
A kind of thermotropic liquid crystal polyarylate fiber and preparation method thereof Download PDFInfo
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- CN106757476A CN106757476A CN201611216408.8A CN201611216408A CN106757476A CN 106757476 A CN106757476 A CN 106757476A CN 201611216408 A CN201611216408 A CN 201611216408A CN 106757476 A CN106757476 A CN 106757476A
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- 239000000835 fiber Substances 0.000 title claims abstract description 109
- 229920001230 polyarylate Polymers 0.000 title claims abstract description 38
- 239000004974 Thermotropic liquid crystal Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 69
- 238000010438 heat treatment Methods 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000004132 cross linking Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 32
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 24
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 238000009987 spinning Methods 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000002074 melt spinning Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000005452 bending Methods 0.000 description 5
- 229920000106 Liquid crystal polymer Polymers 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000784 Nomex Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- QOBLJVUECBDJGF-UHFFFAOYSA-N [Mg].CC(O)=O Chemical compound [Mg].CC(O)=O QOBLJVUECBDJGF-UHFFFAOYSA-N 0.000 description 1
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000005410 aryl sulfonium group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003700 hair damage Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004763 nomex Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000005409 triarylsulfonium group Chemical group 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
- 235000013904 zinc acetate Nutrition 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/065—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids the hydroxy and carboxylic ester groups being bound to aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3804—Polymers with mesogenic groups in the main chain
- C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/001—Treatment with visible light, infrared or ultraviolet, X-rays
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a kind of thermotropic liquid crystal polyarylate (TLCPAR) fiber and preparation method thereof.Thermotropic liquid crystal polyarylate fiber of the invention, there is micro- cross-linked structure along fiber horizontal direction between polyarylate macromolecular, micro- cross-linked structure is by making to contain monomer of some side chain with double bond in polymerized monomer, and after polymerisation the phase add light trigger, then heat treatment of fiber process simultaneously carry out photo-crosslinking obtained from.According to the TLCPAR fibers between macromolecular prepared by the method for the present invention with micro- cross-linked structure, excellent mechanical property is respectively provided with the axially and transversely direction of fiber.Also, the present invention solve traditional TLCPAR fibers because lateral junction is poor with joint efforts between macromolecular, Anisotropy and skin-core structure it is serious the problems brought.
Description
Technical field
It is more particularly to a kind of in fiber the present invention relates to a kind of thermotropic liquid crystal polyarylate fiber and preparation method thereof
Axially and transversely the mechanical property in direction is very excellent and solves traditional TLCPAR fibers because of lateral junction between macromolecular
The high-performance thermotropic liquid crystal polyarylate fiber of the problems that poor with joint efforts, Anisotropy and skin-core structure seriously bring
And preparation method thereof.
Background technology
Du pont company successfully develops the high-performance liquid crystal fiber Kelvar based on Nomex within 1972, opens
The history of liquid crystal polymer practical application has been created, the development and industrialization of liquid crystal polymer has also greatly been have stimulated.Due to this
Liquid crystal polymer is to be formed in the solution and can not molded, and excites people for not needing solvent, is had under melt state
The research of the thermotropic liquid crystalline polymer of liquid crystal liquid crystal property.Trade name U- was successfully developed first from Unitika companies of Japan in 1973
The thermotropic liquid crystal polyarylate (TLCPAR) of polymer simultaneously realizes industrialization, and people are just devoted to polyarylate new varieties always
Development and application.Contain a large amount of phenyl ring in TLCPAR main chains, can be in liquid crystal after heated melting with linear upright and outspoken chain configuration
Polyarylate macromolecular in state, thus spinning melt is easily orientated under the shear action in spinneret aperture, and due to firm
Property molecule slack time it is more long, this structure height-oriented along fiber direction of principal axis cooling when be almost fully retained under
Come, therefore thermotropic liquid crystal polyarylate fiber has high intensity and modulus in fiber direction of principal axis.Additionally, TLCPAR fibers are also
The features such as with excellent heat resistance, anti-flammability, chemical resistance, weatherability and agent of low hygroscopicity, low creep, thus extensively should
For the field such as aerospace and military, high-performance rope and net, protective articles, sports equipment.
Traditional TLCPAR fibre structures are as shown in Figure 1, on the one hand, what the axial direction of TLCPAR fibers was highly directional, and just
Hard macromolecular chain is in extended configuration, it is impossible to folds, is not as flexible macromolecule such as polyethylene, polypropylene, poly terephthalic acid
Butanediol ester, nylon66 fiber are produced between folded-chain structure, TLCPAR macromoleculars almost without chain entanglement like that；On the other hand, along fibre
Dimension axial direction has the strong covalent bond of TLCPAR macromoleculars, and is not any horizontal direction perpendicular to fiber axial direction
Covalent bond or hydrogen bond link, only with weaker Van der Waals force equimolecular intermolecular forces.This two big factor result in TLCPAR
Fiber transverse strength and modulus have extremely obvious far below the intensity and modulus on fiber axial direction, i.e. TLCPAR fibers
Anisotropy.This fiber is axially and the huge difference of horizontal mechanical performance brings problems.Such as, TLCPAR is worked as
When fiber is laterally pressurized, compression position occurs a number of longitudinal layered, and this causes TLCPAR fibers in textile process,
When being particularly pressurized between the roller that pressurizes or be pressurized at warp and weft interweaving point, obvious impression is easily produced, occurred when serious
Longitudinal splitting；Torsional property is poor, easily longitudinal layered when fiber is reversed, thus loss of strength is bright during TLCPAR Yarn twistings
Aobvious, this is to the operation of TLCPAR Yarn twistings with difficulty.Additionally, TLCPAR fibers being bent, shear action when also easily
Destroyed.The weak point above-mentioned for TLCPAR fibers, existing disclosed technology cannot also properly be tackled and improved.
The content of the invention
The present invention provides a kind of high-performance thermotropic liquid crystal polyarylate fiber and preparation method thereof.Using preparation of the invention
Method, can prepare the TLCPAR fibers with micro- cross-linked structure between macromolecular so that TLCPAR fibers are in fiber
Axially and transversely direction is respectively provided with excellent mechanical property, solve traditional TLCPAR fibers because between macromolecular lateral junction make a concerted effort
The problems that difference, Anisotropy and skin-core structure are serious and bring.Also, it is fine using the TLCPAR prepared by the present invention
The fracture strength and initial modulus of dimension are up to 28~32cN/dtex and 1000~1200cN/dtex respectively, relative to tradition
TLCPAR fibers are obviously improved.
A kind of thermotropic liquid crystal polyarylate fiber that the present invention is provided, along fiber horizontal direction between polyarylate macromolecular
With micro- cross-linked structure, micro- cross-linked structure be by making the monomer with double bond containing some side chain in polymerized monomer, and
Phase addition light trigger, then carries out ultraviolet light cross-linking reaction simultaneously through melt spinning and in heat treatment of fiber process after polymerisation
Obtained from.
A kind of preparation method of high-performance thermotropic liquid crystal polyarylate fiber of the invention is comprised the following steps：(1)
The polymerization of TLCPAR and granulation, the drying of (2) TLCPAR sections and spinning, the ultraviolet light irradiation and Re Chu of (3) TLCPAR fibers
Reason, wherein the polymerized monomer of TLCPAR for monomer A, monomer B and monomer C mixture, and monomer A, monomer B and monomer C thing
The amount (being designated as n (A), n (B) and n (C) respectively) of matter meets following quantitative relation：
The monomer A is following one kind：
Wherein R is double bond containing side base；The monomer B and the monomer C are free of the side base with double bond.
In a preferred embodiment of the invention, the R side bases of the monomer A are one kind of following structural：
In a preferred embodiment of the invention, the monomer B is following one kind：
In a preferred embodiment of the invention, the monomer C is following one kind：
Wherein, X is the one kind in following structural：
In a preferred embodiment of the invention, the polymerization of TLCPAR using gradually temperature-rising method in reactor such as reactor
Melt polymerization is carried out, reactions steps are：Polymerized monomer, acetic anhydride and catalyst are disposably dosed into reactor (preferably
It is reactor) in, 100~160 DEG C of 1~4h of reaction are warming up to, 160~200 DEG C of 1~2h of reaction are then heated to, then be warming up to
200~250 DEG C of 1~2h of reaction, then to addition light trigger and sensitizer in reactor, and are continuously heating to 270~300 DEG C
0.5~1.5h of reaction, vacuumizes to reactor afterwards, is decompressed to 0.1~1KPa and reacts 0.5~1h.The granulation of TLCPAR is preferred
Ground is carried out discharge and is granulated by granulating system by linking the screw rod of the reactor after reaction to be polymerized terminates, and is obtained
To TLCPAR sections.
Preferably, the light trigger is one kind of triaryl salt compounded of iodine and triaryl sulfonium salts, the light trigger
Addition is the 0.5~1.5% of polymerized monomer A, B and C gross masses.
Preferably, the sensitizer is one kind of 2,3- bihydrogen-1-indenones or anthracene, and the addition of the sensitizer is polymerization
The 0.5~1% of monomer A, B and C gross mass.
Preferably, the addition of the acetic anhydride, is 1.1~1.3 times of n (A)+n (B)+n (C) with the gauge of material.
Preferably, the catalyst is the one kind in magnesium acetate, zinc acetate and calcium acetate, and the addition of the catalyst is
The 0.1~0.5% of polymerized monomer A, B and C gross masses.
In a preferred embodiment of the invention, the drying and spinning of the TLCPAR sections is comprised the following steps：By step
(1) TLCPAR sections obtained in dry 4~12h at 100~140 DEG C, are preferably disposed in drum dried case and are dried；Then
TLCPAR as-spun fibres, spinning-drawing machine 18~30mm of screw diameter, draw ratio 20~30, spinning temperature are prepared using melt spinning machine
250~320 DEG C.The fracture strength of step gained as-spun fibre is 8~12cN/dtex, and initial modulus is 450~650cN/
dtex。
In a preferred embodiment of the invention, the ultraviolet light irradiation and heat treatment method of the TLCPAR fibers are：Will step
Suddenly the TLCPAR as-spun fibres that (2) obtain are heat-treated on the Dynamic heat-treatment machine equipped with ultraviolet light generator so that fine
The solid-phase polymerization of ultraviolet light irradiation cross-linking reaction and heat treatment process in dimension between TLCPAR macromoleculars is carried out simultaneously.
Preferably, the heat treatment be divided to two temperature sections to carry out, and first stage heat treatment temperature is 220~280 DEG C, it is hot at
8~12h of reason time, second stage heat treatment temperature is 240~300 DEG C, 4~6h of heat treatment time；Heat treatment is in dynamic nitrogen
Carried out under gas atmosphere；The ultraviolet light irradiation is started simultaneously at heat treatment of fiber, and is terminated after 0.5~2h, ultraviolet wavelength
It is 250~320nm.The ultraviolet light generator can use medium-pressure or high pressure mercury lamp.
Can by the TLCPAR fibrous fractures intensity of the invention and initial modulus that are obtained after ultraviolet light irradiation and heat treatment
Respectively up to 28~32cN/dtex and 1100~1400cN/dtex.
The present invention also provides a kind of polymer obtained by the polymerization of above-mentioned steps (1).
The present invention also provides a kind of TLCPAR by being obtained after the polymer prills for obtaining of above-mentioned steps (1) and cuts into slices.
The present invention also provides a kind of TLCPAR as-spun fibres obtained by above-mentioned steps (2).
TLCPAR fibers prepared by the present invention not only maintain traditional TLCPAR fiber heights and take in fiber axial direction
To characteristic, and there is micro- cross-linked structure between fiber horizontal direction macromolecular, thus, TLCPAR prepared by the present invention is fine
Dimension has excellent comprehensive mechanical property, is mainly reflected in three below aspect：
(1) traditional TLCPAR fibers transverse strength is low, Anisotropy substantially brings bending resistance, antitorque, anti-is solved
The problem of pressure and anti-shearing damage capability difference；
(2) existing TLCPAR fibers are also easy to produce obvious skin-core structure, the TLCPAR fibers that the present invention is provided, molecule it
Between have micro- cross-linked structure, enhance the adhesion between each layer of TLCPAR fibers, make its fiber in big bending deformation be difficult hair
Damage layer estranged；
(3) fracture strength and initial modulus of the TLCPAR fibers that the present invention is provided respectively up to 28~32cN/dtex and
1100~1400cN/dtex, 15~40% and 20~50% have been respectively increased relative to traditional thermotropic liquid crystal polyarylate fiber.
Certainly, implement any product of the invention to it is not absolutely required to while reaching all the above advantage.
Brief description of the drawings
Fig. 1 is the structural representation of polyarylate fiber of the prior art；
Fig. 2 is the structural representation of polyarylate fiber of the invention.
Specific embodiment
The present invention provides a kind of thermotropic liquid of high-performance for being axially respectively provided with excellent mechanical performance with horizontal direction in fiber
Brilliant polyarylate fiber and preparation method thereof.The present invention is prepared by special Molecular Design and processing and forming technology
The thermotropic liquid crystal polyarylate fiber with micro- cross-linked structure, not only solves traditional thermotropic liquid crystal between a kind of macromolecular chain
Anti-shearing, bending that polyarylate fiber is because lateral junction is poor with joint efforts between macromolecular, Anisotropy seriously brings, compression and turn round
Turn the problem of damage capability difference, and alleviate thermotropic liquid crystal polyarylate fiber to a certain extent because skin-core structure seriously brings
Bending when easy delamination failure problem.Further, since this micro- cross-linked structure limits the phase between macromolecular when fiber is stretched
To sliding, the fracture of the thermotropic liquid crystal polyarylate fiber provided relative to traditional thermotropic liquid crystal polyarylate fiber, the present invention
Intensity and initial modulus are obviously improved, and can respectively be up to 28~32cN/dtex and 1100~1400cN/dtex.
The present invention carries out melting contracting from TLCPAR Molecular Designs, the polyarylate monomer that selection side chain contains double bond
Poly- reaction, and after polymerisation the phase add light trigger, so as to obtain containing on light trigger and macromolecular with double bond of side chain
TLCPAR cuts into slices.TLCPAR makes the macromolecular in TLCPAR fibers that side to occur again through melt spinning, ultraviolet light irradiation and heat treatment
Cross-linking reaction between chain, the TLCPAR fibers between finally giving macromolecular with micro- cross-linked structure.
The structure of the TLCPAR fibers that the present invention is provided is as shown in Figure 2.The TLCPAR fibers of this special construction are not only solved
The problems that above-mentioned traditional TLCPAR fibers transverse strength of having determined is low, Anisotropy substantially brings, and bring simultaneously
Following two beneficial effects：
(1) orientation of existing TLCPAR fibers is influenceed by shear stress in process, is also easy to produce obvious core-skin
Structure, adhesion is weaker between each layer, in big bending deformation, can cause material that delamination failure occurs rapidly；And the present invention is carried
Have between the macromolecular chain of the TLCPAR fibers of confession between micro- cross-linked structure, TLCPAR fiber macromoleculars and link with chemical bond,
Fiber horizontal direction interacts strong, can obviously relieve fibrous inside mechanical property that TLCPAR fiber skin-core structures bring not
The problem of even, flexible delamination failure；
(2) knowable to the tensile failure mechanism of fiber, the fracture of fiber produces Relative sliding between depending on internal macromolecular,
Between the TLCPAR fibers with micro- cross-linked structure significantly enhance polyarylate macromolecular between strand provided by the present invention
Interaction, the Relative sliding between macromolecular when fiber is stretched can be limited, so as to further improve TLCPAR fibers axial direction sides
Upward intensity and modulus.
Herein, the scope for being represented by " numerical value to another numerical value ", is that one kind avoids enumerating in the description
The summary representation of all numerical value in the scope.Therefore, the record of a certain special value scope, covers the number range
Interior any number and the relatively fractional value scope defined by any number in the number range, as bright in the description
Text writes out any number as should be compared with fractional value scope.
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate this hair
It is bright, rather than limit protection scope of the present invention.Those skilled in the art are according to changing that the present invention makes in actual applications
Enter and adjust, still fall within protection scope of the present invention.
Embodiment 1
The preparation of the high-performance thermotropic liquid crystal polyarylate fiber of the present embodiment includes following three step：
(1) polymerization of TLCPAR and granulation.
The polymerization of TLCPAR carries out melt polymerization using gradually temperature-rising method in reactor, and reactions steps are：Will
Polymerized monomer, acetic anhydride and catalyst acetic acid magnesium are disposably dosed into reactor, are warming up to 100~110 DEG C of reaction 1h, then
160~170 DEG C of reaction 2h are warming up to, then are warming up to 200~210 DEG C of reaction 1h, then to addition light trigger three in reactor
Aryl salt and sensitizer 2,3- bihydrogen-1-indenones, and 270~280 DEG C of reaction 0.5h are continuously heating to, afterwards to reactor
Vacuumize, be decompressed to 0.5KPa reactions 0.5h.The granulation of TLCPAR is by linking the reactor after reaction to be polymerized terminates
Screw rod carry out discharge and granulated by granulating system, obtain TLCPAR section.
Wherein the polymerized monomer of TLCPAR is the mixture of monomer A, monomer B and monomer C, and monomer A, monomer B and monomer C
The amount (being designated as n (A), n (B) and n (C) respectively) of material meet following quantitative relation：
The monomer A is：
Wherein, the R side bases are：
The monomer B is：
The monomer C is：
The addition of the light trigger is the 0.5% of polymerized monomer A, B and C gross masses, the addition of the sensitizer
It is the 0.5% of polymerized monomer A, B and C gross masses, the addition of the acetic anhydride, with the gauge of material, is n (A)+n (B)+n
(C) 1.1 times, the addition of the catalyst is the 0.1% of polymerized monomer A, B and C gross masses.
(2) drying and spinning of TLCPAR sections.
TLCPAR sections obtained in step (1) are placed in drum dried case and dry 12h at 100 DEG C；Then using melting
Spinning-drawing machine prepares TLCPAR as-spun fibres, spinning-drawing machine screw diameter 18mm, draw ratio 30,280 DEG C of spinning temperature.Step gained
The fracture strength of as-spun fibre is 8cN/dtex, and initial modulus is 450cN/dtex.
(3) ultraviolet light irradiation of TLCPAR fibers and heat treatment.
The TLCPAR as-spun fibres that step (2) is obtained carry out heat on the Dynamic heat-treatment machine equipped with ultraviolet light generator
Treatment so that the solid-phase polymerization of ultraviolet light irradiation cross-linking reaction and heat treatment process in fiber between TLCPAR macromoleculars is same
Shi Jinhang.
The heat treatment be divided to two temperature sections to carry out, and first stage heat treatment temperature is 250 DEG C, heat treatment time 10h, the
Two-stage heat treatment temperature is 270 DEG C, heat treatment time 4h；Heat treatment is carried out under dynamic nitrogen atmosphere；The ultraviolet light
Irradiation is started simultaneously at heat treatment of fiber, and is terminated after 0.5h, a length of 320nm of ultraviolet light wave.The ultraviolet light generator makes
Use medium pressure mercury lamp.
The TLCPAR fibrous fractures intensity and initial modulus of the present embodiment obtained by ultraviolet light irradiation and after being heat-treated
28cN/dtex and 1200cN/dtex can respectively be reached.
Embodiment 2
The preparation of the high-performance thermotropic liquid crystal polyarylate fiber of the present embodiment includes following three step：
(1) polymerization of TLCPAR and granulation.
The polymerization of TLCPAR carries out melt polymerization using gradually temperature-rising method in reactor, and reactions steps are：Will
Polymerized monomer, acetic anhydride and catalyst acetic acid zinc are disposably dosed into reactor, are warming up to 150~160 DEG C of reaction 4h, then
190~200 DEG C of reaction 2h are warming up to, then are warming up to 240~250 DEG C of reaction 2h, then to addition light trigger three in reactor
Arylsulfonium salts and sensitizer anthracene, and 290~300 DEG C of reaction 1.5h are continuously heating to, reactor is vacuumized afterwards, it is decompressed to
0.1KPa reacts 1h.The granulation of TLCPAR reaction preferably to be polymerized is carried out after terminating by linking the screw rod of the reactor
Discharge is simultaneously granulated by granulating system, obtains TLCPAR sections.
Wherein the polymerized monomer of TLCPAR is the mixture of monomer A, monomer B and monomer C, and monomer A, monomer B and monomer C
The amount (being designated as n (A), n (B) and n (C) respectively) of material meet following quantitative relation：
The monomer A is：
Wherein,
The R side bases are：
The monomer B is：
The monomer C is：
Wherein, X is：
The addition of the light trigger is the 1.5% of polymerized monomer A, B and C gross masses, the addition of the sensitizer
It is the 1% of polymerized monomer A, B and C gross masses, the addition of the acetic anhydride, with the gauge of material, is n (A)+n (B)+n (C)
1.3 times, the addition of the catalyst is the 0.5% of polymerized monomer A, B and C gross masses.
(2) drying and spinning of TLCPAR sections.
TLCPAR sections obtained in step (1) are placed in drum dried case and dry 4h at 140 DEG C；Then spun using melting
Wire feed mechanism is for TLCPAR as-spun fibres, spinning-drawing machine screw diameter 30mm, draw ratio 20,350 DEG C of spinning temperature.Step gained is just
The fracture strength of raw fiber is 12cN/dtex, and initial modulus is 650cN/dtex.
(3) ultraviolet light irradiation of TLCPAR fibers and heat treatment.
The TLCPAR as-spun fibres that step (2) is obtained carry out heat on the Dynamic heat-treatment machine equipped with ultraviolet light generator
Treatment so that the solid-phase polymerization of ultraviolet light irradiation cross-linking reaction and heat treatment process in fiber between TLCPAR macromoleculars is same
Shi Jinhang.
The heat treatment be divided to two temperature sections to carry out, and first stage heat treatment temperature is 270 DEG C, heat treatment time 12h, the
Two-stage heat treatment temperature is 290 DEG C, heat treatment time 5h；Heat treatment is carried out under dynamic nitrogen atmosphere；The ultraviolet light
Irradiation is started simultaneously at heat treatment of fiber, and is terminated after 2h, a length of 250nm of ultraviolet light wave.The ultraviolet light generator is used
High-pressure sodium lamp.
Can by the TLCPAR fibrous fractures intensity of the invention and initial modulus that are obtained after ultraviolet light irradiation and heat treatment
32cN/dtex and 1400cN/dtex is reached respectively.
(usually 22cN/dtex is left for the intensity not more than 25cN/dtex of traditional thermotropic liquid crystal polyarylate fiber
It is right), modulus not more than 900cN/dtex (usually 700-800cN/dtex or so), the TLCPAR fibers that the present invention is provided
Fracture strength and initial modulus be respectively increased 15~40% and 20 relative to traditional thermotropic liquid crystal polyarylate fiber~
50%.
TLCPAR fibers prepared by the present invention also solve traditional TLCPAR fibers because of horizontal integration between macromolecular simultaneously
The problems that power is poor, Anisotropy and skin-core structure seriously bring, enhance the knot between each layer of TLCPAR fibers
With joint efforts.
Under the teaching of the present invention and above-described embodiment, those skilled in the art are easy to it is envisioned that the present invention is cited
Or each raw material for enumerating or its equivalent alterations, each processing method or its equivalent alterations can realize the present invention, and each original
The parameter bound value of material and processing method, interval value can realize the present invention, embodiment numerous to list herein.
Claims (10)
1. a kind of thermotropic liquid crystal polyarylate fiber, it is characterised in that have along fiber horizontal direction between polyarylate macromolecular
Have micro- cross-linked structure, micro- cross-linked structure be by making the monomer with double bond containing some side chain in polymerized monomer, and
The polymerization later stage adds light trigger, then carry out ultraviolet light cross-linking reaction simultaneously through melt spinning and in heat treatment of fiber process and
Obtain.
2. the preparation method of the thermotropic liquid crystal polyarylate fiber described in a kind of claim 1, it is characterised in that including following step
Suddenly：
(1) polymerization of TLCPAR and granulation, are obtained TLCPAR sections；
(2) drying and spinning of TLCPAR sections, are obtained TLCPAR as-spun fibres；
(3) ultraviolet light irradiation of TLCPAR as-spun fibres and heat treatment；
Wherein, the polymerized monomer of TLCPAR is the mixture of monomer A, monomer B and monomer C, and monomer A, monomer B and monomer C
The amount (being designated as n (A), n (B) and n (C) respectively) of material meets following quantitative relation：
The monomer A is following one kind：
Wherein R is double bond containing side base；The monomer B and the monomer C are free of the side base with double bond.
3. the preparation method of thermotropic liquid crystal polyarylate fiber as claimed in claim 2, it is characterised in that the R of the monomer A
Side base is one kind of following structural：
4. the preparation method of thermotropic liquid crystal polyarylate fiber as claimed in claim 2, it is characterised in that the monomer B is
Following one kind：
The monomer C is following one kind：
Wherein, X is the one kind in following structural：
5. the preparation method of thermotropic liquid crystal polyarylate fiber as claimed in claim 2, it is characterised in that the polymerization of TLCPAR
Reactions steps are：Polymerized monomer, acetic anhydride and catalyst are disposably dosed into reactor, 100~160 DEG C of reactions are warming up to
1~4h, then heats to 160~200 DEG C of 1~2h of reaction, then is warming up to 200~250 DEG C of 1~2h of reaction, then to reactor
It is interior to add light trigger and sensitizer, and 270~300 DEG C of 0.5~1.5h of reaction are continuously heating to, reactor is taken out very afterwards
Sky, is decompressed to 0.1~1KPa and reacts 0.5~1h；The addition of the light trigger is the 0.5 of polymerized monomer A, B and C gross masses
~1.5%；The addition of the sensitizer is the 0.5~1% of polymerized monomer A, B and C gross masses；The addition of the acetic anhydride
Amount, is 1.1~1.3 times of n (A)+n (B)+n (C) with the gauge of material；The addition of the catalyst is polymerized monomer A, B
With the 0.1~0.5% of C gross masses.
6. the preparation method of thermotropic liquid crystal polyarylate fiber as claimed in claim 2, it is characterised in that the TLCPAR cuts
The drying and spinning of piece are comprised the following steps：TLCPAR sections obtained in step (1) are dried into 4~12h at 100~140 DEG C；
Then TLCPAR as-spun fibres, spinning-drawing machine 18~30mm of screw diameter, draw ratio 20~30, spinning are prepared using melt spinning machine
250~320 DEG C of temperature.
7. the preparation method of thermotropic liquid crystal polyarylate fiber as claimed in claim 2, it is characterised in that the TLCPAR is fine
The ultraviolet light irradiation and heat treatment method of dimension be：The TLCPAR as-spun fibres that step (2) is obtained are equipped with ultraviolet light generator
Dynamic heat-treatment machine on be heat-treated so that in fiber between TLCPAR macromoleculars ultraviolet light irradiation cross-linking reaction and heat at
The solid-phase polymerization of reason process is carried out simultaneously；
The heat treatment be divided to two temperature sections to carry out, and first stage heat treatment temperature is 220~280 DEG C, and heat treatment time 8~
12h, second stage heat treatment temperature is 240~300 DEG C, 4~6h of heat treatment time；Heat treatment is entered under dynamic nitrogen atmosphere
OK；The ultraviolet light irradiation is started simultaneously at heat treatment of fiber, and is terminated after 0.5~2h, and ultraviolet light wave a length of 250~
320nm。
8. the polymer that the polymerization of any described step (1) is obtained in a kind of 2-7 by claim.
9. the TLCPAR sections that any described step (1) is obtained in a kind of 2-7 by claim.
10. the TLCPAR as-spun fibres that any described step (2) is obtained in a kind of 2-7 by claim.
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| CN109957853A (en) * | 2017-12-22 | 2019-07-02 | 江苏集萃智能液晶科技有限公司 | A kind of liquid crystal complex fiber and preparation method thereof |
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