CN110498760A - A kind of aromatic thermosetting liquid crystal fiber and preparation method thereof - Google Patents
A kind of aromatic thermosetting liquid crystal fiber and preparation method thereof Download PDFInfo
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- CN110498760A CN110498760A CN201910803586.8A CN201910803586A CN110498760A CN 110498760 A CN110498760 A CN 110498760A CN 201910803586 A CN201910803586 A CN 201910803586A CN 110498760 A CN110498760 A CN 110498760A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/70—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/84—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/121—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20
- C07F7/127—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20 by reactions not affecting the linkages to the silicon atom
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- 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
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- 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
- C09K19/3823—Polymers with mesogenic groups in the main chain containing heterocycles having at least one nitrogen as ring hetero atom
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- 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
-
- 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
- D01F6/82—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from polyester amides or polyether amides
-
- 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
-
- 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
- D01F6/86—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from polyetheresters
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- 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
- C09K2219/00—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used
- C09K2219/01—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used in the form of fibres, e.g. fibres after polymerisation of LC precursor
Abstract
The present invention relates to a kind of aromatic thermosetting liquid crystal fibers and preparation method thereof, comprising: reactive liquid crystalline oligomer, the thermosetting liquid crystal fiber that then melt spinning process will obtain is made in one kettle way melt polycondensation reaction.Fiber polymer chain of the invention is in the rigid chain that stretches, forms the microfibrillar structure of high-sequential, and it is intermolecular there are stronger interactions, to impart the characteristic of the high breaking strength of fiber.Network structure is formed by after acetylenic active end group heat cure reaction with excellent flame retardant property, good corrosion resistance, to make the fiber be more suitable for adverse circumstances, there is the great potential for being served in the fields such as high-performance composite materials reinforcement, ocean cable, optical cable reinforcing member.
Description
Technical field
The invention belongs to liquid crystal fiber and its preparation field, in particular to a kind of aromatic thermosetting liquid crystal fiber and its system
Preparation Method.
Background technique
In generation nineteen sixty, just researcher used low temperature poly condensation method, is prepared and is aligned as raw material using p-benzoyl chlorine
The complete fragrant amide polymer replaced, this complete fragrant amide polymer is a kind of liquid crystal polymer with excellent spinnability, this
It comes out it was found that facilitating Kevlar series fiber product such as, with high temperature resistant, high-strength, Gao Mo characteristic.But complete fragrant amide
Polymer needs to be dissolved in the concentrated sulfuric acid, and lysotropic liquid crystal is made and carries out solution-polymerized SBR, spinning technique is more complicated, exists simultaneously
The problem of solvent recovery, therefore the interest that Thermotropic Liquid Crystal Fibers cause various countries researcher bigger is (referring to document: Picken, S
J,Sikkema,D J,Boerstoel,H,Dingemans,T J,van der Zwaag,S,Liquid crystal main-
chain polymers for high-performance fibre applications[J].Liquid Crystals,
2011,38(11-12):1591-1605)。
Later period the 1970s people start to carry out basic research to Thermotropic Liquid Crystal Fibers, to the existing industry eighties
Metaplasia produces.Wherein the most successfully surely belong to the Vectra developed by Celanese company, the U.S.TMSerial Thermotropic Liquid Crystal Fibers.But
It is VectraTMSerial to belong to thermoplastic polymer with other Thermotropic Liquid Crystal Fibers, their glass transition temperature (Tg) is low
In 120 DEG C, it is caused to be restricted using temperature and application field.For example, 102443873 A of CN discloses a kind of aromatic series
Liquid crystalline copolyester fiber and preparation method thereof need to spin to make aromatic polyester macromolecule form the microfibrillar structure of high-sequential
It takes the stable heated inert gas containing nonionic substance to handle as-spun fibre after silk, passes through inorganic halide salt solution
Dipping pretreatment is heated, then is heat-treated.But this method can't improve its Tg, and the thermotropic liquid crystalline polyester fiber prepared is still fallen within
In the strand of straight configuration disorientation can occur for thermoplastic polymer at high temperature.102115597 A of CN discloses one kind
Including having the composite material for substrate of the inorganic filler of negative thermal expansion coefficient and liquid crystal thermosetting oligomer, takes and draw
Enter more rigid nanofiller and the purpose for improving liquid crystal polymer Tg is not implemented, simultaneously because nanofiller additive amount is usual
Higher (> 10vol%), brings difficulty to the processing and forming of liquid crystal polymer.Therefore, how not destroyed again while improving Tg
The problem of the processability of liquid crystal fiber or a pendulum in face of researcher.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of aromatic thermosetting liquid crystal fiber and preparation method thereof, gram
Taking prior art thermoplastic liquid crystal polymer Tg lower, easy disorientation, the high additive amount of nanofiller leads to the technology of poor in processability
Defect.The stiff backbone mesomorphic member of liquid crystal fiber of the invention contains ester bond, amido bond, imide bond or ether by AA, BB or AB type
Monomer of key or combinations thereof is constituted, and is blocked main chain using acetylene class, phenylacetylene class or silicon substrate acetylene class isoreactivity group, is passed through
Reactive liquid crystalline oligomer is made in one kettle way melt polycondensation reaction, and molecular weight passes through melt between 1000-10000 grams/mol
Thermosetting liquid crystal fiber is made in obtained reactive liquid crystalline oligomer by spin processes.
A kind of liquid crystal oligomer as shown in general formula I of the invention,
Wherein, X is that the monomer or combinations thereof by AA, BB or AB type containing ester bond, amido bond, imide bond or ehter bond is constituted
Liquid crystal backbone；Wherein E and E ' is independently selected from acetylene class, phenylacetylene class or silicon substrate acetylene class active group.
The E and E ' are independently selected from:
Wherein, Y is amino, imino group；Z is hydroxyl, carboxyl, ether or carbon-based；R, R ' and R " is independently selected from hydrogen, containing six
Or less carbon atom alkyl, the aryl containing the carbon atom less than ten, the low-carbon alkoxy containing six or less carbon atoms, contain
Low-carbon aryloxy group, fluorine, chlorine, the bromine or iodine of ten or less carbon atoms.
The X is selected from:
Further, liquid crystal oligomer main chain only has one or more structural repeat units composition of benzene ring system.
The Ar1、Ar2It is independently chosen from:
The liquid crystal oligomer is chosen in particular from:
Wherein n=2~
20；
Its
Middle n=2~20；
Wherein n
=3~30；
Wherein n
=1~12；
Wherein n
=2~20；
Its
Middle n=2~20；
Wherein n=1~12.
The molecular weight ranges of the oligomer are at 1000~10000 grams/mol.
A kind of one kettle way of the invention prepares the preparation method of liquid crystal oligomer, comprising:
Reaction monomers, active end group and acetic anhydride solvent are added in reactor simultaneously, under inert gas protection, instead
It answers temperature by being heated to 300~320 DEG C under the conditions of 140~150 DEG C, inert gas is then switched into vacuum, and keep
10~30 minutes, cooling, grinding, solid state condensation reacts to get liquid crystal oligomer.
The preferred embodiment of above-mentioned preparation method is as follows:
The reactant monomer be AA, BB or AB type containing ester bond, amido bond, imide bond, ehter bond monomer or they
Any combination.
The feed ratio of the monomer and active end group are as follows: according to predetermined oligomer molecules amount, pass through Carothers formula
(referring to document: Carothers, W H, Polymerization [J] .Chemical Reviews, 1931,8 (3): 353-426)
Calculate the feed ratio of monomer and active end group, it may be assumed that
Macromolecular sum=structural unit number * the degree of polymerization
The heating ramp rate is 0.5~1.5 DEG C/min；The temperature of solid state condensation reaction is 200~280 DEG C, the time
It is 12~48 hours.
A kind of liquid crystal fiber of the invention, by one or more of described liquid crystal oligomer, by precuring, melting is spun
Silk, post-processing are made.
The precuring is precuring 5~60 minutes under conditions of 300~370 DEG C；Melt-spinning technology parameter are as follows: liquid crystal
One or more of oligomer melt spinning is shaped to as-spun fibre in the distance apart from 5~50cm of spinning nozzle by stablizing
Atmosphere keep the temperature at 200~300 DEG C, and pressure cooling is carried out in the distance apart from 50~550cm of spinning nozzle
To 15~28 DEG C；Post-processing: it is completed under the conditions of 300~350 DEG C.
A kind of application of liquid crystal fiber of the invention.
Beneficial effect
1, present invention design has synthesized a kind of liquid crystal blocked by acetylene class, phenylacetylene class or silicon substrate acetylene class active group
Oligomer, molecular weight is controllable, has lower melting (liquid crystal phase transition) temperature than corresponding uncapped high molecular weight homologue
Degree, melt viscosity and superior processing performance；
2, in general, the heat cure of reactive model compound is carried out at a high temperature of being enough to cause main chain crosslinking.So
And main chain crosslinking usually makes the product brittle after solidifying.But in the present invention, acetylene class, phenylacetylene class or silicon substrate acetylene class are living
Property end group between reaction can lower than cause that liquid crystal oligomer backbone is obviously crosslinked at a temperature of carry out.
3, liquid crystal oligomer produced by the present invention, which is melted, processes and is spun into fiber, due to foring cross-linked network in system
The Tg of structure, liquid crystal fiber is significantly improved, to expand the application range of liquid crystal fiber.
4, liquid crystal oligomer produced by the present invention itself is free of any solvent, also gives birth to without any small molecule in solidification process
At, during ontology melt spinning be not necessarily to desolventizing, washing, the drying and other steps of existing spinning technique are eliminated, so that fine
It is easier, efficient, environmentally friendly to tie up preparation process；
5, fiber polymer chain of the invention is in the rigid chain stretched, forms the microfibrillar structure of high-sequential, and intermolecular
There are stronger interactions, to impart the very high intensity of fiber, are formed by after acetylenic active end group heat cure reaction
There is network structure excellent flame retardant property, good corrosion resistance to have so that the fiber be made to be more suitable for adverse circumstances
It is served in the great potential in the fields such as high-performance composite materials reinforcement, ocean cable, optical cable reinforcing member.
Detailed description of the invention
Fig. 1 is the embodiment of the present invention 1 and aromatic series thermotropic liquor polyester oligoamide and high polymer that comparative example 1 provides
Synthetic reaction flow diagram；
Fig. 2 is the PLM with heating stage microphoto of 1 aromatic series thermotropic liquid crystal oligomer of the present embodiment；
Fig. 3 is the PLM with heating stage microphoto of the 1 uncapped high polymer of aromatic series thermotropic liquid crystal of this comparative example；
Fig. 4 is the SEM figure of the aromatic thermosetting Thermotropic Liquid Crystal Fibers of the present embodiment 1；
Fig. 5 is the SEM figure of 1 aromatic thermoplastic Thermotropic Liquid Crystal Fibers of this comparative example；
Fig. 6 is aromatic thermosetting in the present embodiment 1 and comparative example 1 and thermoplasticity Thermotropic Liquid Crystal Fibers dynamic force credits
Analyse (DMTA) storage modulus (E ') curve；
Fig. 7 is aromatic thermosetting in the present embodiment 1 and comparative example 1 and thermoplasticity Thermotropic Liquid Crystal Fibers dynamic force credits
Analyse (DMTA) loss modulus (E ") curve；
Fig. 8 be aromatic series thermotropic liquor polyester amide, polyester oligomer and comparative example 1 that the present embodiment 1,3,4 provides
Differential scanning calorimetry (DSC) curve of the aromatic series thermotropic liquor polyester amide high polymer powder sample of offer；
Fig. 9 is aromatic series thermotropic liquor polyester amide, polyester oligomer and the comparative example 1 that the embodiment of the present invention 1,4 provides
The aromatic series thermotropic liquor polyester amide high polymer powder sample of offer is bent in 330 DEG C of constant temperature 80 minutes complex viscosities-time
Line chart；
Figure 10 is the process that liquid crystal fiber is made by melt spinning for 1 aromatic series thermotropic liquid crystal oligomer of the embodiment of the present invention
Figure.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
The test method of inherent viscosity in embodiment: in 1-7 of the embodiment of the present invention and comparative example 1, aromatic series is thermotropic
Liquid crystal polymer or oligomer are dissolved in Pentafluorophenol, are made into the solution of 0.5g/dL, at 60 DEG C, are surveyed using Ubbelohde viscometer method
.
In 1-7 of the embodiment of the present invention and comparative example 1, used raw material is purchased from the limited public affairs of Shanghai lark prestige chemical technology
Department, 100g/ bottles, purity > 98%.
Embodiment 1
1, the preparation of aromatic series thermotropic liquor polyester oligoamide
In 250 milliliters of three neck round bottom flask be added 4.15g terephthalic acid (TPA), 47.05g 2,6- naphthalenediol,
5.86g 3- amino phenylacetylene, 50ml acetic anhydride and 4mg potassium acetate.Flask is equipped with seal glass dasher, a nitrogen
Inlet tube and a heat preservation still head.It is passed through moderate nitrogen stream, is heated reaction mixture 4 hours in drift sand bath, reaction
Temperature rises to 310 DEG C by 140 DEG C.At this point, reaction system is slowly evacuated, and kept for 30 minutes.Opaque is molten
Body is cooled to room temperature, and by product by removing in flask, and is ground to fine powder.The solid state condensation in vacuum drying oven at 250 DEG C
To get a kind of aromatic series thermotropic liquor polyester oligoamide (inherent viscosity=0.5dL/g) is arrived, melting is contracted within 24 hours for reaction
Poly- reaction process is shown in Fig. 1 Route B.
2, the preparation of aromatic series thermotropic liquor polyester nylon
By liquid crystal oligomer obtained put into Small-size Twin-Screw Extruders extruder in, 300 DEG C precuring 30 minutes.Melt is from spray
Silk head forms melt stream after spraying, and the air set molding below spinning head, and as-spun fibre is apart from spinning nozzle
Pass through one section of stable nitrogen atmosphere in the distance of 25cm, is heated by outside, the temperature of the atmosphere is made to be maintained at 300
DEG C, and carry out forcing to be cooled to 25 DEG C in the distance apart from spinning nozzle 50cm.Speed of wrap is 100m/ minutes, jet stretch
Than being 5.A kind of aromatic thermosetting thermotropic liquor polyester amide is made finally by post-processing 20 minutes under the conditions of 350 DEG C
Fiber.
Comparative example 1
1, the preparation of aromatic series thermotropic liquor polyester amide high polymer
4.15g terephthalic acid (TPA), 47.05g 2,6- naphthalenediol, 50ml are added in 250 milliliters of three neck round bottom flask
Acetic anhydride and 4mg potassium acetate.Flask is equipped with seal glass dasher, a nitrogen inlet tube and a heat preservation still head.
It is passed through moderate nitrogen stream, is heated reaction mixture 4 hours in drift sand bath, reaction temperature rises to 310 DEG C by 140 DEG C.
At this point, reaction system is slowly evacuated, and kept for 30 minutes.Opaque melt is cooled to room temperature, by product by burning
It is removed in bottle, and is ground to fine powder.Solid state condensation reacts 24 hours to get a kind of virtue is arrived in vacuum drying oven at 250 DEG C
The uncapped polyesteramide high polymer of fragrant race's thermotropic liquid crystal (inherent viscosity=0.95dL/g), melt polycondensation reaction process is shown in figure
1Route A。
2, the preparation of aromatic series thermotropic liquor polyester nylon
Liquid crystal high polymers obtained are put into Small-size Twin-Screw Extruders extruder, 300 DEG C is maintained at and is formed homogeneously for about 10 minutes
Melt forms melt stream after spinning head ejection, and the air set molding below spinning head, and as-spun fibre is in distance
Pass through one section of stable nitrogen atmosphere in the distance of spinning nozzle 25cm, is heated by outside, keep the temperature of the atmosphere
At 300 DEG C, and carry out forcing to be cooled to 25 DEG C in the distance apart from spinning nozzle 50cm.Speed of wrap is 100m/ minutes, spray head
Draw ratio is 5.A kind of aromatic thermoplastic thermotropic liquor polyester is made finally by post-processing 20 minutes under the conditions of 350 DEG C
Nylon.
Embodiment 1 provided by the invention and the synthesis of 1 aromatic series thermotropic liquor polyester oligoamide of comparative example and high polymer
Schematic diagram is reacted, as shown in Figure 1, the reaction is high-temperature fusion polycondensation reaction.
Thermal station polarisation of the 1 aromatic series thermotropic liquor polyester oligoamide of embodiment provided by the invention at 300 DEG C is aobvious
Micro mirror microphoto has good mobility as shown in Fig. 2, it is rendered as typical nematic liquid crystal schlieren texture.
Thermal station polarisation of the 1 aromatic series thermotropic liquor polyester amide high polymer of comparative example provided by the invention at 300 DEG C is aobvious
Micro mirror microphoto, as shown in figure 3, it equally shows typical nematic liquid crystal schlieren texture and good mobility.
The SEM of aromatic thermosetting thermotropic liquor polyester nylon made from embodiment 1 provided by the invention schemes, and such as schemes
Shown in 4, it can be seen that fiber size is uniform, and diameter is about 0.8~1 μm.
The SEM of aromatic thermoplastic thermotropic liquor polyester nylon made from comparative example 1 provided by the invention schemes, and such as schemes
Shown in 5, it can be seen that fiber size uniformity is more slightly worse than embodiment, and diameter is about 0.2~1 μm, illustrates 1 polyesteramide of embodiment
Oligomer has more preferably stability of spinning process.
The energy storage mould of aromatic series thermotropic liquor polyester nylon made from comparative example 1 provided by the invention and embodiment 1
Curve comparison figure is measured, as shown in Figure 6.Their storage modulus is 6GPa at 25 DEG C.1 storage modulus of comparative example is with temperature liter
Height decline is obvious, especially when reaching its crystalline state-liquid crystal state transition temperature T(K-N)When, storage modulus, which glides rapidly, causes sample disconnected
It splits.Embodiment 1 has more stable storage modulus variation with temperature relationship, when temperature is lower than its glass transition temperature (Tg)
When storage modulus be held essentially constant；When temperature is higher than Tg, sample enters rubbery state, and storage modulus remains at 100Mpa,
This is because in thermosetting property thermotropic liquor polyester nylon, there are cross-linked network structures.
The loss mould of aromatic series thermotropic liquor polyester nylon made from comparative example 1 provided by the invention and embodiment 1
Curve comparison figure is measured, as shown in fig. 7, the peak value of loss modulus curve is defined as the Tg of fiber by the present invention.The former (comparative example 1)
Tg be about 110 DEG C, and the latter's (embodiment 1), due to the presence of cross-linked network structure, Tg is up to 240 DEG C.Although CN
Its Tg value, but the thermotropic liquid crystal polymer in 102443873 A of CN is not disclosed in 102443873 A and 102115597 A of CN
With VectraTMSeries is identical, their Tg value is below 120 DEG C；And from 102115597 A thermal expansion coefficient test curve of CN
In known to the Tg value of its each sample be below 200 DEG C, it is seen that the present invention overcomes prior art thermoplastic liquid crystal polymer Tg compared with
Low technological deficiency.
It is above-mentioned statistics indicate that, aromatic thermosetting Thermotropic Liquid Crystal Fibers disclosed by the invention overcome existing aromatic series thermoplastic
Property Thermotropic Liquid Crystal Fibers present in the low disadvantage of Tg, and there is good stability of spinning process and fiber size uniformity.
Embodiment 2
1, the preparation of aromatic series thermotropic liquor polyester oligomer
4.15g terephthalic acid (TPA), 37.24g 4,4'- dihydroxy connection are added in 250 milliliters of three neck round bottom flask
Benzene, 5.86g 3- amino phenylacetylene, 50ml acetic anhydride and 5mg sodium acetate.Flask is equipped with seal glass dasher, a nitrogen
Gas inlet tube and a heat preservation still head.It is passed through moderate nitrogen stream, by reaction mixture heating 5 hours in drift sand bath, instead
Temperature is answered to rise to 320 DEG C by 140 DEG C.At this point, reaction system is slowly evacuated, and kept for 30 minutes.Opaque
Melt is cooled to room temperature, and by product by removing in flask, and is ground to fine powder.Solid-state contracts in vacuum drying oven at 260 DEG C
It is poly- to react 24 hours to get a kind of aromatic series thermotropic liquor polyester oligomer (inherent viscosity=0.65dL/g) is arrived.
2, the preparation of aromatic series thermotropic liquor polyester fiber
By liquid crystal oligomer obtained put into Small-size Twin-Screw Extruders extruder in, 310 DEG C precuring 30 minutes.Melt is from spray
Silk head forms melt stream after spraying, and the air set molding below spinning head, and as-spun fibre is apart from spinning nozzle
Pass through one section of stable nitrogen atmosphere in the distance of 45cm, is heated by outside, the temperature of the atmosphere is made to be maintained at 200
DEG C, and carry out forcing to be cooled to 15 DEG C in the distance apart from spinning nozzle 550cm.Speed of wrap is 200m/ minutes, jet stretch
Than being 6.It is fine that a kind of aromatic thermosetting thermotropic liquor polyester is made finally by post-processing 60 minutes under the conditions of 300 DEG C
Dimension.
Embodiment 3
1, the preparation of aromatic series thermotropic liquor polyester oligomer
100.83g 4- P-hydroxybenzoic acid, 50.80g 6- acetic acid are added in 500 milliliters of three neck round bottom flask
Base -2- naphthoic acid, 10.14g N- (4- carboxyl phenyl) -4- phenylacetylene base phthalic acid imides, 10.53g N- (4- acetic acid
Phenol ester group) -4- phenylacetylene base phthalic acid imides, 150ml acetic anhydride and 10mg potassium acetate.Flask is equipped with seal glass
Dasher, a nitrogen inlet tube and a heat preservation still head.It is passed through moderate nitrogen stream, it is in drift sand bath that reaction is mixed
It closes object to heat 4 hours, reaction temperature rises to 310 DEG C by 150 DEG C.At this point, reaction system is slowly evacuated, and keep
30 minutes.Opaque melt is cooled to room temperature, and by product by removing in flask, and is ground to fine powder.It is true at 250 DEG C
In empty baking oven solid state condensation react 24 hours to get to a kind of aromatic series thermotropic liquor polyester oligomer (inherent viscosity=
0.55dL/g)。
2, the preparation of aromatic series thermotropic liquor polyester fiber
By liquid crystal oligomer obtained put into Small-size Twin-Screw Extruders extruder in, 350 DEG C precuring 5 minutes.Melt is from spray
Silk head forms melt stream after spraying, and the air set molding below spinning head, and as-spun fibre is apart from spinning nozzle
Pass through one section of stable nitrogen atmosphere in the distance of 50cm, is heated by outside, the temperature of the atmosphere is made to be maintained at 300
DEG C, and carry out forcing to be cooled to 28 DEG C in the distance apart from spinning nozzle 50cm.Speed of wrap is 1000m/ minutes, jet stretch
Than being 15.It is fine that a kind of aromatic thermosetting thermotropic liquor polyester is made finally by post-processing 40 minutes under the conditions of 320 DEG C
Dimension.
Embodiment 4
1, the preparation of aromatic series thermotropic liquor polyester oligomer
In 250 milliliters of three neck round bottom flask be added 16.61g terephthalic acid (TPA), 16.61g M-phthalic acid,
82.87g 4- P-hydroxybenzoic acid, 37.24g 4,4' dihydroxy diphenyl, 2.52g N- (4- carboxyl phenyl) -4- phenylacetylene base
Phthalic acid imides, 2.61g N- (4- acetoxyphenyl base) -4- phenylacetylene base phthalic acid imides, 130ml second
Acid anhydrides and 5mg sodium acetate.Flask is equipped with seal glass dasher, a nitrogen inlet tube and a heat preservation still head.It is logical
Enter moderate nitrogen stream, is heated beyond reaction mixture 6 hours in drift sand bath, reaction temperature rises to 300 by 145 DEG C
℃.At this point, reaction system is slowly evacuated, and kept for 30 minutes.Opaque melt is cooled to room temperature, by product by
It is removed in flask, and is ground to fine powder.Solid state condensation reacts 24 hours to get one kind is arrived in vacuum drying oven at 270 DEG C
Aromatic series thermotropic liquor polyester oligomer (inherent viscosity=0.75dL/g).
2, the preparation of aromatic series thermotropic liquor polyester fiber
By liquid crystal oligomer obtained put into Small-size Twin-Screw Extruders extruder in, 310 DEG C precuring 30 minutes.Melt is from spray
Silk head forms melt stream after spraying, and the air set molding below spinning head, and as-spun fibre is apart from spinning nozzle
Pass through one section of stable nitrogen atmosphere in the distance of 45cm, is heated by outside, the temperature of the atmosphere is made to be maintained at 200
DEG C, and carry out forcing to be cooled to 15 DEG C in the distance apart from spinning nozzle 550cm.Speed of wrap is 200m/ minutes, jet stretch
Than being 12.It is fine that a kind of aromatic thermosetting thermotropic liquor polyester is made finally by post-processing 60 minutes under the conditions of 300 DEG C
Dimension.
Referring to attached drawing 8, it is that the aromatic series thermotropic liquor polyester amide that embodiment 1,3,4 provides in the present invention, polyester are low
The DSC curve for the aromatic series thermotropic liquor polyester amide high polymer powder sample that polymers and comparative example 1 provide.It can therefrom see
Out, the fusing point of aromatic series thermotropic liquor polyester amide made from comparative example 1 is about 330 DEG C, and fragrance made from embodiment 1,3,4
The fusing point of race's thermotropic liquor polyester amide and polyester oligomer significantly reduces, and melts peak area and be obviously reduced, this is because not
The symmetry of strand is destroyed with the addition of type aromatic monomer (amide) or unsymmetric structure monomer (M-phthalic acid),
The crystallinity of polymer is greatly reduced, introduces more amorphous phases for system.The introducing of aryne active end group shortens molecule
Chain length significantly reduces melting (liquid crystal phase transition), improves processability.
Referring to attached drawing 9, it is the aromatic series thermotropic liquor polyester amide that embodiment 1,4 provides in the present invention, polyester oligomeric
The aromatic series thermotropic liquor polyester amide high polymer powder sample that object and comparative example 1 provide is in 330 DEG C of constant temperature 80 minutes compound
Viscosity profile over time.As seen from the figure, aromatic series thermotropic liquor polyester amide made from comparative example 1 330 DEG C constant temperature 25 minutes,
Viscosity rises after there is slightly decline, causes molecular weight to increase this is because further polycondensation reaction occurs in this temperature in it
Greatly.Aromatic series thermotropic liquor polyester amide made from embodiment 1 and 4 and polyester oligomer are opened in 330 DEG C of initial phase viscosity
Begin to decline, and its minimal viscosity value is the 1/15~1/10 of 1 minimal viscosity value of comparative example, this mainly has benefited from aryne active end group
Introducing shorten molecular chain length.Although aromatic series thermotropic liquor polyester amide and polyester oligomer made from embodiment 1 and 4
It was then the viscosity because the curing reaction that crosslinks of aryne active end group causes molecular weight to increase at 330 DEG C constant temperature 30 minutes
It begins to ramp up, but such melting window is enough to complete machine-shaping.
Referring to attached drawing 10, it is 1 aromatic series thermotropic liquid crystal oligomer of the embodiment of the present invention by the obtained liquid crystal of melt spinning
The flow chart of fiber.
Embodiment 5
1, the preparation of aromatic series thermotropic liquor polyester oligoamide
41.53g terephthalic acid (TPA), 37.79g 4- acetamido benzene are added in 250 milliliters of three neck round bottom flask
Phenol, 94.09g6- acetate -2- naphthoic acid, 2.20g N- (4- carboxyl phenyl) -4- phenylacetylene base phthalic acid imides,
2.29g N- (4- acetoxyphenyl base) -4- phenylacetylene base phthalic acid imides, 105ml acetic anhydride and 5mg sodium acetate.It burns
Bottle is equipped with seal glass dasher, a nitrogen inlet tube and a heat preservation still head.It is passed through moderate nitrogen stream, is being flowed
Reaction mixture is heated 3 hours in sand-bath, reaction temperature rises to 300 DEG C by 150 DEG C.At this point, slowly by reaction system
It is evacuated, and is kept for 25 minutes.Opaque melt is cooled to room temperature, and by product by removing in flask, and is ground to fine
Powder.Solid state condensation reacts 48 hours to get low to a kind of aromatic series thermotropic liquor polyester amide in vacuum drying oven at 230 DEG C
Polymers (inherent viscosity=0.64dL/g).
2, liquid crystal oligomer obtained investment Small-size Twin-Screw Extruders are squeezed in the preparation of aromatic series thermotropic liquor polyester nylon
Out in machine, 390 DEG C precuring 5 minutes.Melt forms melt stream after spinning head ejection, and the air below spinning head
Middle curing molding, as-spun fibre pass through one section of stable nitrogen atmosphere in the distance apart from spinning nozzle 45cm, are added by outside
Heat makes the temperature of the atmosphere be maintained at 200 DEG C, and carries out forcing to be cooled to 15 in the distance apart from spinning nozzle 250cm
℃.Speed of wrap is 400m/ minutes, jet stretch ratio 5.It is made finally by post-processing 40 minutes under the conditions of 300 DEG C
A kind of aromatic thermosetting thermotropic polyesters amide liquid crystal fiber.
Embodiment 6
1, the preparation of aromatic series thermotropic liquor polyester imide oligomer
In 250 milliliters of three neck round bottom flask be added 20.66g N- (3'- phenylol) trimellitimide,
23.51g 4- P-hydroxybenzoic acid, 16.94g 6- acetyl group -2- naphthoic acid, 4.19g N- (4- carboxyl phenyl)-dimethyl-silicon -
1,4- tolans, 4.347g N- (4- acetoxyphenyl base)-dimethyl-silicon -1,4- tolans, 130ml acetic anhydride and 6mg
Sodium acetate.Flask is equipped with seal glass dasher, a nitrogen inlet tube and a heat preservation still head.It is passed through moderate nitrogen
Air-flow heats reaction mixture 6 hours in drift sand bath, and reaction temperature rises to 300 DEG C by 143 DEG C.At this point, by reactant
System is slowly evacuated, and is kept for 30 minutes.Opaque melt is cooled to room temperature, and by product by removing in flask, and is ground
Mill is fine powder.Solid state condensation reacts 48 hours to get poly- to a kind of aromatic series thermotropic liquid crystal in vacuum drying oven at 220 DEG C
Ester acid imide oligomer (inherent viscosity=0.76dL/g).
2, the preparation of aromatic series thermotropic liquor polyester imide fiber
By liquid crystal oligomer obtained put into Small-size Twin-Screw Extruders extruder in, 310 DEG C precuring 35 minutes.Melt is from spray
Silk head forms melt stream after spraying, and the air set molding below spinning head, and as-spun fibre is apart from spinning nozzle
Pass through one section of stable nitrogen atmosphere in the distance of 35cm, is heated by outside, the temperature of the atmosphere is made to be maintained at 250
DEG C, and carry out forcing to be cooled to 20 DEG C in the distance apart from spinning nozzle 550cm.Speed of wrap is 600m/ minutes, jet stretch
Than being 10.A kind of aromatic thermosetting thermotropic liquor polyester acyl is made finally by post-processing 60 minutes under the conditions of 300 DEG C
Imine fiber.
Embodiment 7
1, the preparation of aromatic series thermotropic liquor polyester ether oligomer
In 500 milliliters of three neck round bottom flask be added 18.27g terephthalic acid (TPA), 18.27g M-phthalic acid,
91.16g 4- P-hydroxybenzoic acid, 44.47g 4,4'- dihydroxy diphenyl ether, 2.77g N- (4- carboxyl phenyl) -4- phenylacetylene
Base phthalic acid imides, 2.87g N- (4- acetoxyphenyl base) -4- phenylacetylene base phthalic acid imides, 140ml
Acetic anhydride and 5mg sodium acetate.Flask is equipped with seal glass dasher, a nitrogen inlet tube and a heat preservation still head.
It is passed through moderate nitrogen stream, is heated reaction mixture 6 hours in drift sand bath, reaction temperature rises to 320 DEG C by 140 DEG C.
At this point, reaction system is slowly evacuated, and kept for 25 minutes.Opaque melt is cooled to room temperature, by product by burning
It is removed in bottle, and is ground to fine powder.Solid state condensation reacts 24 hours to get a kind of virtue is arrived in vacuum drying oven at 260 DEG C
Fragrant race's thermotropic liquor polyester ether oligomer (inherent viscosity=0.82dL/g).
2, the preparation of aromatic series thermotropic liquor polyester ether fiber
By liquid crystal oligomer obtained put into Small-size Twin-Screw Extruders extruder in, 310 DEG C precuring 30 minutes.Melt is from spray
Silk head forms melt stream after spraying, and the air set molding below spinning head, and as-spun fibre is apart from spinning nozzle
Pass through one section of stable nitrogen atmosphere in the distance of 45cm, is heated by outside, the temperature of the atmosphere is made to be maintained at 200
DEG C, and carry out forcing to be cooled to 15 DEG C in the distance apart from spinning nozzle 250cm.Speed of wrap is 300m/ minutes, jet stretch
Than being 15.A kind of aromatic thermosetting thermotropic liquor polyester ether is made finally by post-processing 60 minutes under the conditions of 300 DEG C
Fiber.
Referring to table 1, it is that aromatic series thermotropic liquor polyester amide, polyester, polyester acyl that 1-7 of the embodiment of the present invention is provided are sub-
Mechanics, the fire-retardant, corrosion resistance for the aromatic series thermotropic liquor polyester nylon that amine, polyester ether fiber and comparative example 1 provide
As a result.
As can be seen from the table, the mechanics for all kinds of aromatic thermosetting fibers that embodiment 1-7 is provided, flame retardant property are excellent
In the aromatic thermoplastic fiber that comparative example 1 provides；Embodiment 1,5,6 provide all kinds of aromatic thermosetting fibers it is corrosion-resistant
Property be superior to comparative example 1 offer aromatic thermoplastic fiber.Because thermosetting fibre macromolecular chain is in the rigid chain stretched, shape
At the microfibrillar structure of high-sequential, retained in the curing process, and it is intermolecular there are stronger interactions, to assign
Fiber very high intensity.Meanwhile be formed by after acetylenic active end group heat cure reaction network structure have it is excellent fire-retardant
Property and corrosion resistance.The undisclosed fire-retardant and corrosion resistance of 102115597 A of CN 102443873 A and CN, in mechanical property
Energy aspect, the polyester fiber that 102443873 A of CN is provided have the aromatic series thermotropic liquid crystal provided with 1-7 of the embodiment of the present invention
Polyesteramide, polyester, polyesterimide, the comparable breaking strength of polyester ether fiber (12.9~19.6cN/dtex).It is overall next
It sees, aromatic series thermotropic liquor polyester amide, polyester, polyesterimide, the polyester ether fiber of 1-7 of embodiment of the present invention offer have
More preferably comprehensive performance.
Aromatic series thermotropic liquor polyester amide, the polyester, polyesterimide, polyester of 1. 1-7 of the embodiment of the present invention of table offer
The mechanics for the aromatic series thermotropic liquor polyester nylon that ether fiber and comparative example 1 provide, fire-retardant, corrosion resistance result:
aThe measurement of GB/T 3923.1-1997 textile, fabric tension performance, ultimate strength and elongation at break: it is pressing from both sides
It clamps center and clamps sample, to guarantee midpoint of the center of drag line by clamp.Start tester, makes moveable clamper
Mobile, tensile sample takes off to disconnected.Ultimate strength is recorded, unit is newton (N)；Record extension at break or elongation at break, unit
Millimeter (mm) or percentage (%).Each direction at least 5 samples of sample.It is strong to calculate separately the fracture through broadwise (or vertically and horizontally)
The average value of power and elongation at break；Wherein tensile speed 1.0mm/min.
bGB/T5454-1997 textile combustion performance test oxygen index method: sample is placed under vertical experiment condition, In
In the oxygen-nitrogen mixture stream flowed up, sample upper end is lighted, observes its combustion characteristics, and it is continuous compared with defined limiting value
Fire time or char length；By the test of samples a series of in different oxygen concentrations, sample can be measured and just maintain to burn
Required minimum oxygen concentration, i.e. limit oxygen index (LOI%).To have 40%~60% in test specimens is more than defined afterflame and yin
Fire time or char length；Wherein fiber sample length 15cm.
cIt there is no national standard that can test using solvent soaking method for reference: dry sample being weighed and records quality at present
M1, be separately immersed in acid (sulfuric acid, nitric acid, hydrochloric acid, acetic acid etc.), alkaline (sodium hydroxide solution etc.), oiliness (gasoline, diesel oil,
Kerosene etc.) 24 hours in solvent, takes out sample and simultaneously remove solvent, quality m2 is weighed and record after dry again, before calculating test
△ m=m1-m2 of poor quality afterwards successively judges the corrosion resistance of sample.
Claims (11)
1. a kind of liquid crystal oligomer as shown in general formula I,
Wherein, X is the liquid crystal that the monomer or combinations thereof by AA, BB or AB type containing ester bond, amido bond, imide bond or ehter bond is constituted
Main chain；Wherein E and E ' is independently selected from acetylene class, phenylacetylene class or silicon substrate acetylene class active group.
2. liquid crystal oligomer according to claim 1, which is characterized in that the E and E ' are independently selected from:
Wherein, Y is amino, imino group；Z is hydroxyl, carboxyl, ether or carbon-based；R, R ' and R " is independently selected from hydrogen, containing six or more
The alkyl of few carbon atom, the low-carbon alkoxy containing six or less carbon atoms, contains ten at the aryl containing the carbon atom less than ten
Or low-carbon aryloxy group, fluorine, chlorine, the bromine or iodine of less carbon atom.
3. oligomer according to claim 1, which is characterized in that the X is selected from:
4. oligomer according to claim 3, which is characterized in that the Ar1、Ar2It is independently chosen from:
5. oligomer according to claim 1, which is characterized in that described to be chosen in particular from:
Wherein n=2~20；
Wherein n=
2~20；
Wherein n=3~30；
Wherein n=1~
12；
Its
Middle n=2~20；
Wherein n=2~20；
Its
Middle n=1~12.
6. oligomer according to claim 1, which is characterized in that the molecular weight ranges of the oligomer are 1000~10000
Gram/mol.
7. a kind of preparation method of liquid crystal oligomer, comprising:
Reaction monomers, active end group and acetic anhydride solvent are added in reactor simultaneously, under inert gas protection, reaction temperature
Degree is heated to 300~320 DEG C by 140~150 DEG C of conditions, inert gas is then switched to vacuum, and keep 10~30
Minute, cooling, grinding, solid state condensation reacts to get liquid crystal oligomer.
8. preparation method according to claim 7, which is characterized in that the heating ramp rate is 0.5~1.5 DEG C/min；
The temperature of solid state condensation reaction is 200~280 DEG C, and the time is 12~48 hours.
9. a kind of liquid crystal fiber, which is characterized in that by one or more of liquid crystal oligomer described in claim 1, by pre-
Solidification, melt spinning, post-processing are made.
10. liquid crystal fiber according to claim 9, which is characterized in that the precuring is pre- under conditions of being 300~370 DEG C
Solidification 5~60 minutes；Melt-spinning technology parameter are as follows: one or more of liquid crystal oligomer melt spinning is shaped to nascent fibre
Dimension is keeping the temperature at 200~300 DEG C by stable atmosphere apart from interior apart from 5~50cm of spinning nozzle, and in distance
It carries out forcing to be cooled to 15~28 DEG C in the distance of 50~550cm of spinning nozzle；Post-processing: it is completed under the conditions of 300~350 DEG C.
11. a kind of application of liquid crystal fiber described in claim 9.
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| CN115490629A (en) | 2022-12-20 |
| CN115322135A (en) | 2022-11-11 |
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