CN108085771A - A kind of spinning technique of thermotropic liquid crystalline polyester fiber - Google Patents
A kind of spinning technique of thermotropic liquid crystalline polyester fiber Download PDFInfo
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- CN108085771A CN108085771A CN201711337994.6A CN201711337994A CN108085771A CN 108085771 A CN108085771 A CN 108085771A CN 201711337994 A CN201711337994 A CN 201711337994A CN 108085771 A CN108085771 A CN 108085771A
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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
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
Abstract
The invention discloses a kind of spinning techniques of thermotropic liquid crystalline polyester fiber, it uses technique to be pre-processed for the polyester resin of solid phase, it vacuumizes, screw extruder melting, melt metering pump, forced filtration, spinning pack, strand crystallisation by cooling, winding doffing produce spun filament, spun filament is heat-treated, and obtains the thermotropic liquid crystalline polyester fiber containing nanometer-sized inorganic oxide powder.The product macromolecule of the present invention is the aromatic polyester using solid phase polycondensation synthesis, make the linear rigid chain of polyester macromolecule chain of solid phase simultaneously, in spun filament after high-temperature heat treatment, intrastitial thermotropic liquid crystalline polyester strand is in high-sequential arrangement architecture, and it is intermolecular there are stronger interaction, especially after suitably nanometer materials are mixed into, improving the elastic strength and modulus of fiber, and then the special performance characteristic of fiber is imparted, fiber is made to be more suitable for adverse circumstances.
Description
Technical field
The invention belongs to high-performance fiber production technical fields, are related to a kind of based on thermotropic on the basis of petchem
The spinning technique of liquid crystal fiber, more particularly to a kind of spinning technique of the thermotropic liquid crystalline polyester fiber of solid phase.
Technical background
In the early 1960s, du pont company is raw material through low-temperature polycondensation with p-benzoyl chlorine, contraposition is prepared
The complete fragrant amide polymer of substitution（PAB）, while find that PAB can generate the liquid crystal polymer with excellent spinnability, this hair
Now so that the high mould lysotropic liquid crystal fiber product of high-temperature-resistant high comes out, such as kevlar range of commercial products.But lysotropic liquid crystal fiber because
Using solution-polymerized SBR, spinning technique is more complicated, the problem of existing simultaneously solvent recovery.Therefore Thermotropic Liquid Crystal Fibers cause various countries
The interest of researcher's bigger.
The polyester and long filament of solid phase are disclosed in 13-43473494, essentially describes high molecular building-up process, is closed
It is the threadiness that fineness is 0.5tex then to be described only melt drawn under inert gas shielding in the preparation of long filament, heat treatment
Technique is 2h at 200 DEG C, is elaborated in 7h at 200 304 DEG C, US 4503005A in 250 450 DEG C, preferably 300 400
Melt spinning at DEG C is heat-treated 0.5 30h in the range of 100 350 DEG C.Solid phase is described in US-4743416A
The melt spinning process of polyester fiber, by controlling nozzle extrusion pressure in 3kg/fcm2Or more, come promote fiber have compared with
Good orientation assigns fiber higher intensity and modulus.Although above with respect to the polyester fiber preparation method of solid phase
Report very early, but is crystallized since the polyester of solid phase just generates in the molten state, and the melt cooling and solidifying time is especially
It is short so that make in a short time fiber have it is height-oriented be difficult, so using briefly above melt spinning be heat-treated work
Skill, it is impossible to obtain the ideal tensile strength that its rigid structure should possess.
In Chinese patent number：CN201110283218. describe in 9 a kind of aromatic copolyester liquid crystal fiber and its
Preparation method, preparation process include the processes such as pretreatment of raw material, drying, melt spinning and post processing.To nascent fibre after spinning
Dimension takes the stable heated inert gas containing nonionic substance to handle, and fiber is impregnated by the heating of inorganic halide salt solution
Pretreatment, then be heat-treated.
Due in the spinning process of liquid crystal fiber, it is necessary to certain finish, while because of the molecular weight of liquid-crystal polyester resin
Problem so that melt spun fibre may bond so that subsequent heat treatment of fiber becomes difficult, it is therefore desirable to handle fiber
The finish on surface, and then make technological process is opposite to lengthen, it is also desirable to be handled using other chemical substances, so as to increase
Production cost.
In Chinese patent：Liquid crystalline polyester fiber and its manufacturer are described in CN201280015765.1
Method is provided in the coated inorganic particle on strand as obtained by liquid crystal polyester melt spinning（A）With phosphoric acid based compound（B）,
Then the manufacturing method of the liquid crystalline polyester fiber of solid phase is carried out.The reticulated made of the liquid crystalline polyester fiber.Thus
It provides the deposit (scum silica frost) in weaving process less and the process small, in weaving process that changes of traveling tension passes through
Property and the excellent liquid crystalline polyester fiber of product yield and its manufacturing method, reticulated.The production technology stream of the fiber in fact
Cheng Zhong, fiber surface coating inorganic particulate for silica, mainly reduce between fiber strand silk and strand and spinning work
The caking property of the equipment such as the draw-off godet of skill flow, and then finished product rate is improved, however, coated inorganic particle is with improving product
It can be there is no direct relation.
In Chinese patent number：Polyphenylene sulfide as-spun fibre drafting forming technique is described in CN201110066323.7,
" V " font interlayer thermal treatment catheter of the polyphenylene sulfide as-spun fibre by the series connection of conduction oil heated at constant temperature is disposably stretched and determined
Type.Technological process poly-p-phenylene sulfide ether as-spun fibre using the present invention disposably stretches and sizing, not only shortens fiber and leads
Stretching process flow improves work efficiency the yield rate with drawn fiber, reduces production cost, heat setting temperature 180 ± 2
DEG C process conditions, but since liquid crystalline polyester fiber needs to be passed through nitrogen, argon gas, carbon dioxide gas during heat treatment
Body is protected, it is necessary to carry out necessary improvement to the annealing device.
The content of the invention
The object of the present invention is to provide a kind of spinning technique of thermotropic liquid crystalline polyester fiber, in the liquid crystal polyester using solid phase
On the basis of molecular resin amount is relatively large, a small amount of nanometer grade silica or titanium dioxide powder are suitably mixed into resin,
Under the situation for not influencing liquid crystalline polyester fiber spinning and heat treatment, the intensity of aromatic polyester liquid crystal fiber is not only increased,
But also the yield rate of fiber is improved, meanwhile, the treatment process process of fiber surface finish is omitted, and then reduces and is produced into
This.
The technical scheme is that：
The spinning technique of thermotropic liquid crystalline polyester fiber is pre-processed using the polyester resin of solid phase, vacuumized, screw extruder melts
Melting, melt metering pump, forced filtration, spinning pack, strand crystallisation by cooling, winding doffing produces spun filament, and spun filament is heat-treated,
Concrete technology condition includes：
（1）In the polyester resin of powdery solid phase add in 0.1~3%wt, grain size be 3~6nm nanometer grade silica or
Titanium dioxide powder is inserted in homogenizer, in stir speed (S.S.) under conditions of 2800~3300rpm, 36~48min of stirring it
Afterwards, single screw extrusion machine is inputted, under conditions of vacuumizing, by the solid polycondensation containing nanometer grade silica or titanium dioxide powder
The polyester resin extrusion of conjunction is cut into a length of 3~6mm, the resin slicer of a diameter of 1~2mm；
（2）By step（1）Obtained resin slicer inserts temperature as in 160~180 DEG C of vacuum drying ovens, vacuum degree for-
0.06-0.8Mpa, dry 38~48h；
（3）By step（2）The polyester resin for the solid phase containing nanometer grade silica or titanium dioxide powder being dried to obtain
Section is directly inputted in double screw extruder, is set respectively above the 3rd heating zone of extruder, the 6th heating zone and the 9th heating zone
The interface that vacuumizes of a diameter of 60mm is put, vacuum degree is-0.06-0.8Mpa, and double screw extruder melts resin
Temperature is 260~330 DEG C, and temperature setting is in Gaussian curve shape substantially, consolidating containing nanometer grade silica or titanium dioxide powder
The polyester resin melt of phase-polymerization input temp after double screw extruder squeezes out spins case for 310~330 DEG C of heat preservations, by keeping the temperature
Spin metering pump input 4~6 spinning packs of configuration configured on case, the solid phase containing nanometer grade silica or titanium dioxide powder
The polyester resin melt of polymerization at 80~380mm of lower section of spinneret, is blown into temperature after the spinneret of spinning pack sprays
For 6~16 DEG C of carbon dioxide, strand is made to crystallize cooling rapidly, strand after cooling directly inputs the strand closed reel of lower end, receives
It is rolled into the polyester fiber spun filament of the solid phase containing nanometer grade silica or titanium dioxide powder；Spinning rate therein is
800~1400m/min；Draft ratio is 3.6~4.8；The draw ratio of double screw extruder is 68：1；Double screw extruder it is each
Heating region temperature setting：First 60~80 DEG C of area, 260~275 DEG C of the secondth area, 275~290 DEG C of the 3rd area, the 4th area 295~
305 DEG C, 310~315 DEG C of the 5th area, 325~330 DEG C of the 6th area, 325~330 DEG C of District 7,315~320 DEG C of Section Eight,
Nine 300~310 DEG C of areas, 290~305 DEG C of the tenth area, 290~300 DEG C of the 11st area, 290~300 DEG C of No.12 District；
（4）By step（3）Obtained spun filament inserts series connection interlayer thermal treatment catheter, and length is 2x800mm and V-shaped company
It connects, interlayer thermal treatment catheter internal diameter is 60~80mm, installs the draw-off godet of one a diameter of 200 in the bottom of " V " font, together
When in the axial direction of series connection interlayer thermal treatment catheter cut the slit that a 8mm is convenient for fiber feeding, wherein series connection 4 " V " fonts folder
Thermal treatment catheter is covered, along strand direction of motion input temp is 160~180 DEG C of high temperature titanium dioxide in the inside of thermal treatment catheter
Carbon, in the chuck for 4 " V " font chuck thermal treatment catheters initially connected, input temp is 250~270 DEG C of conduction oil,
In temperature under conditions of 250~270 DEG C, strand draft ratio is 1.0~1.06, strand heat treatment time is 4~8min, silk
Operating rate is 160~480cm/min；
（5）By step（4）Initially heat treated liquid crystalline polyester fiber is inserted at 4~8 " V " the font chucks heat then connected
In the chuck for managing conduit, input temp is 310~330 DEG C of conduction oil, and under conditions of temperature is 310~330 DEG C, strand is led
It is 3.0~3.6 to stretch multiplying power, and strand heat treatment time is 4~8min, and strand operating rate is 160~480cm/min；
（6）By step（5）Heat treated liquid crystalline polyester fiber inserts 4 " V " font chuck thermal treatment catheters then connected
Chuck in, input temp is 350~370 DEG C of conduction oil, under conditions of temperature is 350~370 DEG C, strand draft ratio
For 3.0~3.6, strand heat treatment time is 4~8min, and strand operating rate is 160~480cm/min；
（7）By step（6）Fiber input series connection thermal treatment catheter through Overheating Treatment, length is 2x600mm and V-shaped company
It connecing, thermal treatment catheter internal diameter is 60~80mm, installs the draw-off godet of one a diameter of 200 in the bottom of " V " font, while
The axial direction of series connection thermal treatment catheter cuts the slit that a 8mm is convenient for fiber feeding, wherein 6~8 " V " font heat treatments of series connection are led
Pipe, the inside of thermal treatment catheter along the room temperature water content that strand direction of motion input temp is 20~30 DEG C be 0.001~
The carbon dioxide of 0.003% wt makes the polyester fiber finished product of the solid phase containing nanometer-sized inorganic oxide powder connect
Room temperature is cooled in thermal treatment catheter, thermotropic liquid crystalline polyester fiber has thus been made.
Beneficial effects of the present invention：
Since the liquid-crystal polyester resin of solid phase is that solid phase contracting occurs on the basis of the small molecule polyester resin of polycondensation synthesis
Poly- reaction improves the molecular weight of liquid-crystal polyester resin, although liquid-crystal polyester resin improves molecular weight by solid phase
It is many, still, due to during Polymer Synthesizing, there are molecular weight distribution index it is wide and narrow the problem of, when molecular weight divides
When cloth is wide, the as ratio of weight average molecular weight and number-average molecular weight is larger, then, the low polymer phase in high molecular material
For molecular weight distribution index it is narrow in the case of content it is more, it is appropriate to need to carry out the liquid-crystal polyester resin of solid phase therefore
Purifying, although purifying method it is very much, however, it is possible to by vacuumizing to reduce wherein low point to liquid-crystal polyester resin melt
Sub- polymer content.
It is that the strand of polymer extends to single direction since solid phase polycondensation is that polymerisation occurs in the surface of solids,
So that the polyester macromolecule amount of solid phase further increases, and then make molecular structure more symmetrical, so that liquid crystal polyester tree
Fat is converted by amorphous phase system towards crystalline phase system, the linear rigid chain of liquid crystal polyester macromolecular chain of solid phase so that by
The spun filament of resinoid weaving forms the microfibrillar structure of high-sequential arrangement by high-temperature heat treatment, and between macromolecular chain
There are strong interaction, and then impart the higher tensile strength of fiber and modulus.
The thermotropic liquid crystalline polyester fiber of the present invention has high dimensional stability, extremely low regain and excellent counter-bending tired
Labor and crocking resistance.The thermotropic liquid crystalline polyester fiber applications field of this solid phase is very wide, can be used for fishery, aviation etc.
Industry, for manufacturing cable line, net rope, plastic reinforcement, landing umbrella line, various sporting equipments, gloves for protection etc..
The present invention is by carrying out molecule microstructure certain adjustment, in the preprocessing process of raw material, by making
During standby resin slicer, vacuum is extracted to liquid crystalline resin melt, the purpose is to the oligomer in melt is made to drop to certain journey
Degree then under vacuum, continues to remove oligomer and volatile materials and in fiber forming process, at further vacuum
Reason removes oligomer and volatile compound, the purpose is to the greatest extent to greatest extent by the oligomer in liquid-crystal polyester resin melt and
Volatile compound drops to the degree close to zero, and then improves liquid crystalline polyester fiber finished product yield.
In the manufacturing process of the liquid crystalline polyester fiber of the present invention, scope of certain size controlling in 3~6nm is suitably added
Within nanometer grade silica or titanium dioxide powder, the purpose is to improve the intensity of liquid crystalline polyester fiber, and then expand liquid crystal
The application field of polyester fiber；The purpose for controlling nanometer-sized inorganic oxide grain size is the spinning prevented in liquid crystalline polyester fiber
Cheng Zaocheng spinneret hole plugs.
Due to the spinning technique of the thermotropic liquid crystalline polyester fiber of solid phase, the parameter setting of melt-spinning technology can be used for reference,
But the species and impurity by resin component are influenced, according to actual conditions, it is necessary to be carried out suitably to equipment and parameter setting
Adjustment.
In the spinning technique flow of the thermotropic liquid crystalline polyester fiber of the solid phase of the present invention, the temperature of each heating region of extruder
Scope：First 60~80 DEG C of area, 260~275 DEG C of the secondth area, 275~290 DEG C of the 3rd area, 295~305 DEG C of the 4th area, the 5th area
310~315 DEG C, 325~330 DEG C of the 6th area, 325~330 DEG C of District 7,315~320 DEG C of Section Eight, the 9th area 300~310
DEG C, 290~305 DEG C of the tenth area, 290~300 DEG C of the 11st area, 290~300 DEG C of No.12 District, which is in high substantially
This curve sets the pumping of an a diameter of 60mm respectively above the 3rd heating zone of extruder, the 6th heating zone and the 9th heating zone
Vacuum interface, to remove vaporized oligomer, volatile compound and other impurities；All volume pipelines must all be kept the temperature,
Its temperature is maintained on polyester resin fusing point in the range of 30~50 DEG C, meanwhile, it is shown according to the pressure gauge configured on metering pump
The pressure shown, even if the temperature of adjustment double screw extruder each heating region, when pressure show it is relatively high when, suitably by double spiral shells
Each heating region of bar extruder is heightened a bit, on the contrary, it is necessary to turn down the temperature of each heating region of double screw extruder, so that whole
The limit of spun filament of the pressure and temperature of a spinning system and the melt composition sprayed from spinneret keeps relative stability,
So that the process control condition of the heat treatment procedure of subsequent liquid crystalline polyester fiber spun filament keeps relative stability, thus
The property retention of finished fiber can be made to stablize relatively, be conducive to the application of liquid crystalline polyester fiber.
Metering pump variable-frequency motor frequency is limited by the number of feeding and the line density of fiber, and frequency is generally 15~60
Change within the scope of hertz.
General spin pack pressure is maintained between 0.3~1.0Mpa, is made box temperature degree and also be preferably must be held in polyester resin and melts
On point in the range of 30~40 DEG C.
Spinning pack will be also maintained on polyester resin fusing point using preceding pretreatment temperature in the range of 30~40 DEG C.
On the one hand strand crystallisation solidification area will suitably be adjusted according to when ground temperature, another aspect also according to fiber line density or
Degree of draft is come the characteristics of adjusting, while cured according to thermotropic liquid crystalline polyester melt and fiber characteristic in itself, it is necessary to which fiber is carried out
Cool drying while fiber viscosity is reduced, is reduced the treatment process process of fibre finishing.
How much limitations of feeder feeding be on the one hand subject to for up- coiler variable-frequency motor frequency, it is contemplated that production fiber line
The size of density limitation and draw-off godet diameter determines the frequency of its variable-frequency motor, and general up- coiler variable-frequency motor frequency is general
Control is in the range of 100 hertzs.
The characteristics of according further to thermotropic liquid crystalline polyester fiber, it is necessary to the draft ratio of appropriate control as-spun fibre, generally 3.6
It is selected in the range of~4.8 times.
Although the present invention is on the basis of relatively large using the liquid-crystal polyester resin molecular weight of solid phase, by liquid
The influence of brilliant polyester resin, meanwhile, after by spinning, the various performances of fiber are simultaneously satisfactory.
The present invention is suitably mixed into a small amount of nanometer-sized inorganic oxide powder in the liquid-crystal polyester resin of solid phase, not
Influence under the situation of liquid crystalline polyester fiber spinning and heat treatment and do not influence the row of polyester molecule chain in fiber after being heat-treated
Row order, after being suitably mixed into nanometer-sized inorganic oxide, on the one hand improves the speed of heat treatment of fiber, the opposing party
Face, reduces between fiber and fiber and the bonding between fiber and spinning technique equipment, so not only increases fragrant adoption
The intensity of ester liquid crystal fiber, but also improve the yield rate of fiber, meanwhile, it is omitted the treatment process work of fiber surface finish
Sequence, and then reduce production cost.
Due to the influence of liquid-crystal polyester resin polymer molecular structure, contain in the molecular chain structure of liquid-crystal polyester resin
There is-[- Ar-COO-]-link configuration unit, wherein " Ar " is aryl, " COO " is ester group, and ester group is parent in the structural unit
Aqueous group, can be because in air if the spun filament of liquid crystalline polyester fiber carries out the orientation heat treatment of strand in air
With ester group hydrophily reaction occurs for moisture, so that the symmetry of-[- Ar-COO-]-link configuration unit is broken, Jin Erhui
Reduce the ordered arrangement of liquid crystalline polyester fiber finished fiber microstructure so that the various reduced performances of finished fiber, for this purpose, being
The various characteristics of fiber are improved, liquid crystalline polyester fiber spun filament needs are heat-treated under the protection of inert gas, simultaneously
Also need to control the water content of these inert gases.
In addition, the carbon dioxide in liquid crystalline polyester fiber spun filament heat treatment process of the present invention needs to recycle profit again
With, recovery process need not be discussed further in the technological process of the present invention, meanwhile, when recycling, it is necessary to making
Carry out moisture control process with carbon dioxide later, technological process the present invention technological process also without
It is described in further detail.
The present invention is in order to further improve the performance of liquid crystalline polyester fiber, in the heat treatment of liquid crystalline polyester fiber spun filament
When, using three-level heat treatment process, the purpose is in initial heat treatment, make the microfibrillar structure fundamental form of liquid crystalline polyester fiber
Into, meanwhile, the intensity of fiber is also improved to some extent, then under conditions of temperature and draft ratio is improved, further
The ordered arrangement of fiber is improved, and then further improves the intensity of fiber.
The present invention can also be heat-treated according to liquid crystal fiber after performance characteristic, increase or decrease the series of heat treatment, with
Just the liquid crystalline polyester fiber finished product of performance stabilization is obtained.
In the technological process of the present invention, in order to reduce the blocking of twin-screw extrusion machine inlet, present inventor passes through upper
Hundred experiments find that the first heating zone of double screw extruder needs low temperature to set, are squeezed with reducing liquid-crystal polyester resin with twin-screw
Go out the caking property of machine screw rod, be conducive to the input of liquid-crystal polyester resin, and then make liquid-crystal polyester resin inlet amount more stable.
Description of the drawings：
Fig. 1 shows be thermotropic liquid crystalline polyester as-spun fibre heat treatment process flow.
What Fig. 2 was represented is the part performance indicator after thermotropic liquid crystalline polyester as-spun fibre drawing-off.
Specific embodiment
Present invention process flow brief introduction：
First by with the nanometer-sized inorganic oxide of certain mass percent, mixed at high speed stirring machine is added in, with certain rotating speed
Nanometer-sized inorganic oxide is uniformly mixed with the polyester resin of solid phase；It subsequently inputs equipped with the single screw rod for vacuumizing interface
Extrusion mechanism is cut into slices into liquid-crystal polyester resin, then inserts in vacuum drying oven resin slicer and processing certain time is dried,
Partly to remove low point of object and volatile materials in section, it is furnished with by the input of dried resin slicer and vacuumizes interface
Liquid crystal polyester melt is made in double screw extruder, and babinet is spun in melt pipe input, and on babinet is spun, equipped with metering pump, liquid crystal gathers
Ester melt inputs a certain number of spinning packs by metering pump, is sprayed by the spinneret of spinning pack, the liquid that spinneret sprays
Brilliant polyester fondant is cooled to strand spinning the cooling gas that blows out below case quickly, under the traction of winding draw-off godet, strand with
Certain draft ratio is wound into thermotropic liquid crystalline polyester fiber spun filament, which inserts annealing device and carry out hot place immediately
Reason, through obtaining the thermotropic liquid crystalline polyester fibrous finished product of the nanometer-sized inorganic oxide containing certain mass percent after Overheating Treatment.
Heat treatment process brief introduction of the present invention：
Referring to Fig. 1：It is by the identical heat-conducting oil heating constant temperature of temperature in the interlayer thermal treatment catheter of the present invention, conduction oil is from Re Chu
It manages and enters at the bottom 1 of conduit " V " font, flowed out at the left side 2 of thermal treatment catheter " V " font, input conduction oil constant temperature adds
Thermal.Conduction oil enters at the bottom 3 of thermal treatment catheter " V " font, is flowed at the right 4 of thermal treatment catheter " V " font
Go out, input conduction oil constant temperature heating device.The carbon dioxide of certain temperature is inputted at " E " of fiber entry simultaneously, it should
Carbon dioxide is discharged at " F " of " V " font.
The as-spun fibre of the present invention is fed from the left side A of thermal treatment catheter " V " font, by pacifying in the bottom of " V " font
It after filling a diameter of 40 draw-off godet, is come out from the right B of " V " font thermal treatment catheter, in one a diameter of 200 lead of process
After wire tray, the left side C feedings from thermal treatment catheter " V " font are inputted, by installing a diameter of 40 in the bottom of " V " font
After draw-off godet, after the right D of " V " font thermal treatment catheter comes out, such a " V " font thermal treatment catheter is by 4 strings
It is unified into the initial heat treatment process process of fiber and is then connected into fiber Final Heat Treatment Process process by 4 and then uses
6~8 cooling technique process compositions for being connected into heat treatment of fibre, are wound into cylinder, thus after Overheating Treatment and cooling
The thermotropic liquid crystalline polyester as-spun fibre of the solid phase containing nanometer-sized inorganic oxide powder is disposably heat-treated to qualification
Finished fiber.
The technique of the present invention is described in further detail with reference to embodiment.
Embodiment 1
0.1%wt is added in the polyester resin of powdery solid phase, the nanometer grade silica powder that grain size is 6nm, insert height
In fast mixer, under conditions of stir speed (S.S.) is 3300rpm, after stirring 36min, single screw extrusion machine is inputted, it is true taking out
It is a length of by being cut into containing the polyester resin of nanometer grade silica or the solid phase of titanium dioxide powder extrusion under conditions of sky
The resin slicer of 6mm, a diameter of 2mm；Obtained resin slicer inserts temperature as in 180 DEG C of vacuum drying ovens, vacuum degree for-
After 0.8Mpa, dry 38h；The polyester resin section of the obtained solid phase containing nanometer grade silica or titanium dioxide powder
It directly inputs in double screw extruder, one is set respectively above the 3rd heating zone of extruder, the 6th heating zone and the 9th heating zone
A a diameter of 60mm's vacuumizes interface, and vacuum degree is -0.8Mpa, and the temperature setting that double screw extruder melts resin exists
Within the scope of 260~330 DEG C, the draw ratio of double screw extruder is 68：1；Each heating region temperature setting of double screw extruder：
First 60 DEG C of area, 260 DEG C of the secondth area, 275 DEG C of the 3rd area, 295 DEG C of the 4th area, 310 DEG C of the 5th area, 325 DEG C of the 6th area, District 7
325 DEG C, 315 DEG C of Section Eight, 300 DEG C of the 9th area, 295 DEG C of the tenth area, 290 DEG C of the 11st area, 290 DEG C of No.12 District；Temperature is set
It puts substantially in Gaussian curve shape, the polyester resin melt of the solid phase containing nanometer grade silica or titanium dioxide powder passes through
Input temp spins case for 330 DEG C of heat preservations after double screw extruder squeezes out, by metering pump input 6 spinnerets of configuration configured on spinning case
Component, spinneret of the polyester resin melt through spinning pack of the solid phase containing nanometer grade silica or titanium dioxide powder
After ejection, at the lower section 80mm of spinneret, temperature is blown into as 6 DEG C of carbon dioxide, strand is made to crystallize cooling rapidly, it is after cooling
Strand directly inputs the strand closed reel of lower end, is wound into the solid phase containing nanometer grade silica or titanium dioxide powder
Polyester fiber spun filament；Spinning rate therein is 800m/min；Draft ratio is 4.8.
Obtained spun filament is inserted into series connection interlayer thermal treatment catheter, length is 2x800mm and V-shaped connection, is pressed from both sides
Layer thermal treatment catheter internal diameter is 60mm, and the draw-off godet of one a diameter of 200 is installed in the bottom of " V " font；It is pressed from both sides simultaneously in series connection
The axial direction of layer thermal treatment catheter cuts the slit that a 8mm is convenient for fiber feeding, wherein 4 " V " font chuck heat treatments of series connection are led
Pipe, in the inside of thermal treatment catheter along the high temperature carbon dioxide that strand direction of motion input temp is 180 DEG C, what is initially connected
In the chuck of 4 " V " font chuck thermal treatment catheters, input temp is 270 DEG C of conduction oil, in the condition that temperature is 270 DEG C
Under, strand draft ratio is 1.06, and strand heat treatment time is 8min, and strand operating rate is 160cm/min；
Initially heat treated liquid crystalline polyester fiber is inserted to the chuck for 4 " V " font chuck thermal treatment catheters then connected
In, input temp is 310 DEG C of conduction oil, and under conditions of temperature is 310 DEG C, strand draft ratio is 3.0；Strand is heat-treated
Time is 4min, and strand operating rate is 160cm/min；
Heat treated liquid crystalline polyester fiber is inserted in the chuck for 4 " V " font chuck thermal treatment catheters then connected, it is defeated
Enter the conduction oil that temperature is 350 DEG C, under conditions of temperature is 350 DEG C, strand draft ratio is 3.0；Strand heat treatment time
For 4min, strand operating rate is 160cm/min；
By the fiber input series connection thermal treatment catheter after heat treatment, length is led for 2x600mm and V-shaped connection, heat treatment
Bore is 60mm, and the draw-off godet of one a diameter of 200 is installed in the bottom of " V " font；Simultaneously in series connection thermal treatment catheter
The slit that a 8mm is convenient for fiber feeding is axially cut, wherein 6 V-shape thermal treatment catheters of series connection, in the inside of thermal treatment catheter
Be that 30 DEG C of room temperature water content is the carbon dioxide of 0.001% wt along strand direction of motion input temp, make containing nanoscale without
The polyester fiber finished product of the solid phase of machine oxide powder is cooled to room temperature in thermal treatment catheter of connecting, and is thus made
The thermotropic liquid crystalline polyester fiber of solid phase.
The liquid crystal polyester finished fiber of acquisition, specific part performance characteristic are listed among Fig. 2.
Embodiment 2
3%wt is added in the polyester resin of powdery solid phase, the nanometer grade silica powder that grain size is 3nm, inserted at a high speed
In mixer, under conditions of stir speed (S.S.) is 3300rpm, after stirring 48min, single screw extrusion machine is inputted, is being vacuumized
Under conditions of, will containing the polyester resin of nanometer grade silica or the solid phase of titanium dioxide powder squeeze out be cut into a length of 3mm,
The resin slicer of a diameter of 1mm；Obtained resin slicer inserts temperature as in 160 DEG C of vacuum drying ovens, vacuum degree for-
After 0.06Mpa, dry 48h；The polyester resin of the obtained solid phase containing nanometer grade silica or titanium dioxide powder is cut
Piece is directly inputted in double screw extruder, is set respectively above the 3rd heating zone of extruder, the 6th heating zone and the 9th heating zone
One a diameter of 60mm's vacuumizes interface, and vacuum degree is -0.06Mpa, and double screw extruder melts the temperature setting of resin
Within the scope of 260~330 DEG C, the draw ratio of double screw extruder is 68：1；Each heating region temperature of double screw extruder is set
It puts：First 80 DEG C of area, 275 DEG C of the secondth area, 290 DEG C of the 3rd area, 305 DEG C of the 4th area, 315 DEG C of the 5th area, 330 DEG C of the 6th area,
Seven 330 DEG C of areas, 320 DEG C of Section Eight, 310 DEG C of the 9th area, 305 DEG C of the tenth area, 300 DEG C of the 11st area, 300 DEG C of No.12 District；Temperature
Degree is set substantially in Gaussian curve shape, the polyester resin melt of the solid phase containing nanometer grade silica or titanium dioxide powder
Input temp spins case for 310 DEG C of heat preservations after double screw extruder squeezes out, by the metering pump input configuration 4 configured on spinning case
Spinning pack, spray of the polyester resin melt through spinning pack of the solid phase containing nanometer grade silica or titanium dioxide powder
After filament plate sprays, at the lower section 380mm of spinneret, the carbon dioxide that temperature is 16 DEG C is blown into, strand is made to crystallize cooling rapidly,
Strand after cooling directly inputs the strand closed reel of lower end, is wound into consolidating containing nanometer grade silica or titanium dioxide powder
The polyester fiber spun filament of phase-polymerization；Spinning rate therein is 1400m/min；Draft ratio is 3.6；
Obtained spun filament is inserted into series connection interlayer thermal treatment catheter, length is 2x800mm and V-shaped connection, and interlayer is warm
Processing catheter diameter is 80mm, and the draw-off godet of one a diameter of 200 is installed in the bottom of " V " font；Simultaneously in series connection interlayer heat
The axial direction of processing conduit cuts the slit that a 8mm is convenient for fiber feeding, wherein 4 " V " font chuck thermal treatment catheters of series connection,
The inside of thermal treatment catheter is along the high temperature carbon dioxide that strand direction of motion input temp is 180 DEG C, in 4 initially to connect
In the chuck of " V " font chuck thermal treatment catheter, input temp is 250 DEG C of conduction oil, under conditions of temperature is 250 DEG C,
Strand draft ratio is 1.0, and strand heat treatment time is 4min, and strand operating rate is 480cm/min；
Initially heat treated liquid crystalline polyester fiber is inserted to the chuck for 4 " V " font chuck thermal treatment catheters then connected
In, input temp is 330 DEG C of conduction oil, and under conditions of temperature is 330 DEG C, strand draft ratio is 3.6；Strand is heat-treated
Time is 4min, and strand operating rate is 480cm/min；
Heat treated liquid crystalline polyester fiber is inserted in the chuck for 4 " V " font chuck thermal treatment catheters then connected, it is defeated
Enter the conduction oil that temperature is 370 DEG C, under conditions of temperature is 370 DEG C, strand draft ratio is 3.6；Strand heat treatment time
For 4min, strand operating rate is 480cm/min；
By the fiber input series connection thermal treatment catheter after heat treatment, length is led for 2x600mm and V-shaped connection, heat treatment
Bore is 80mm, and the draw-off godet of one a diameter of 200 is installed in the bottom of " V " font；Simultaneously in series connection thermal treatment catheter
The slit that a 8mm is convenient for fiber feeding is axially cut, wherein 8 V-shape thermal treatment catheters of series connection, in the inside of thermal treatment catheter
Be that 30 DEG C of room temperature water content is the carbon dioxide of 0.003% wt along strand direction of motion input temp, make containing nanoscale without
The polyester fiber finished product of the solid phase of machine oxide powder is cooled to room temperature in thermal treatment catheter of connecting, and is thus made
The thermotropic liquid crystalline polyester fiber of solid phase.
The liquid crystal polyester finished fiber of acquisition, specific part performance characteristic are listed among Fig. 2.
Comparison example 1
Single screw extrusion machine is inputted in the polyester resin of powdery solid phase, under conditions of vacuumizing, by solid phase
Polyester resin extrusion is cut into a length of 6mm, the resin slicer of a diameter of 2mm；Obtained resin slicer inserts temperature as 180 DEG C of vacuum
In baking oven, vacuum degree is -0.8Mpa, after dry 38h；The obtained solid phase containing nanometer grade silica or titanium dioxide powder
The polyester resin section of polymerization is directly inputted in double screw extruder, is added in the 3rd heating zone of extruder, the 6th heating zone and the 9th
Set above hot-zone a diameter of 60mm's to vacuumize interface respectively, vacuum degree is-0.06-0.8Mpa, and twin-screw squeezes
Go out the temperature setting of machine melting resin within the scope of 260~330 DEG C, the draw ratio of double screw extruder is 68：1；Twin-screw
Each heating region temperature setting of extruder：First 80 DEG C of area, 275 DEG C of the secondth area, 290 DEG C of the 3rd area, 305 DEG C of the 4th area, the 5th
315 DEG C of area, 330 DEG C of the 6th area, 330 DEG C of District 7,320 DEG C of Section Eight, 310 DEG C of the 9th area, 305 DEG C of the tenth area, the 11st area
300 DEG C, 300 DEG C of No.12 District；Temperature setting is in Gaussian curve shape substantially, containing nanometer grade silica or titanium dioxide powder
The polyester resin melt of solid phase input temp after double screw extruder squeezes out spins case for 330 DEG C of heat preservations, by spinning case
Metering pump input 6 spinning packs of configuration of configuration, the solid phase containing nanometer grade silica or titanium dioxide powder gather
Ester resin melt is after the spinneret of spinning pack sprays, and at the lower section 380mm of spinneret, is blown into temperature as 16 DEG C of titanium dioxides
Carbon, makes strand crystallize cooling rapidly, and strand after cooling directly inputs the strand closed reel of lower end, is wound into containing nanoscale two
The polyester fiber spun filament of the solid phase of silica or titanium dioxide powder；Spinning rate therein is 1400m/min；Drawing-off times
Rate is 4.8；
Obtained spun filament is inserted into series connection interlayer thermal treatment catheter, length is 2x800mm and V-shaped connection, and interlayer is warm
Processing catheter diameter is 80mm, and the draw-off godet of one a diameter of 200 is installed in the bottom of " V " font；Simultaneously in series connection interlayer heat
The axial direction of processing conduit cuts the slit that a 8mm is convenient for fiber feeding, wherein 4 " V " font chuck thermal treatment catheters of series connection,
The inside of thermal treatment catheter is along the high temperature carbon dioxide that strand direction of motion input temp is 180 DEG C, in 4 initially to connect
In the chuck of " V " font chuck thermal treatment catheter, input temp is 270 DEG C of conduction oil, under conditions of temperature is 270 DEG C,
Strand draft ratio is 1.06, and strand heat treatment time is 4min, and strand operating rate is 480cm/min；
Initially heat treated liquid crystalline polyester fiber is inserted to the chuck for 4 " V " font chuck thermal treatment catheters then connected
In, input temp is 330 DEG C of conduction oil, and under conditions of temperature is 330 DEG C, strand draft ratio is 3.6；Strand is heat-treated
Time is 4min, and strand operating rate is 480cm/min；
Heat treated liquid crystalline polyester fiber is inserted in the chuck for 4 " V " font chuck thermal treatment catheters then connected, it is defeated
Enter the conduction oil that temperature is 370 DEG C, under conditions of temperature is 370 DEG C, strand draft ratio is 3.6；Strand heat treatment time
For 8min, strand operating rate is 480cm/min；
By the fiber input series connection thermal treatment catheter after heat treatment, length is led for 2x600mm and V-shaped connection, heat treatment
Bore is 80mm, and the draw-off godet of one a diameter of 200 is installed in the bottom of " V " font；Simultaneously in series connection thermal treatment catheter
The slit that a 8mm is convenient for fiber feeding is axially cut, wherein 8 V-shape thermal treatment catheters of series connection, in the inside of thermal treatment catheter
Be that 30 DEG C of room temperature water content is the carbon dioxide of 0.003% wt along strand direction of motion input temp, make containing nanoscale without
The polyester fiber finished product of the solid phase of machine oxide powder is cooled to room temperature in thermal treatment catheter of connecting, and is thus made
The thermotropic liquid crystalline polyester fiber of solid phase.
The liquid crystal polyester finished fiber of acquisition, specific part performance characteristic are listed among Fig. 2.
Embodiment 3：
2%wt is added in the polyester resin of powdery solid phase, the nanoscale titanium powder that grain size is 4nm, insert high-speed stirring
It mixes in machine, under conditions of stir speed (S.S.) is 3000rpm, after stirring 44min, single screw extrusion machine is inputted, what is vacuumized
Under the conditions of, it will be squeezed out containing the polyester resin of nanometer grade silica or the solid phase of titanium dioxide powder and be cut into a length of 4mm, straight
Footpath is the resin slicer of 1.5mm；Obtained resin slicer inserts temperature as in 160~180 DEG C of vacuum drying ovens, vacuum degree for-
After 0.07Mpa, dry 44h；The polyester resin of the obtained solid phase containing nanometer grade silica or titanium dioxide powder is cut
Piece is directly inputted in double screw extruder, is set respectively above the 3rd heating zone of extruder, the 6th heating zone and the 9th heating zone
One a diameter of 60mm's vacuumizes interface, and vacuum degree is-0.06-0.8Mpa, and double screw extruder melts the temperature of resin
Degree is arranged within the scope of 260~330 DEG C, and the draw ratio of double screw extruder is 68：1；Each heating region of double screw extruder
Temperature setting：First 70 DEG C of area, 270 DEG C of the secondth area, 280 DEG C of the 3rd area, 300 DEG C of the 4th area, 310 DEG C of the 5th area, the 6th area 328
DEG C, 328 DEG C of District 7,318 DEG C of Section Eight, 308 DEG C of the 9th area, 303 DEG C of the tenth area, 298 DEG C of the 11st area, No.12 District 298
℃；Temperature setting is in Gaussian curve shape substantially, the polyester tree of the solid phase containing nanometer grade silica or titanium dioxide powder
Fat melt input temp after double screw extruder squeezes out spins case for 320 DEG C of heat preservations, is inputted by the metering pump configured on spinning case
6 spinning packs are configured, the polyester resin melt of the solid phase containing nanometer grade silica or titanium dioxide powder is through spinneret
After the spinneret of component sprays, at the lower section 180mm of spinneret, temperature is blown into as 11 DEG C of carbon dioxide, strand is made to tie rapidly
Crystalline substance cooling, strand after cooling directly input the strand closed reel of lower end, are wound into containing nanometer grade silica or titanium oxide
The polyester fiber spun filament of the solid phase of powder；Spinning rate therein is 1000m/min；Draft ratio is 4.0；
Obtained spun filament is inserted into series connection interlayer thermal treatment catheter, length is 2x800mm and V-shaped connection, and interlayer is warm
Processing catheter diameter is 70mm, and the draw-off godet of one a diameter of 200 is installed in the bottom of " V " font；Simultaneously in series connection interlayer heat
The axial direction of processing conduit cuts the slit that a 8mm is convenient for fiber feeding, wherein 4 " V " font chuck thermal treatment catheters of series connection,
The inside of thermal treatment catheter is along the high temperature carbon dioxide that strand direction of motion input temp is 170 DEG C, in 4 initially to connect
In the chuck of " V " font chuck thermal treatment catheter, input temp is 260 DEG C of conduction oil, under conditions of temperature is 260 DEG C,
Strand draft ratio is 1.03, and strand heat treatment time is 6min, and strand operating rate is 280cm/min；
Initially heat treated liquid crystalline polyester fiber is inserted to the chuck for 4 " V " font chuck thermal treatment catheters then connected
In, input temp is 320 DEG C of conduction oil, and under conditions of temperature is 320 DEG C, strand draft ratio is 3.3；Strand is heat-treated
Time is 6min, and strand operating rate is 330cm/min；
Heat treated liquid crystalline polyester fiber is inserted in the chuck for 4 " V " font chuck thermal treatment catheters then connected, it is defeated
Enter the conduction oil that temperature is 360 DEG C, under conditions of temperature is 360 DEG C, strand draft ratio is 3.3；Strand heat treatment time
For 6min, strand operating rate is 330cm/min；
By the fiber input series connection thermal treatment catheter after heat treatment, length is led for 2x600mm and V-shaped connection, heat treatment
Bore is 70mm, and the draw-off godet of one a diameter of 200 is installed in the bottom of " V " font；Simultaneously in series connection thermal treatment catheter
The slit that a 8mm is convenient for fiber feeding is axially cut, wherein 7 V-shape thermal treatment catheters of series connection, in the inside of thermal treatment catheter
The carbon dioxide that the room temperature water content for being 26 DEG C along strand direction of motion input temp is 0.002%wt, makes containing nano grade inorganic
The polyester fiber finished product of the solid phase of oxide powder is cooled to room temperature in thermal treatment catheter of connecting, and has thus been made solid
The thermotropic liquid crystalline polyester fiber of phase-polymerization；
The liquid crystal polyester finished fiber of acquisition, specific part performance characteristic are listed among Fig. 2.
Embodiment 4
1.8%wt is added in the polyester resin of powdery solid phase, the nanoscale titanium powder that grain size is 5nm, inserted at a high speed
In mixer, under conditions of stir speed (S.S.) is 3100rpm, after stirring 39min, single screw extrusion machine is inputted, is being vacuumized
Under conditions of, will containing the polyester resin of nanometer grade silica or the solid phase of titanium dioxide powder squeeze out be cut into a length of 4mm,
The resin slicer of a diameter of 2mm；Obtained resin slicer inserts temperature as in 168 DEG C of vacuum drying ovens, vacuum degree for-
After 0.076Mpa, dry 46h；The polyester resin of the obtained solid phase containing nanometer grade silica or titanium dioxide powder is cut
Piece is directly inputted in double screw extruder, is set respectively above the 3rd heating zone of extruder, the 6th heating zone and the 9th heating zone
One a diameter of 60mm's vacuumizes interface, and vacuum degree is -0.076Mpa, and double screw extruder melts the temperature setting of resin
Within the scope of 260~330 DEG C, the draw ratio of double screw extruder is 68：1；Each heating region temperature of double screw extruder is set
It puts：First 75 DEG C of area, 273 DEG C of the secondth area, 286 DEG C of the 3rd area, 299 DEG C of the 4th area, 313 DEG C of the 5th area, 326 DEG C of the 6th area,
Seven 329 DEG C of areas, 316 DEG C of Section Eight, 306 DEG C of the 9th area, 301 DEG C of the tenth area, 299 DEG C of the 11st area, 299 DEG C of No.12 District；Temperature
Degree is set substantially in Gaussian curve shape, the polyester resin melt of the solid phase containing nanometer grade silica or titanium dioxide powder
Input temp spins case for 326 DEG C of heat preservations after double screw extruder squeezes out, by the metering pump input configuration 4 configured on spinning case
Spinning pack, spray of the polyester resin melt through spinning pack of the solid phase containing nanometer grade silica or titanium dioxide powder
After filament plate sprays, at the lower section 280mm of spinneret, temperature is blown into as 13 DEG C of carbon dioxide, strand is made to crystallize cooling rapidly, it is cold
But the strand after directly inputs the strand closed reel of lower end, is wound into the solid phase containing nanometer grade silica or titanium dioxide powder
The polyester fiber spun filament of polymerization；Spinning rate therein is 1200m/min；Draft ratio is 4.3；
Obtained spun filament is inserted into series connection interlayer thermal treatment catheter, length is 2x800mm and V-shaped connection, and interlayer is warm
Processing catheter diameter is 75mm, and the draw-off godet of one a diameter of 200 is installed in the bottom of " V " font；Simultaneously in series connection interlayer heat
The axial direction of processing conduit cuts the slit that a 8mm is convenient for fiber feeding, wherein 4 " V " font chuck thermal treatment catheters of series connection,
The inside of thermal treatment catheter is along the high temperature carbon dioxide that strand direction of motion input temp is 175 DEG C, in 4 initially to connect
In the chuck of " V " font chuck thermal treatment catheter, input temp is 268 DEG C of conduction oil, under conditions of temperature is 268 DEG C,
Strand draft ratio is 1.04, and strand heat treatment time is 7min, and strand operating rate is 430cm/min；
Initially heat treated liquid crystalline polyester fiber is inserted to the chuck for 4 " V " font chuck thermal treatment catheters then connected
In, input temp is 321 DEG C of conduction oil, and under conditions of temperature is 321 DEG C, strand draft ratio is 3.4；Strand is heat-treated
Time is 7min, and strand operating rate is 430cm/min；
Heat treated liquid crystalline polyester fiber is inserted in the chuck for 4 " V " font chuck thermal treatment catheters then connected, it is defeated
Enter the conduction oil that temperature is 366 DEG C, under conditions of temperature is 366 DEG C, strand draft ratio is 3.4；Strand heat treatment time
For 7min, strand operating rate is 430cm/min；
By the fiber input series connection thermal treatment catheter after heat treatment, length is led for 2x600mm and V-shaped connection, heat treatment
Bore is 75mm, and the draw-off godet of one a diameter of 200 is installed in the bottom of " V " font；Simultaneously in series connection thermal treatment catheter
The slit that a 8mm is convenient for fiber feeding is axially cut, wherein 8 V-shape thermal treatment catheters of series connection, in the inside of thermal treatment catheter
Be that 26 DEG C of room temperature water content is the carbon dioxide of 0.0023% wt along strand direction of motion input temp, make containing nanoscale without
The polyester fiber finished product of the solid phase of machine oxide powder is cooled to room temperature in thermal treatment catheter of connecting, and is thus made
The thermotropic liquid crystalline polyester fiber of solid phase.
The liquid crystal polyester finished fiber of acquisition, specific part performance characteristic are listed among Fig. 2.
Comparison example 2
0.05%wt is added in the polyester resin of powdery solid phase, the nanoscale titanium powder that grain size is 18nm, insert height
In fast mixer, under conditions of stir speed (S.S.) is 2800rpm, after stirring 48min, single screw extrusion machine is inputted, it is true taking out
It is a length of by being cut into containing the polyester resin of nanometer grade silica or the solid phase of titanium dioxide powder extrusion under conditions of sky
The resin slicer of 3mm, a diameter of 1mm；Obtained resin slicer inserts temperature as in 160 DEG C of vacuum drying ovens, vacuum degree for-
After 0.06Mpa, dry 48h；The polyester resin of the obtained solid phase containing nanometer grade silica or titanium dioxide powder is cut
Piece is directly inputted in double screw extruder, is set respectively above the 3rd heating zone of extruder, the 6th heating zone and the 9th heating zone
One a diameter of 60mm's vacuumizes interface, and vacuum degree is -0.8Mpa, and the temperature setting that double screw extruder melts resin exists
Within the scope of 260~330 DEG C, the draw ratio of double screw extruder is 68：1；Each heating region temperature setting of double screw extruder：
First 60 DEG C of area, 260 DEG C of the secondth area, 275 DEG C of the 3rd area, 295 DEG C of the 4th area, 310 DEG C of the 5th area, 325 DEG C of the 6th area, District 7
325 DEG C, 315 DEG C of Section Eight, 300 DEG C of the 9th area, 295 DEG C of the tenth area, 290 DEG C of the 11st area, 290 DEG C of No.12 District；Temperature is set
It puts substantially in Gaussian curve shape, the polyester resin melt of the solid phase containing nanometer grade silica or titanium dioxide powder passes through
Input temp spins case for 310 DEG C of heat preservations after double screw extruder squeezes out, by metering pump input 4 spinnerets of configuration configured on spinning case
Component, spinneret of the polyester resin melt through spinning pack of the solid phase containing nanometer grade silica or titanium dioxide powder
After ejection, at the lower section 80mm of spinneret, temperature is blown into as 6 DEG C of carbon dioxide, strand is made to crystallize cooling rapidly, it is after cooling
Strand directly inputs the strand closed reel of lower end, is wound into the solid phase containing nanometer grade silica or titanium dioxide powder
Polyester fiber spun filament；Spinning rate therein is 800m/min；Draft ratio is 3.6；
Obtained spun filament is inserted into series connection interlayer thermal treatment catheter, length is 2x800mm and V-shaped connection, and interlayer is warm
Processing catheter diameter is 60mm, and the draw-off godet of one a diameter of 200 is installed in the bottom of " V " font；Simultaneously in series connection interlayer heat
The axial direction of processing conduit cuts the slit that a 8mm is convenient for fiber feeding, wherein 4 " V " font chuck thermal treatment catheters of series connection,
The inside of thermal treatment catheter is along the high temperature carbon dioxide that strand direction of motion input temp is 160 DEG C, in 4 initially to connect
In the chuck of " V " font chuck thermal treatment catheter, input temp is 250 DEG C of conduction oil, under conditions of temperature is 250 DEG C,
Strand draft ratio is 1.0, and strand heat treatment time is 8min, and strand operating rate is 160cm/min；
Initially heat treated liquid crystalline polyester fiber is inserted to the chuck for 4 " V " font chuck thermal treatment catheters then connected
In, input temp is 310 DEG C of conduction oil, and under conditions of temperature is 310 DEG C, strand draft ratio is 3.0；Strand is heat-treated
Time is 8min, and strand operating rate is 160cm/min；
Heat treated liquid crystalline polyester fiber is inserted in the chuck for 4 " V " font chuck thermal treatment catheters then connected, it is defeated
Enter the conduction oil that temperature is 350 DEG C, under conditions of temperature is 350 DEG C, strand draft ratio is 3.0；Strand heat treatment time
For 8min, strand operating rate is 160cm/min；
By the fiber input series connection thermal treatment catheter after heat treatment, length is led for 2x600mm and V-shaped connection, heat treatment
Bore is 60mm, and the draw-off godet of one a diameter of 200 is installed in the bottom of " V " font；Simultaneously in series connection thermal treatment catheter
The slit that a 8mm is convenient for fiber feeding is axially cut, wherein 6 V-shape thermal treatment catheters of series connection, in the inside of thermal treatment catheter
Be that 20 DEG C of room temperature water content is the carbon dioxide of 0.001% wt along strand direction of motion input temp, make containing nanoscale without
The polyester fiber finished product of the solid phase of machine oxide powder is cooled to room temperature in thermal treatment catheter of connecting, and is thus made
The thermotropic liquid crystalline polyester fiber of solid phase.
The liquid crystal polyester finished fiber of acquisition, specific part performance characteristic are listed among Fig. 2.
Claims (4)
1. a kind of spinning technique of thermotropic liquid crystalline polyester fiber is pre-processed using the polyester resin of solid phase, vacuumized, Screw Extrusion
Machine melts, melt metering pump, forced filtration, spinning pack, strand crystallisation by cooling, and winding doffing produces spun filament, spun filament heat
Processing；It is characterized in that：The spinning technique concretely comprises the following steps：
（1）The nanometer-sized inorganic oxide powder of 0.1~3%wt is added in the polyester resin of powdery solid phase, is inserted at a high speed
In mixer, under conditions of stir speed (S.S.) is 2800~3300rpm, after stirring 36~48min, Single screw extrusion is inputted
The polyester resin extrusion of solid phase containing nanometer-sized inorganic oxide powder under conditions of vacuumizing, is cut into length by machine
For 3~6mm, the resin slicer of a diameter of 1~2mm；
（2）By step（1）Obtained resin slicer inserts temperature as in 160~180 DEG C of vacuum drying ovens, vacuum degree for-
0.06-0.8Mpa, dry 38~48h；
（3）By step（2）The polyester resin section for the solid phase containing nanometer-sized inorganic oxide powder being dried to obtain is straight
It connects in input double screw extruder, one is set respectively above the 3rd heating zone of extruder, the 6th heating zone and the 9th heating zone
A diameter of 60mm's vacuumizes interface, and vacuum degree is-0.06-0.8Mpa, and the temperature that double screw extruder melts resin is
260~330 DEG C, temperature setting is in Gaussian curve shape, the polyester resin of the solid phase containing nanometer-sized inorganic oxide powder
Melt input temp after double screw extruder squeezes out spins case for 310~330 DEG C of heat preservations, and the metering configured on case is spun by heat preservation
Pump input 4~6 spinning packs of configuration, the polyester resin melt of the solid phase containing nanometer-sized inorganic oxide powder is through spray
After the spinneret of silk component sprays, at 80~380mm of lower section of spinneret, temperature is blown into as 6~16 DEG C of carbon dioxide, makes silk
Item crystallizes rapidly cooling, and strand after cooling directly inputs the strand closed reel of lower end, is wound into and is aoxidized containing nano grade inorganic
The polyester fiber spun filament of the solid phase of object powder；The spinning rate is 800~1400m/min；The draft ratio is
3.6~4.8；The draw ratio of the double screw extruder is 68：1；Each heating region temperature of the double screw extruder is first
60~80 DEG C of area, 260~275 DEG C of the secondth area, 275~290 DEG C of the 3rd area, 295~305 DEG C of the 4th area, the 5th area 310~315
DEG C, 325~330 DEG C of the 6th area, 325~330 DEG C of District 7,315~320 DEG C of Section Eight, 300~310 DEG C of the 9th area, the tenth area
290~305 DEG C, 290~300 DEG C of the 11st area, 290~300 DEG C of No.12 District；
（4）By step（3）Obtained spun filament inserts series connection interlayer thermal treatment catheter, and length is 2x800mm and V-shaped company
It connects, interlayer thermal treatment catheter internal diameter is 60~80mm, installs the draw-off godet of one a diameter of 200 in the bottom of " V " font, together
When in the axial direction of series connection interlayer thermal treatment catheter cut the slit that a 8mm is convenient for fiber feeding, wherein series connection 4 " V " fonts folder
Thermal treatment catheter is covered, along strand direction of motion input temp is 160~180 DEG C of high temperature titanium dioxide in the inside of thermal treatment catheter
Carbon, in the chuck for 4 " V " font chuck thermal treatment catheters initially connected, input temp is 250~270 DEG C of conduction oil,
In temperature under conditions of 250~270 DEG C, strand draft ratio is 1.0~1.06, strand heat treatment time is 4~8min, silk
Operating rate is 160~480cm/min；
（5）By step（4）Initially heat treated liquid crystalline polyester fiber inserts 4 " V " the font chucks heat treatment then connected
In the chuck of conduit, input temp is 310~330 DEG C of conduction oil, under conditions of temperature is 310~330 DEG C, strand drawing-off
Multiplying power is 3.0~3.6, and strand heat treatment time is 4~8min, and strand operating rate is 160~480cm/min；
（6）By step（5）Heat treated liquid crystalline polyester fiber inserts 4 " V " font chuck thermal treatment catheters then connected
Chuck in, input temp is 350~370 DEG C of conduction oil, under conditions of temperature is 350~370 DEG C, strand draft ratio
For 3.0~3.6, strand heat treatment time is 4~8min, and strand operating rate is 160~480cm/min；
（7）By step（6）Fiber input series connection thermal treatment catheter through Overheating Treatment, length is 2x600mm and V-shaped company
It connecing, thermal treatment catheter internal diameter is 60~80mm, installs the draw-off godet of one a diameter of 200 in the bottom of " V " font, while
The axial direction of series connection thermal treatment catheter cuts the slit that a 8mm is convenient for fiber feeding, wherein 6~8 V-shape heat treatments of series connection are led
Pipe along strand direction of motion input temp is 20~30 DEG C of room temperature carbon dioxide in the inside of thermal treatment catheter, is made containing receiving
The polyester fiber finished product of the solid phase of meter level inorganic oxide powder is cooled to room temperature in thermal treatment catheter of connecting, thus
Thermotropic liquid crystalline polyester fiber has been made.
2. thermotropic liquid crystalline polyester fiber spinning process according to claim 1, it is characterised in that：The water content of the carbon dioxide
For 0.001~0.003%wt.
3. thermotropic liquid crystalline polyester fiber spinning process according to claim 1, it is characterised in that：The nanometer-sized inorganic oxide
Powder is silica or titanium oxide；The powder diameter is 3~6nm.
4. thermotropic liquid crystalline polyester fiber spinning process according to claim 1, it is characterised in that：The heat treatment of the liquid crystal fiber
In technological process, 3 grades of heat treatment process processes may be employed, the wherein second level and the third level is the continuous heat work of series connection
Skill.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114134590A (en) * | 2021-12-30 | 2022-03-04 | 浙江甬川聚嘉新材料科技有限公司 | High-performance liquid crystal polyarylester fiber and preparation method and production equipment thereof |
| CN117328154A (en) * | 2023-11-24 | 2024-01-02 | 烟台泰和新材高分子新材料研究院有限公司 | Method and equipment for continuously producing liquid crystal polyester fiber |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111139547A (en) * | 2019-12-31 | 2020-05-12 | 上海普利特化工新材料有限公司 | Preparation method of wholly aromatic liquid crystal polyester nascent fiber |
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| CN117328154A (en) * | 2023-11-24 | 2024-01-02 | 烟台泰和新材高分子新材料研究院有限公司 | Method and equipment for continuously producing liquid crystal polyester fiber |
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