CN1155305A - Method for preparing polybenzoxazole or polybenzothiazole fibers - Google Patents

Abstract

In a process for preparing polybenzoxazole or polybenzothiazole filaments by extruding a polybenzoxazole or polybenzothiazole dope, drawing the dope filament across an air gap, and coagulating the dope filament; the number of filament breaks can be reduced by placing a stress isolation device after extruding but before coagulating the filament.

Description

The method for making of polybenzoxazole or polybenzothiozole fiber

The present invention relates to polybenzoxazole or polybenzothiozole long filament and fiber preparation method.

In the method for the long filament of easily molten polybenzoxazole (" PBO ") of a typical preparation and polybenzothiozole (" PBT ") or fiber, the spinning solution of PBO or PBT polymer and an acid flux material passes through one or more holes of spinning head and extrudes generation one or many spinning solution long filaments.The spinning solution long filament is stretched, make the diameter of silk reduce to desired fineness degree.By making it it be condensed with a kind of liquid contact.Used liquid can dilute this acid flux material, and this liquid itself is not the solvent of polymer.If what generate is multifilament, they can be combined into one or many fibers in condensing or after condensing.Obviously, hope can be in full process can make the highest speed of productivity ratio, and promptly the optimization linear velocity makes long filament or fiber operation.

But, at long filament in conjunction with before generating endless tow or fiber, the fracture of long filament regular meeting, thus production process interrupt, silk need be connected in series again, but this is time-consuming operation, productivity ratio is reduced.Know all that generally long filament or fiber move fast more (being that linear velocity is high more) in process, silk may rupture more.Reduce linear velocity, fracture can reduce, but productivity ratio can reduce.

Wish under arbitrary linear velocity to reduce the number of fracture of wire always, or raising speed and don't the fracture of wire number is unacceptably increased.

Therefore, the present invention is a kind of method for preparing polybenzoxazole or polybenzothiozole long filament.This method comprises extrudes polybenzoxazole or polyphenyl thiazole spinning solution long filament, stretch spinning stoste long filament in an air gap; Make the same stress separator contact of spinning solution long filament, at this moment silk is arranged in the air gap; And each step such as the spinning solution long filament that condenses.

Have been found that before condensing and to handle spinning solution long filament or fiber.By before condensing, inserting a stress separator, can prepare PBO and PBT silk and fiber effectively.This method has reduced the fracture of wire number under given linear velocity, and, improved linear velocity and do not made fracture of wire or the protruding end number reaches the increase of unacceptable degree.

1 and 2 can help to understand the present invention with reference to the accompanying drawings.Fig. 1 and 2 is the diagram of a specific embodiments of the inventive method.Fig. 3 is the diagram of second specific embodiments of the inventive method.

Now, the specific embodiments that more specifically represents at Fig. 1 and 2. PBO or PBT spinning solution are extruded through the hole, and a spinning solution long filament 30 is extruded in each hole of spinning head 10; Be expressed as in the drawings the silk of three separation. When not only a spinning solution long filament generated, then spinning solution long filament 30 can be combined into multifilament fiber (being expressed as fiber 60 in specific embodiments) in process.

Spin liquid long filament 30 from spinning head 10 out enter Fig. 1 14 and Fig. 2 in 16 zone or " gap ", this zone is between spinning head 10 and long filament homocoagulation liquid 74 contact positions. This zone generally is called " the air gap ", although not necessarily contain air here, it can contain any can not causing and condense or can be with the gas of spinning solution generation adverse effect, such as air, nitrogen, argon gas, helium or carbon dioxide.

The air gap extends to from spinning head and spins the liquid long filament and condense.In theory, spin the fracture strength of liquid long filament and the power that produced by the deadweight of long filament has limited the maximum length of air gap.Concerning typical PBO or PBT spinning, minimum headroom crack is about 5 centimetres and adds the required space of upper stress separator, if be used in the air gap, and the space of the stretching device of still needing.In a word, it is about 100 that the maximum length of air gap preferably is less than, and more preferably less than about 10, most preferably is less than about 5 meters.

In the specific embodiments of being represented by accompanying drawing, the air gap comprises a shock chamber 20, and this chamber part has been surrounded the long filament that leaves spinning head 10.Though it is dispensable that shock chamber 20 is arbitrarinesses, spin the liquid long filament and after spinning head 10 begins to extrude, be exposed to the quite constant atmosphere but preferably use it for to make, for example by inert gas flow through long filament with the temperature that keeps shock chamber in 0 ℃～100 ℃, one denier filament leaves shock chamber, just can be exposed under the atmospheric conditions, condense up to it.

To spin the liquid long filament in the air gap and stretch, make polymer directional simultaneously so that its diameter is reduced to desired fineness degree.Though the long filament boundling can become fiber after-drawing long filament, in general, great majority or all stretchings were finished before long filament forms fibre bundle with a step or multistep.Yet the independent long filament that can stretch makes its boundling become fiber, carries out wire drawing to an increment again in fiber thereupon, but general increment is not too big.Stretch howsoever, no matter where stretching device is positioned at, the stretching of all is to occur in the air gap in fact.In case condense, just be difficult for drawn yarn.Like this, silk reaches linear velocity (being limit velocity) in the air gap, and this speed will keep at whole condensation process.Preferably, the defined spin-draw ratio of ratio of coiling speed and extruded velocity is at least about 10, more preferably is at least about 20, most preferably be at least about 40.The spinning process of PBT and PBO is technical well-known, and U.S.Patent5 is arranged as a reference, 296,185 and the unsettled U.S.Patent Application Serial No.207 that files an application on March 8th, 1994,989.

Be positioned within Fig. 1 and 2 air gap 14 and 16 separately and also have a stress separator 25, this device comprises a pair of non-live- roller 40 and 50 in the specific embodiments of being described.In the specific embodiments of being described, independent long filament boundling forms fiber 60.After passing through on roller 40 and 50, spin the non-solvent contact of liquid fiber 60 with a kind of polymer.In the specific embodiments that Fig. 1 describes, the condensation water 74 that spins in the liquid fiber 60 homocoagulation funnels 70 contacts.Then, the fiber 80 after condensing is through the stretching device 85 in this specific embodiments, and this device is by the live- roller 90 and 100 expressions of elongate filaments.Then, fiber is on spooler 110.In being depicted in the specific embodiments of Fig. 2, fiber 60 processes contain the coagulation bath 72 of condensation water 74, and pass through on live- roller 90 and 100, and this roller elongate filaments is then on spooler 110.

In the specific embodiments that Fig. 3 describes, spinning solution is extruded through the hole of spinning head 10, and each hole is extruded one and spun the liquid long filament, generates and spins liquid long filament 30, is combined into multifilament fiber 60 then.Pass through on the stretching device 85 of fiber 60 in specific embodiments, this stretching device comprises a pair of live-roller 42 and 44.Stretching device 85 so that polymer directional, and makes the diameter of silk be reduced to desired thickness degree from spinneret draft long filament 30.Live- roller 42 and 44 also plays the stress separator.Subsequently, fiber 60 is by containing the funnel 70 that condenses of condensation water 74.Fiber 80 process live- rollers 90 and 100 after condensing, and on spooler 110.

Though do not plan bound by theory, but can think, between extruding and condense, inserts spinning solution a stress separator, can make by spinning the contact of liquid long filament or fibre bundle homocoagulation liquid and cause that any turbulent flow or other unstability and individual fibers stretching are separated, like this, just reduced fracture of wire at drawing process.If the applied stress separator does not cause the unstability of fiber fracture of wire to remedy to improve long-term stability of spinning process by reducing linear velocity in the process.The stress separator has been arranged, can keep same linear velocity and improvement stability simultaneously (being that fracture of wire is few), perhaps improved linear velocity and don't can cause the unacceptable increase of broken wires purpose.Though many factors are depended in too much fracture, comprise the characteristic of drawing process and the spinning solution that is extruded, in general, the fracture of wire in per two days continuous spinnings should be less than 4, more preferably for being less than 2 approximately, most preferably being and being less than 1 approximately.

In the various compositions and process steps of the specific embodiments that illustrates, the stress separator can be any device that spins the liquid long filament that acts on, and causes the process turbulent flow or the instable migration of fracture of wire with minimizing.In a word, leave spinning head from serving production line to long filament, when homocoagulation liquid contacted, the stress separator had reduced the amplitude of the downstream turbulent flow of spinning liquid long filament experience.As long as can finish this function.Any device can be used as the stress separator.

Effectively the example of stress separator comprises: firm non rotatable thread guide (is shown in fiber and textile technology dictionary (the Dictionary of Fiber﹠amp of nineteen ninety by Hoechst Celanese Corporation; Terxile Technology) 74 page); Brake; Single roller; Non-live-roller or live-roller; And the non-live-roller and the live-roller that are a matched pair.Also can play the function of stretching utensil as the live-roller of stress separator.Firm acid metal or pottery or to be coated with acidproof metal or ceramic coating on suitable matrix be the structural material of being competent at as the stress separator.In a word, the stress separator can extruded and any part between the operation of condensing, and most preferably many factors are depended in the position, comprise the used character of stress separator own, linear velocity, the stretching condition of silk, and the spinning solution characteristic that is extruded.In general, the stress separator is preferably placed at the final velocity that reaches long filament (promptly stretch and finish in fact) afterwards or simultaneously.By extrude and condense between mobile stress separator between fracture of wire and linear velocity, reach optimum balance, thereby can find the optimum position of stress separator at an easy rate.

Any device that makes silk obtain stretching after extruding all can be used as stretching device.In a word, the stretching device elongate filaments so that its diameter reduce to desirable degree and make polymer directional.Amount of tension is selected to make finished silk or fiber have desirable size and physical property, and any device that stretches in right amount can use.Effectively the example of stretching device and separator comprise by can anti-repetition with such as the used live-roller that is present in the contacted material preparation of strong acid in the spinning solution long filament of stress separator.If use a pair of above live-roller in the method, just elongate filaments, i.e. multi-step tension method more than once.For example, can be with two groups of live-rollers.At this moment, first group of roller turns round with a kind of speed, extruding the after-drawing long filament, and second group of roller with second kind higher speed running with further elongate filaments.Second group of roller can place the long filament boundling to become before or after the fiber.In a word, stretching device can be in any suitable position (comprising as shown in Figure 1) of the process of being placed on of condensing, or places coagulation bath (as shown in Figure 2).The special stretching device of best use and position are that these factors comprise desirable amount of tension and used concrete stretching device according to overdetermined perhaps.

The long filament of preparation institute's number required and size need be selected spinning head.In practice of the present invention, desired spinning number is 50-1500, is preferably 100-1000,150-750 more preferably, PBT or PBO silk are extruded through single spinning head, and these generally make is every silk 1-3, be preferably 1-2.5, more preferably 1.5 dawn, therefore will select spinning head.In general, silk combination or boundling become DENIER to be at least about 50, preferably at least about 350, more preferably be at least about 400, be lower than approximately 5000, preferably be less than about 4500 and more preferably from about be lower than the fiber of 2500 DENIER, most preferred fiber has about 500,1000 or the number and the DENIER of the long filament of about 2000 DENIER and corresponding selection.In general, most preferred fiber is to be made by the long filament of every long filament 1.5 DENIER, and 166 long filaments are made the fiber of 250 DENIER, and 333 long filament boundlings are made the fiber of 500 DENIER; 667 long filament boundlings are made the fiber of 1000 DENIER, and 1333 long filament boundlings are made the fiber of 2000 DENIER.In a word, for preparing these long filaments, the diameter of spinneret hole is 0.1-0.5, is preferably 0.1-0.3,0.15-0.25 millimeter more preferably, and the hole that bore dia is 0.18,0.20 and 0.22 millimeter is most preferred.

Use the non-solvent of the polymer long filament that condenses, but this liquid diluting polymer solvent, thereby from long filament, remove the spinning solution solvent.Appropriate liquid includes water and the water mixture with polyphosphoric acid, and preferred condensation water is a water.These method and apparatus can condense with any method and any equipment, as long as can provide the contact that suits between condensation water and the long filament to remove the spinning solution solvent effectively.In a word, condense in the funnel or make fiber through spray or bathe and condense one.In this specialty coagulation method technical be known.U.S.Patent No.4,896,860 and 4,298,565 and U.S.Patent Applica-tion Seri al No.08/110,149 can be used as the reference of these technology.

Use method that this specialty is known collect and dry through condense and wash after fiber.After drying, if desired, fiber can be heat-treated with its tensile modulus of further raising.The method of collection, drying and heat treatment of fibre can be with reference to U.S.Patent No.5,288,452 and 5,288, the common unsettled U.S.Patent Application Serial No.162 that filed an application on December 3rd, 445 and 1993,724 and 142526 (on November 2nd, 1993 filed an application).

Condense and the process of washing the fibre is to carry out under the linear velocity of optimal production, limited maximum linear velocity by the processing of being accepted.In general, terminal velocity or winding speed are no more than about 10,000 meters of per minute usually, preferably are less than about 5000m, more preferably are less than about 2000 meters, and in a word, tag wire speed should surpass 200, are preferably 400 and more preferably 600 meters/minute.

The spinning solution that is used for preparing PBO or PBT polymer is the solution that polymer is dissolved in a kind of solvent.Many documents random, the order and the block copolymer of PBT, PBO and they, " liquid-crystalline polymer composition, method and product " (LiguidCrystalline Polymer Compositions as people such as Wolfe, Process and Products), U.S.Patent 4,703,103 (October 27,1987); People's such as Wolfe " liquid-crystalline polymer composition, method and product " (Liquid Crystalline Polymer Compositions, Processand Products), U.S.Patent 4,533,692 (August 6,1985); People's such as Wolfe " liquid crystal gathers (2, the 6-benzothiazole) composition, method and product " (Liguid CrystallinePoly (2,6-Benzothiazole) Compositions, Process and Products), U.S.Patent 4,533,724 (August 6,1985); " liquid-crystalline polymer composition, method and the product " of Wolfe (Liguid Crystalline Polymer Compositions, Processand Products), U.S.Patent 4,533,693 (August 6,1985); " thermoplasticity stable connect to Ben Bing Er oxazole with to benzo dithiazole polymer " (Ther-mooxidatively Stable Articulated p-Benzobisoxazole and P-Benzo-bisthiazole Polymers) of Evers, U.S.Patent 4,359,567 (November 16,1982); People's such as Sybert U.S.Patent 4,772,678 (September 20,1988); The U.S.Patent 4 of Harris, 847,350 July 11,1989) and " manufacture method of heterocycle block copolymer " (Method for Making HeterocyclicBlock Copolymer) of people such as Tsai, U.S.Patent 4,578,432 (March 25,1986). at the PBO or the PBT polymer that in dehydrated solvent acid, can obtain high molecular under higher temperature and the high shear rapidly, for example can be referring to people's such as Gregory U.S.Patent 5,089,591.

The preferred unit of selecting PBO or PBT polymer makes polymer become the liquid crystal of Yi Rong, has enumerated preferred monomeric unit below.More preferably polymer comes down to be made up of these monomeric units of enumerating.Most preferred polymer comes down to be made up of suitable-polybenzoxazole, anti--polybenzoxazole or anti--polybenzothiozole.

Suitable-polybenzoxazole gathers [benzo (1,2-d:5,4-d ') two oxazoles-2,6-two bases-1,4-phenylene] Instead-polybenzoxazole poly-[benzo (1,2-d:4,5-d ') Shuan oxazole-2,6-two bases-1,4-phenylene] Instead-polybenzothiozole Suitable-polybenzothiozole

AB-PBO gathers (2, the 5-benzoxazole) Poly-(2, the 5-benzothiazole)

AB-PBO gathers (2, the 6-benzoxazole)

Poly-(2, the 6-benzothiazole)

Be applicable to that the solvent that generates PBO or PBT polymer spun silk stock solution comprises cresols and non-oxide acid that can dissolve polymer.The example of suitable sour solvent comprises sulfuric acid and these sour mixtures of polyphosphoric acid, methanesulfonic acid and high concentration.Preferred solvent is polyphosphoric acid and methanesulfonic acid.Most preferred solvent is a polyphosphoric acid.

The spinning solution for preparing desired solvent and polymer concentration.Though polymer and solvent strength can extensively change according to many factors, these factors comprise used specific solvent and polymer and the SOLUTION PROPERTIES that will obtain, but the spinning solution that preferably makes contains the polymer at least about 7% weight, preferred 10% polymer that is at least about, most preferred 14% polymer that is at least about.Cmax mainly is subjected to the restriction such as practical factors such as polymer dissolution degree and spinning solution viscosity.The Cmax of polymer generally is not higher than about 20% weight, is more preferably to be lower than about 18% weight polymer.Most preferred spinning solution contains polymer about 14% based on the gross weight meter of polymer and solvent.

Embodiment

Below all embodiment be in order to prove the present invention, rather than limit the scope of the invention.Unless otherwise indicated, all umbers and percentage are by weight.

Embodiment 1

The equipment that use is described on Fig. 1 is at 178 ℃ of spinning solutions of extruding the polyphosphoric acid that contains suitable-polybenzoxazole of 14% (is that the logarithmic viscosity number in 25 ℃ of mensuration was about 33 under 0.046 Grams Per Minute rose the saturated solution with in concentration almost at methanesulfonic acid at the methanesulfonic acid acid anhydride) and 86% from the spinning head that 42 holes are arranged.Every bore dia at the spinning head at the place of extruding is 0.22 millimeter, and the PBO spinning solution is 3.2 meters/minute by the speed in every hole, and the PBO throughput in every hole is 0.24 gram/minute.

Silk stretches on the stress separator, and this stress separator is positioned at apart from spinning head 142 centimeters, comprises one meter live-roller, enters coagulation bath after the stretching, and coagulation bath contains deionized water at room temperature apart from 282 centimetres at spinning head; The air gap is about 282 centimetres like this, in the present embodiment.The speed that silk enters coagulation bath is 200 meters/minute.On the stress separator, silk is combined into fiber.Be positioned at of the speed running of second live-roller of coagulation bath, be used for drawn yarn with 200 meters of per minutes.After condensing, with silk (or fiber) washing, dry and on the curled hair tube.The stability of the method is equivalent to per hour 0.02 fracture of wire, and this shows that the evaluation of spinnability is outstanding.Comparative Examples A

Repeat the spinning process that embodiment 1 is narrated, but fiber stretches without the stress separator, but come out to stretch immediately from spinning head, through condensing funnel, silk forms fiber on a non-live-roller then.The air gap of this situation is 43 centimetres.The stability of this method is equivalent to per hour 0.04 fracture of wire, and this shows that spinnability can only be chosen as well.

The tensile strength of the pbo fiber of making in embodiment 1 and Comparative Examples A, tensile modulus and percentage elongation are tested, and it the results are shown in the Table I.

Table I

Fibre property	Unit	Embodiment 1	Comparative Examples A
				Tensile strength	The capital handkerchief	????5.7	????5.7
Tensile modulus	The capital handkerchief	????201	????201
				Elongation at break	????％	????3	????3

These results show, keep identical linear velocity by insert a stress separator in the air gap, and the whole spinnability that shows by the minimizing of broken wires per hour is improved simultaneously, can produce the fiber with suitable performance.Embodiment 2

The equipment that use is described at Fig. 3 is at 170 ℃ of spinning solutions of extruding the polyphosphoric acid that contains 14% suitable-polybenzoxazole (is 27 in the logarithmic viscosity number in 25 ℃ of mensuration in the almost saturated solution of methanesulfonic acid acid anhydride at methanesulfonic acid and under concentration 0.046 Grams Per Minute rises) and 86% by the spinning head that 166 holes are arranged.The diameter of each spinneret orifice is 0.18 millimeter, and the throughput in every hole is 0.24 gram/minute, total throughput be 39.5 the gram spinning solutions/minute, shear velocity is 3500 seconds ^-1, pass through on a pair of live-roller of silk 70 centimeters after being positioned at spinning head of extruding, enter the coagulation bath that contains deionized water at room temperature that is arranged in from 142 centimetres far away at spinning head then.Linear velocity is 200 meters/minute, and spinning the Lapie is 42.The fiber that condenses is through washing, drying; And on the curled hair tube.The stability of the method is equivalent to per hour 0.02 fracture of wire, and this shows that spinnability is evaluated as outstanding.Comparative example B

The process that repetition is narrated in embodiment 2, but on the stress separator, do not stretch, but stretch immediately through the funnel that condenses from spinning head, silk forms fiber on a pair of live-roller then.The air gap of this situation is 70 centimetres.Fiber through washing, dry after on the curled hair tube.Stability is equivalent to approximately per hour 0.04 fracture of wire, and this shows that the spinnability evaluation only is good.Embodiment 3

With preparing pbo fiber (being called fiber 3) with embodiment 2 identical methods, but the diameter in every hole of spinning head is 0.21 millimeter, and the throughput in every hole is 0.48 gram/minute, and the total throughput by spinning head is 79 gram/minute.Linear velocity remains on 400 meters/minute, and spin-draw ratio is 58.Stability is equivalent to per hour 0.04 fracture of wire, and this shows that spinnability is chosen as well.

When comparing with comparative example B, per hour broken wires are then identical with spinnability when speed doubles for method of the present invention.When the method with comparative example C compared, method of the present invention showed better spinnability and less fracture of wire under identical speed.Comparative example C

The spinning process that repetition is discussed at embodiment 3, but be not to stretch through the stress separator, but stretching immediately through coagulation bath from spinning head, silk forms fiber during then through a pair of live-roller.In the air gap of this situation is 70 centimetres.Fiber is through washing, dry and on the curled hair tube then.Stability per hour is equivalent to about 0.08 fracture of wire, and this shows that spinnability is very poor.

Embodiment 2 and 3 and comparative example B and C in tensile strength, tensile modulus and the elongation at break of the pbo fiber that makes test, these tests the results are shown in Table II

Fibre property	Unit	Embodiment 2	Comparative example B	Embodiment 3	Comparative example C
						DENIER	Restrain/9000 meters	????250	????250	????250	????250
Independent silk, DENIER	The dawn/silk	????1.5	????1.5	????1.5	????1.5
						Tensile strength	The capital handkerchief	????5.7	????5.5	????5.8	????5.6
Elongation at break	???％	????3.6	????3.7	????3.6	????3.7
						Tensile modulus	The capital handkerchief	????159	????156	????166	????160

Embodiment 4

Extrude in 170 ℃ of 166 holes through spinning heads contain suitable-polybenzoxazole of 14% (in the almost saturated solution of methanesulfonic acid acid anhydride at methanesulfonic acid under concentration 0.046 Grams Per Minute rises the logarithmic viscosity number in 25 ℃ of mensuration be about 30) and the spinning solution of 86% polyphosphoric acid.The outlet diameter of each spinneret orifice is 0.18 millimeter, and the spinning solution throughput in each hole is 0.24 ml/min, when its shear rate by the spinning solution in each hole is 3500 seconds ^-1The silk of extruding is combined into fiber, the stress separator of fiber by being made up of two pairs of live-rollers.Then, through the coagulation bath drawing of fiber.Fiber is through washing, drying, and on the curled hair tube.Distance between the spinning head and the first pair of live-roller is 70 centimetres, and fiber stretches on these rollers with about 180 meters/minute speed.Spin-draw ratio between spinning head and this first group of roller is 38.2.Second group of live-roller is from about 30 centimetres of first group of roller.The air gap is about 142 centimetres.Fiber stretches on second group of roller with about 200 meters/minute speed.Spin-draw ratio between first group and the second group of roller is 1.1, thereby is 42 by total spin-draw ratio of two sections stretchings.

The stability of process is equivalent to approximately per hour 0.04 fracture of wire, and this shows that the spinnability evaluation is good.Embodiment 5

Repeat embodiment 4, but the first pair of live-roller that is stretching in two centerings of fiber stretches with 200 meters/minute identical in fact speed also at second pair of live-roller with 200 meters/minute speed.Reaching spin-draw ratio in the single stage drawing between the spinning head and the first pair of live-roller is 42, and this stretches different with embodiment 4 multistages.

Tensile strength, elongation at break and the tensile modulus of the fiber of preparation are reported in Table III among the embodiment 4 and 5.

Table III

Fibre property	Unit	Embodiment 4	Embodiment 5
				DENIER	Restrain/9000 meters	????250	????250
The DENIER of independent silk	The dawn/silk	????1.5	????1.5
				Tensile strength	The capital handkerchief	????5.9	????5.5
Elongation at break	????％	????3.4	????3.6
				Tensile modulus	The capital handkerchief	????171	????159

The multistage that this embodiment is illustrated in the silk/fiber that does not condense of air gap stretches, and points out that this can be used for preparing the fiber with remarkable physical property.

Claims (11)

1. method for preparing polybenzoxazole or polybenzothiozole long filament, said method comprise following each step:

(a) extrude polybenzoxazole or polybenzothiozole and spin the liquid long filament;

(b) the liquid long filament is spun in stretching in the air gap;

(c) make and spin the contact of the same stress separator of liquid long filament, at this moment silk is positioned at the air gap; And

(d) condense and spin the liquid long filament.

2. the process of claim 1 wherein that polybenzoxazole or polybenzothiozole spin the liquid long filament and extrude through an above spinneret hole.

3. the method for claim 2 wherein, is extruded more than one and is spun the liquid long filament, before long filament condenses, among or afterwards, long filament is in conjunction with forming fiber.

4. the process of claim 1 wherein that the stress separator also plays the stretching device of elongate filaments.

5. the process of claim 1 wherein, with multi-step tension method elongate filaments.

6. the process of claim 1 wherein that PBT and PBO long filament have the filament denier of every silk 1-2.5 DENIER.

7. the method for claim 6, wherein, PBT and PBO long filament have the silk DENIER of every silk 1.5 DENIER.

8. the method for claim 3, wherein the 100-3500 silk is extruded.

9. the method for claim 8, wherein, silk is combined into the fiber with 350-5000 DENIER.

10. the method for claim 9, wherein, fiber has 500,1000 or 2000 DENIER.

11. the process of claim 1 wherein, tag wire speed be 600-2000 rice/minute.

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