CN1190533C - High speed melt spinning of fluoropolymer fibers - Google Patents

High speed melt spinning of fluoropolymer fibers Download PDF

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Publication number
CN1190533C
CN1190533C CNB008032327A CN00803232A CN1190533C CN 1190533 C CN1190533 C CN 1190533C CN B008032327 A CNB008032327 A CN B008032327A CN 00803232 A CN00803232 A CN 00803232A CN 1190533 C CN1190533 C CN 1190533C
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Prior art keywords
spinning
temperature
plate
spinning plate
melt
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CN1339073A (en
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W·C·乌伊
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • 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
    • D01D4/00—Spinnerette packs; Cleaning thereof
    • 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
    • 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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/08—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons
    • D01F6/12—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons from polymers of fluorinated hydrocarbons
    • 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
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/32—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising halogenated hydrocarbons as the major constituent

Abstract

The processes and apparatus of the present invention concern melt spinning high viscosity fluoropolymers into single filaments or multi-filament yarns at high spinning speeds.

Description

The high speed melt-spinning of fluorine-contained polymerisate fibre
Background of invention
The present invention relates to fluoropolymer is spun into high spinning speed the method and apparatus of monofilament or multifilament textile.
Melt spinning based on the thermoplastic copolymer of tetrafluoroethylene is known.Yet, still have sizable economic potential aspect the fibre spinning speed that further improves this kind high value polymer.The problem that melt spinning method faces is, under high-rate of shear, melt fracture constantly aggravates, and this can become more and more coarse and find out from the surface of extruding fiber.The critical shear rate that begins to occur in view of melt fracture reduces along with the increase of melt viscosity, and the measure of various reduction melt viscosities focuses on the raising melt temperature always.Yet in the polymer that comprises based on the thermoplastic copolymer of tetrafluoroethylene, before any remarkable reduction of the melt viscosity that still is unrealized, thermal degradation just appears earlier in polymer.
The polytetrafluoroethylene (PTFE) homopolymer fibre also has very high value, especially its chemistry and mechanical performance, for example low-friction coefficient, heat endurance and chemical inertness.Yet, adopt melt spinning processing to prove and still make us puzzled so far.In view of the polytetrafluoroethylene (PTFE) homopolymer fibre adopts the dispersion spinning method traditionally always, this relates to many steps and complex device, therefore finds the melt spinning method of this kind fiber to have great economic benefit.
Relevant problem by high-viscosity polymer melt spinning manufacturing fiber was once done research at polyester in the past.United States Patent (USP) 3,437,725 have described a kind of spinning plate assembly, comprise top board, heating plate and base plate, are provided with distance piece so that air-gap to be provided between top board and heating plate.Put into hollow insert in top board, one of each spinneret orifice extends to the lower surface of base plate always.Molten polymer is fed in the plug-in unit so that spinneret orifice (pore) is passed in spinning.Electrical heating head supply heat exceeds at least 60 ℃ with the temperature of keeping base plate, heating plate and insert bottom parts than the molten polymer of supplying.In an embodiment, enumerated heating spinneret orifice temperature as the condition of polyester spinning between 290～430 ℃.Not mentioned any fluoropolymer or temperature required with high spinning speed melt-spinning fluoropolymer.
Summary of the invention
The invention provides a kind of melt spinning method that contains the composition of highly fluorinated thermoplastic polymer or this type of blend polymer, comprise the following steps: to make the composition fusion that contains highly fluorinated thermoplastic polymer or this kind blend polymer, form fusion fluorinated polymers compositions; Under pressure, described fusion fluorinated polymer delivery of composition is arrived the extrusion die of apparatus for melt spinning; Thereby and the molten fluoropolymer composition extruded by this extrusion die form the fusion tow, described die head is at least 450 ℃ temperature, 100s at least -1Shear rate and the spinning speed of 500m/min at least.
The present invention also provides a kind of melt spinning method that contains the composition of polytetrafluoroethylene (PTFE) homopolymers, comprises the following steps: to make the composition fusion that contains the polytetrafluoroethylene (PTFE) homopolymers to form the fusion polyetetrafluoroethycomposition composition; Under pressure, described fusion polyetetrafluoroethycomposition composition is transported to the extrusion die of apparatus for melt spinning; Thereby and the fusion polyetetrafluoroethycomposition composition extruded by this extrusion die form the fusion tow.
The present invention also provides a kind of apparatus for melt spinning, and it comprises: the spinning plate assembly that comprises the filtration means; Spinning plate; Elongated delivery pipeline, described feed-line are arranged between described filtration means and the described spinning plate; Heat the means of described elongated delivery pipeline; Heat the means of described spinning plate; And elongated annealer, be arranged in described spinning plate assembly below.
The accompanying drawing summary
Fig. 1 is the view profile of a traditional apparatus for melt spinning part.
Fig. 2 is a kind of embodiment view profile of the apparatus for melt spinning part of the present invention with elongated spinning plate.
Fig. 3 is a kind of embodiment view profile of the apparatus for melt spinning part of the present invention with the elongated spinning plate of short type.
Fig. 4 is a kind of embodiment view profile of the apparatus for melt spinning part of the present invention with the elongated spinning plate of short type, wherein is provided with heater means in the heart cavity therein, and also is provided with heater means at its outer surface.
Fig. 5 is the decomposition profile diagram of a kind of embodiment of apparatus for melt spinning of the present invention, it is characterized in that, is provided with the elongated delivery pipeline between component filter and spinning plate disk.
Fig. 6 is the view profile after the assembling of Fig. 5 apparatus for melt spinning.
The decomposition view profile of a kind of embodiment of Fig. 7 apparatus for melt spinning of the present invention is characterised in that another embodiment of elongated delivery pipeline and spinning plate disk.
Fig. 8 is the view profile after the assembling of Fig. 7 apparatus for melt spinning.
Fig. 9 is the schematic diagram of a kind of embodiment of apparatus for melt spinning of the present invention.
Figure 10 A and 10B are a kind of embodiment sectional drawings of the annealer that uses among the present invention.Figure 10 B is the partial enlarged view of Figure 10 A.
Figure 11 is example 1 composition in the mapping to SSF (spinneret draft coefficient) of 500 ℃ shear rate (1/s), the spinneret draft coefficient (SSF) when wherein the triangle of blacking is represented first fracture of wire, and hollow triangle is represented the SSF of final fracture of wire.Data comprising some dawn number/intensity/speed/(g/m).
Figure 12 is a width of cloth curve map, is presented under the constant shear rate, and temperature is to the positive-effect of the SSF of first fracture of wire.Round dot is represented 420 ℃ SSF; Square is represented 460 ℃ SSF; Triangle is represented 500 ℃ SSF (also can referring to example 1).
Figure 13 has or when not being with annealer, throughput is to the diagram of the curing distance of leaving spinning plate, here adopt FEP-5100,762 μ m (30-mil)-/30-hole spinning plate, 8cm (3 inches) diameter, the long annealer of 104cm (41 inches), and 380 ℃ (triangles) of spinning plate temperature, 430 ℃ (square) and 480 ℃ (round dot), wherein annealer is not with in the open symbols representative; The blacking symbology adopts annealer.
Figure 14 is having annealer (blacking symbol) and not under the situation with annealer (open symbols), 45.4gpm/6.0pph, leave the diagram of the distance (inch) of spinning plate to the yarn temperature, adopt 480 ℃ of FEP-5100,1000.8 μ m (39.4-mil)/30-hole spinning plate, spinning plate temperature, wherein on behalf of spinning speed, square equal 400mpm (=yarn temperature m/min) time; Yarn temperature when round dot is represented 500mpm; Triangle is represented the yarn temperature under the 700mpm.
Figure 15 be annealer length (inch) to first fracture of wire speed, m/min (mpm), diagram.Adopt: FEP-5100 fluoropolymer, 672 μ m (30 mil)/30-hole spinning plate, 480 ℃ of spinning plate temperature and 44.8g/min (gpm).
Figure 16 is the diagram of the temperature of example 23 to first fracture of wire speed (mpm), wherein is coated with bullet and represents sample of the present invention, and square is represented comparative example.
Describe in detail
The inventive method provides the advantage of high temperature spinning, the shortcoming of avoiding it to bring again simultaneously.In the methods of the invention, the composition that contains highly fluorinated thermoplastic polymer or this kind blend polymer is exposed to the temperature above this depolymerization temperature, open-assembly time be enough to cause viscosity to reduce but deficiency so that significantly degraded takes place in polymer.In melt spinning, melt composition is through extrusion die, the spinneret orifice of apparatus for melt spinning spinning plate for example, transition moment experience high-rate of shear.In the methods of the invention, just in this point, melt composition can be heated to the temperature above this highly fluorinated polymers degradation temperature.Because the temperature height can arrive high pass in the present invention and cross speed (throughput or through-rate), the time of staying of composition in extrusion die remains on extremely short
In view of the above, the invention provides the 1st melt spinning method of the composition that contains highly fluorinated thermoplastic polymer or this kind blend polymer, comprise the following steps: to contain the composition fusion of highly fluorinated thermoplastic polymer or this kind blend polymer, form fusion fluorinated polymers compositions; Under pressure, described fusion fluorinated polymer delivery of composition is arrived the extrusion die of apparatus for melt spinning; Thereby and the molten fluoropolymer composition extruded by this extrusion die form the fusion tow, described die head is at least 450 ℃ temperature, 100s at least -1Shear rate and the spinning speed of 500m/min at least.
In the fusion step, contain the composition generation fusion of highly fluorinated thermoplastic polymer or this kind blend polymer.The highly fluorinated thermoplastic polymer that meets the 1st method needs comprises the homopolymers except that polytetrafluoroethylene (PTFE), for example polyvinylidene fluoride (PVDF) and copolymer, for example tetrafluoroethylene (TFE) with comprise perfluoroolefine such as perfluorovinyl sulfide alkyl compound, perfluoroalkyl vinyl ether and so on the prepared copolymer of comonomer, the perhaps blend of this kind polymer.Term " copolymer " with regard to the object of the invention, is intended to contain and comprises the polymer of two or more comonomers in single polymers.Representative perfluor vinyl alkyl compound is a hexafluoropropene.The representative perfluor alkyl vinyl ether is perfluoro methyl vinyl ether (PMVE); , perfluoroethylvinyl ether (PEVE) and perfluoro propyl vinyl ether (PPVE).Preferred highly fluorinated polymers is by the copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether preparation and the copolymer that is prepared by tetrafluoroethylene and hexafluoropropene.Most preferred copolymer is TFE and 1～20mol% perfluorovinyl sulfide alkyl comonomer, preferred 3～10mol% hexafluoropropene or 3～10mol% hexafluoropropene and 0.2～2mol%PEVE or PPVE, and TFE and 0.5～10mol% perfluoroalkyl vinyl ether, comprise the copolymer of 0.5～3mol%PPVE or PEVE.Be fit to implement the blend that also has highly fluorinated thermoplastic polymer of the present invention, comprise the blend of TFE copolymer.
Be fit to implement the melt flow rate (MFR) that fluoropolymer of the present invention preferably shows 1～about 50g/10min, press ASTM D2116, D3307, D1238 or existing correspondence test, 372 ℃ of mensuration at other highly fluorinated thermoplastic polymers.
The composition that contains highly fluorinated thermoplastic polymer or this kind blend polymer also can comprise additive.This kind additive can comprise, for example pigment and filler.
In the methods of the invention, contain the composition of highly fluorinated polymers or this kind blend polymer, as discussed above, be melted and form a kind of molten fluoropolymer composition.Anyly technically become known for providing the means of melt all can use.Exemplary process can comprise fluoro-containing copolymer composition is incorporated in the extruding machine, and this extruding machine is heated to and is enough to make the composition fusion but is lower than highly fluorinated thermoplastic polymer or the temperature of this kind blend polymer degradation temperature.This temperature depends on the polymer of concrete use.
In a single day composition becomes molten condition, just can be transported to extrusion die under pressure, for example the spinning plate of apparatus for melt spinning.Delivery of composition is known technically to the means of extrusion die, comprised the equipment that has plunger or piston, single screw rod or twin-screw.In the preferred embodiment of the inventive method, come fusion and carry to be fit to melt composition of the invention process with extruder, thereby form monofilament or multifilament fiber product respectively to list or porous silk extrusion die.Extruder barrel and screw rod and die head preferably by resistant material, comprise that (Cabot company, Kokomo IN) makes for high nickeliferous corrosion resisting steel alloy such as Hastelloy C276.Technical knownly have many suitable extruders that available commercial is arranged, and comprises screw type and piston-type.Also can comprise metering device such as gear pump, with the metering of melt between convenient screw rod and the spinning plate.
In the methods of the invention, the molten fluoropolymer delivery of composition is extruded its after extrusion die through extrusion die pore (spinneret orifice), and described die head is at least 450 ℃ temperature, 100s at least -1(melt) shear rate and the spinning speed of 500m/min at least.
The spinneret orifice of extrusion die can be anyly to require section configuration, but is preferred with the circular cross sectional shape.The diameter that it is found that the circular cross section spinneret orifice that is suitable for the inventive method can be between about 0.5～4.0mm, but enforcement of the present invention is not limited to this scope.The draw ratio that can be used for extrusion die spinneret orifice of the present invention is preferably between about 1: 1～about 8: 1.Though the arrangement general layout in hole is unimportant, preferably the hole is arranged in one or more concentric circles, and arranges comparative optimization with single circle.
Fig. 1 has described the part of thermoplastic polymer tradition apparatus for melt spinning, that is, and and spinning plate assembly 10.Express among the figure: adapter 1 (that is, joint), it can be heated by the core formula heater that is inserted in space 9 between the dotted line of adapter 1, and connects the means (not shown) of fluoro-containing copolymer composition conveying and metering device; Cross filter ruffle 2, comprise melt filtration means (or filter material) 3, be typically filter screen; And traditional spinning plate 4, it has panel 5, panel 5 is arranged in an end of spinning plate 4, with the distance of spinning plate 4 other ends be h.Spinning plate 4 is arranged adjacently with the bottom surface 8 of crossing filter ruffle 2, and is fixed on the adapter 1 by lock nut 6 with crossing filter ruffle 2.Spinning (plate) assembly 10 is by strip heater 7 heating around lock nut 6 circumference.In Fig. 1, spinning plate 4 contacts by the conduction with lock nut 6 usually and is heated.
In the traditional design spinning plate assembly of Fig. 1, only there is not approach, because spinning plate 4 entirely is seated in locking ring 6 inside to panel 5 heating of spinning plate 4.Anyly attempt to make panel 5 overheated measures certainly will cause other zones of spinning plate assembly 10 a large portion also to be heated to the temperature of a certain close---if lower slightly---.The panel 5 of spinning plate assembly 10 undesirably is heated to this kind of exterior domain and is equal to or higher than the fluoro-containing copolymer composition degradation temperature, certainly will undesirably cause fluoro-containing copolymer composition to be exposed to high temperature for a long time, and can cause the polymer excessive degradation in some cases.
During the present invention extruded, extrusion die was heated at least 450 ℃ temperature.Here, for some fluoro-containing copolymer composition, extrusion die can be heated to greater than about 500 ℃ temperature.Be heated to such temperature and do not cause the degraded of fluoro-containing copolymer composition again, can by make extrusion die and other zones of apparatus for melt spinning that fluoro-containing copolymer composition may be housed each other heat insulation realize.When the molten fluoropolymer composition began to pass extrusion die, the high temperature induction polymer malt viscosity of die head reduced rapidly, thereby allowed two-forty to pass extrusion die.For avoiding taking place thermal degradation, need to reduce the time of staying of melt at high temperature.In view of the function of temperature is not only in degraded, and be the function of time, if the temperature height so just preferably shortens the time of staying as far as possible.So the present invention is in the most favourable place of high temperature, that is, extrusion die, for example the spinneret capillary wall just in the spinning plate panel, provides maximum temperature.Therefore, extrusion die can keep and other zones of apparatus for melt spinning that may touch fluoro-containing copolymer composition heat insulation each other.
Spinning plate or it comprise the part of panel, can be independent of other zones of filament spinning component and heat.Any height localization heater means that reaches at least 450 ℃ of temperature that provides all can be used for implementing the present invention.This kind means comprise spiral (lead or coil pipe) heater, core formula heater or strip heater and the equipment that passes through radio frequency, conduction, induction or Convective Heating, for example induction heater.Can use insulation, ceramic insulation for example, so that negative function is provided, thereby at panel and may touch between other zones of fluoro-containing copolymer composition heat insulation is provided.Can adopt one or more cooling jackets in spinning plate except that extrusion die or spinning plate device region, so that provide heat insulation for extrusion die.
In order to strengthen the heat insulation of extrusion die, have now found that in one embodiment of this invention satisfied to be, the spinning plate panel is separated from the spinning plate body, that is, strengthen the distance h between traditional spinning plate shown in Figure 1 two ends simply.Strengthen this distance by this kind mode, become as shown in Figure 2, h ' makes the spinning plate panel to separate heating with the body of spinning plate assembly remainder.So, in one embodiment, spinning plate panel of the present invention and the bottom surface of crossing filter ruffle be separated by a distance h ', this distance is enough to allow the spinning plate panel heat separately.
In Fig. 2, express a kind of spinning plate assembly 20, comprise adapter 21 (joint), the latter connects the means (not shown) of fluoro-containing copolymer composition fusion and/or conveying; Cross filter ruffle 22, comprise filter screen 23 and bottom surface 28; Elongated spinning plate 24, it has panel 25, the latter is arranged in an end of spinning plate 24, with spinning plate 4 other ends, just cross the bottom surface 28 of filter ruffle 2, between distance be h ', h '＞h wherein, simultaneously Fig. 1 then keeps equating with other sizes of 2, thereby panel 25 is reached beyond the lock nut 26.Rely on so to protrude from lock nut 26 panel 25 in addition, heater means 29 can be used to heat panel 25 separately, so panel 25 just reaches heat insulation with spinning plate assembly remainder.Heater means 27, for example band shape or spiral heater are along the circumference configuration of lock nut 26.
Fig. 3 represents to be used for filament spinning component replacement scheme of the present invention, as filament spinning component 30.In this embodiment, the lower dimension of the lock nut 26 of Fig. 2 is shortened, and for example lock nut is thinner, referring to the lock nut among Fig. 3 36.Here, the body of elongated spinning plate 34 and the spinning plate of Fig. 2 24 length reduced in comparison, yet spinning plate 34 still is elongated (for the spinning plate 4 of Fig. 1), so that reach beyond the lock nut 46, make panel 35 be able to dependence means 39, be used to heat other zones of spinning plate assembly shown in means 37 separate and heat.Also express adapter 31 among the figure, the means (not shown) that is used to be connected to fusion and/or carries fluoro-containing copolymer composition; Cross filter ruffle 32 and filtration means 33; And runner 38.
In the above-mentioned embodiment of the present invention, the melt composition that is transported in the spinning plate can be by the means heating that is arranged on the spinning plate outer wall circumference, and therefore the melt temperature adjacent with the capillary hole wall is higher than the temperature at melt center.This kind temperature heterogeneity effect, the outside is the highest, and constantly lowers the temperature towards the melt center, and the tow that can cause extruding is towards the spinning plate center curvature.For some fluoro-containing copolymer composition, under high spouting velocity, once observed angle of bend above 45 °.The possible consequence of this kind phenomenon is that accessible high speed silk continuity descends.For reducing any thermograde that exists between outermost and the interpolymer melt, heater means is set in pore 48, core formula heater for example, can be introduced in elongated spinning plate 44 in intracardiac, shown in Fig. 4 spinning plate assembly 40.Also express adapter 41 among Fig. 4, be used to be connected to fluoro-containing copolymer composition fusion and/or transportation means (not shown); Cross filter ruffle 42; Filtration means 43; Lock nut 46; Heater means 47 and 49; And panel 45.
Another embodiment provided by the invention is shown in Fig. 5 and 6, as filament spinning component 50, be intended to melt heating quickly, so the narrowed flow path 62 (for the runner 38 of Fig. 3) by being located at feed-line 58 inside reduces the volume near spinning plate panel 55 upstreams.Shorten the time of staying by reducing this volume.This kind embodiment is utilized heater means 60, for composition provides a kind of chance that causes intermediate temperature area through during the runner 62 of feed-line 58.Like this, the inventive method can further comprise allows fluoro-containing copolymer composition be exposed to greater than the fluoro-containing copolymer composition melt temperature but less than the extrusion die temperature, that is, and and the temperature of spinning plate panel temperature.As shown in the figure, the part of adjacent feed-line 58 can be by heater means 57 heating that are arranged on lock nut 56 circumference with crossing filter ruffle 52.Fluoro-containing copolymer compositions in the runner 62 of feed-line 58 utilize heater means 57 and/or heater means 60 can be preheating at least a kind greater than above-mentioned fluoro-containing copolymer composition melt temperature but less than the medium temperature of panel 55 temperature.Panel 55 is represented as in the present embodiment by the heater means 61 that is fixed in the spinning plate sleeve 59 and heats separately.Feed-line 58 was arranged in the downstream of filter ruffle 52 and filtration means 53, then was, as shown in the figure, had the spinning plate 54 of disc-shape.Spinning plate 54 can be taken off so that clean and change, and does not need to pull down component filter 52.Also express the adapter 51 that is used to be connected to fluoro-containing copolymer composition fusion and/or transportation means (not shown) among the figure.
Fig. 7 and 8 expressions spinning plate assembly 70 of the present invention, this embodiment allows to take off feed-line 78, can hold the disk spinning plate bigger than embodiment diameter shown in Fig. 5 and 6, and for example spinning plate 74.The disk spinning plate 74 that spinning plate nut 79 will have panel 75 is fixed on the bottom surface 82 of feed-line 78.Narrow inner flow passages 83 in the feed-line 78 have reduced the volume of fluoro-containing copolymer composition and in the time of staying of high temperature, thereby further reduce the chance of degraded.Feed-line 78 also provides the means that improve medium temperature between filtration means 73 and spinning plate 74 step by step by its independent heater 80.Meanwhile, the embodiment of feed-line shown in the figure can provide more homogeneous and heat transfer faster.Another bonus of this embodiment is that disk spinning plate 74 can be pulled down and not need to pull down filter ruffle, and disk is easy to make.Go back display adapter 71 among the figure, be used to be connected to the means (not shown) of fluoro-containing copolymer composition fusion and/or conveying; Plate 72, a kind of multiply distribution runner provides the support to filtration means 73; Lock nut 76 is heater means 77 on every side, is disposing cavity 84 between filtration means 73 and feed-line 78; And panel 75.
It is believed that the present invention can provide " the melt self-lubricating is extruded ".So-called " the melt self-lubricating is extruded " is meant, the cortex that has only extrudate, promptly, the direct contact arrangement wall of melt that part of, be heated to extremely high temperature by very hot die head pore surface, thereby cause this part melt viscosity very low, and, the main body of extrudate is remained on lower temperature simultaneously because the contact or the time of staying are short.The exodermis that the quite big degree of viscosity reduces plays the effect that is similar to the thin layer lubricating film, thereby makes extrusion become plug flow, and wherein the extrudate body experiences a kind of speed of homogeneous.
Term used herein " shear rate " is meant the R according to 4Q/ π 3The apparent wall shear rate that (Q=volume flow rate, R=pore radius) calculates.In the methods of the invention, shear rate is 100/s at least.Under given configuration and given temperature conditions, the range of shear rate that can reach satisfied fibers melt spinning narrows down gradually along with the increase of polymer malt viscosity.This opereating specification can be expanded by improving temperature, because this can make the critical shear rate of melt fracture starting point correspondence move to higher rate, yet must avoid depolymerization carefully.Critical-temperature/the shear rate that melt fracture occurs, be by through-rate being increased to always the surface is macroscopic to become coarse giving under fixed temperature and the die head size condition in this article, its sign be melt extrude thing by transparent become opaque slightly, thereby the sign melt fracture beginning.Further increase through-rate and will produce not satisfying surface more coarse and spinning performance and degradation.
The spinning speed of the inventive method is 500m/min at least, here determine according to last roller, therefore, visual fusion melts the configuration of spinning equipment and decides, and this roller may be work beam (the 1st roller or the draw-off godet of contact tow) or may be take up roll (output spinning cake).
Find that in the invention process shear rate and SSF have appreciable impact to the silk intensity of spinning.When increasing shear rate, when reducing SSF simultaneously, can keep intensity constant, vice versa, illustrated like that such as 1 displaying of example and Figure 11.
The inventive method can further comprise the shielding tow.By tow is implemented shielding, the tow ambient air will keep hotlyyer than allowing tow be exposed in the unrestricted surrounding air, thereby prevent the rapid cooling of tow.Unrestricted surrounding air, particularly turbulent air can cause the rapid cooling of tow, why do not wish like this, are because it may be unfavorable to the drawing-off amount that tow is allowed.Therefore, the shielding tow allows that the spinneret draft that applies higher degree attenuates.Once observed in the present invention, the condition that high speed spinning is obtained high SSF is, the curing of molten filament appears at greater than the place of the distance of 50 times of extrusion die diameters (spinneret orifice diameter) (also can referring to Figure 13).Preferably, solidify distance 500 times greater than the spinneret orifice diameter.Shielding can realize by allowing the fusion tow pass annealer.The fusion tow " spinneret draft " that annealer allows to extrude at a high speed arrives very high level, thereby has improved spinning speed.Though passing annealer, the yarn of rapid movement may produce gentle swabbing action, but annealer still can provide a kind of relative static situation that prevents the surrounding air turbulent flow, it makes very hot fusion tow partly cool off but can prevent rapid cooling, thereby makes tow keep one section ratio more than the fusing point not with the longer distance of the spinning plate of annealer at it.This point is illustrated among Figure 13.The use of annealer also makes the curing yarn maintain than not adopting the high temperature of annealer, as shown in figure 14.In addition, the use of annealer is allowed and is taked higher spinning speed, (note: annealer is not with in the representative of 0-inch) as shown in figure 15.
A kind of embodiment that is used for annealer of the present invention is illustrated in Figure 10 A and 10B.As shown in the figure, pipe 202 in annealer 200 comprises, it is a long tube that is configured in one heart in the outer tube 204, the 204th, the pipe that diameter is big slightly can have essentially identical length.Interior pipe 202 can be positioned at outer tube 204 and reach beyond the outer tube 204 from below, thereby the outlet of fusion tow is provided, and is causing a cylinder open 205 at outer tube 204 tops.Opening 205 allows that air is drawn in the inner room 206 of interior pipe 202, and this air annulus between interior pipe 202 and outer tube 204 has in advance passed through preheating.Though outside heat is not provided, annulus 208 can be at spinning duration by from the heat radiation of the heat fusing tow of extruding and be heated.Top flange 210 can have the circumference lip and be seated in the top of outer tube 204.Mesh pipe 212 preferably is made up of the fine mesh silk screen, and 20 purposes for example can be fixed on the top flange 210 and are arranged to adjacent with the inwall of interior pipe 202.Mesh pipe 212 inserts inner room 206 vertically and surpasses opening 205, but the mesh pipe is not managed total length in not needing to extend to.Mesh pipe 212 also can comprise the 2nd layer of thinner mesh, for example 100 order, be fixed on the 1st layer of mesh or near it, entirely play the effect that reduces the air turbulence of coming in, also impel air to distribute substantially equably, so that air is radially flow in the inner room 206 through opening 205.The porous ring-type of also drawing among figure Board for adjusting vision distance 214 is configured between interior pipe 202 and the outer tube 204, and manages on 202 outer surfaces or outer tube 204 inner surfaces in being connected to, and can play interior 202 effects of falling down from outer tube 204 of managing that prevent.On 214, can place fine mesh net 216 and come so that make to blow and prepare to enter into the air-dispersion of opening 205 up and distribute.This kind Board for adjusting vision distance 214 and 216 is chosen wantonly.Optional glass ring 220 can provide the perusal to molten filament and spinning plate face.
The inner and outer pipe of annealer can be by comprising metal such as aluminium, perhaps plastics such as Lucite And so on material make.Annealer can be stood alone, perhaps keeps stable by other suitable installing mechanisms, and this mechanism can be fixed on other key elements of apparatus for melt spinning or be fixed on the other materials motionless to keep it to stablize.
The inventive method also can comprise to be delivered to extrudate on the means of accumulation spinning fibre by quench region with one or more form.Quench region can be in environment temperature or with respect to the state of environment temperature for heating or cooling, specifically depend on the requirement of used special process configuration.
Any means that are used to accumulate fiber all are suitable for enforcement of the present invention.These class means comprise rotary drum, swing cloth silk device, and perhaps take up roll preferably has traversing gear, and all these is technical known.Other means comprise disconnected or the cutting-off method cut of continuous spinning-drawn fiber, are used to produce staple fibre strand or fine strip body.Other other means comprise, are used for spinning-drawn fiber directly is attached to fabric construction or composite construction.Below the described a kind of means that are fit to embodiment of the present invention that it is found that are the formula up-coilers of weaving at a high speed, (Burlington, NC) available commercial is the sort of by Leesona company.
These type of other means that are used for the auxiliary fiber transmission that the fiber spinning technology field is known all can be used as long as need.These means comprise employing godet roller (or draw-off godet), work beam, air exhaust rod, branch silk device and so on.
Antistatic finish can be applied on the fiber.It is well known in the art that this kind oils.
The inventive method also can comprise the drawing-off, relax stage of fiber or the two.Fiber can carry out drawing-off between work beam and one group of drawing roller.This kind drawing-off is the well known means that are used to improve fibre strength and reduce line density.Work beam can have heating, and to give the drawing-off of fiber higher degree, the temperature of drawing-off and degree depend on desired final fibre property.Similarly additional step just as is known to the person skilled in the art, also can join in the inventive method so that make fiber lax.
The present invention also is provided for containing the 2nd melt spinning method of the composition of polytetrafluoroethylene (PTFE) homopolymers, comprises the following steps: that the composition fusion that will contain the polytetrafluoroethylene (PTFE) homopolymers forms the fusion polyetetrafluoroethycomposition composition; Under pressure, described fusion polyetetrafluoroethycomposition composition is transported to the extrusion die of apparatus for melt spinning; Thereby and the fusion polyetetrafluoroethycomposition composition extruded by this extrusion die form the fusion tow.
In the melt spinning method of this homopolymers polytetrafluoroethylene (PTFE), preferred PTFE homopolymers is that those reveal certain melt flow rate at the thermometer that is lower than 480 ℃.Preferred homopolymers comprises Zonyl Fluorochemical additive, the granular molding powder level of PTFE, for example Teflon The pasty state extrusion molding resin that PTFE TE-6472 and PTFE are lubricated, for example Teflon PTFE 62, all can (Wilmington DE) buys from E.I.Du Pont Company.Owing to for the molten properties of flow that shows near the thermal degradation edge requires to adopt extreme temperature, the inventive method is a particular importance for the PTFE melt-processed and the fibre spinning of success.
Above the equipment of the 1st melt spinning method of relevant highly fluorinated thermoplastic compounds and use thereof be equally applicable to the melt spinning method of polyetetrafluoroethycomposition composition.Yet the same restrictions to extrusion die temperature or shear rate or spinning speed that is suitable in the 1st method may not be suitable for current PTFE method.Preferably, the extrusion die temperature is 450 ℃ at least.Spinning speed preferably is 50mpm at least; More preferably 200mpm at least; 500mpm at least most preferably.
The present invention also provides a kind of fibers melt spinning equipment, comprising: the spinning plate assembly wherein comprises the filtration means; Spinning plate; Elongated delivery pipeline, described feed-line are arranged between described filtration means and the described spinning plate; Heat the means of described elongated delivery pipeline; Heat the means of described spinning plate; And elongated annealer, shown in being arranged in below the spinning plate assembly.
Any melt-spun fibre that is used for the melt spinning technology traditionally means of filtering all can be used for the present invention.The structure of spinning plate allows the spinning plate panel is for example comprised the spinning plate part of spinning hole wall that heat separately, this surface can comprise a plate or the inseparable part of spinning plate body of separating with other zones of apparatus for melt spinning.The draw ratio of spinneret orifice is preferably between about 1: 1～about 8: 1 in the spinning plate.The spinneret orifice preferred arrangement of spinning plate becomes to make that institute is porose obtains the pattern that homogeneous heats.Preferably, spinneret orifice is arranged in 2 concentric circles or 1 circle.Preferably, spinning plate can be pulled down from feed-line separately, so that cleaning and replacing.Equally, feed-line preferably can be pulled down from crossing filter ruffle and spinning plate.The means of the means of heating feed-line and heating spinning plate can comprise strip heater, spiral heater, other conduction perhaps well known by persons skilled in the art, convection current or induction heater.
Elongated annealer, as top and go through in an embodiment, pipe and outer tube in preferably including, the two is separated by annulus.Preferably, the internal diameter of interior pipe is between about 8cm (3 inches)～20cm (8 inches).Elongated annealer also can comprise the mesh pipe, is configured in and the inner tube wall position adjacent, extends downward the length of pipe in the few part.Elongated annealer also can comprise at least 1 porous plate, is configured in the annulus, radially extends for the circumference of described outer tube, and is fixed on the outer wall of described interior pipe, the inwall of described outer tube, perhaps on these 2 pipes.
Can on above-mentioned porous plate or near it, put net.Air can enter in the annulus of annealer by opening or interface.Annealer also can comprise the means of measuring and controlling air rate, for example by needle valve or flowmeter.
Present device also can comprise the means that accumulate spun tow.Any technical conventionally known means all can be used, and include but not limited to work beam, drawing roller and take up roll.
A kind of embodiment that is used for the present device of melt spinning is shown in Fig. 9, as apparatus for melt spinning 100.Drawing among the figure feeds the feed hopper 102 of polymer composition, and charging is preferably pellet form.These pellets are heated and sent screw extruder 103.After polymer or the blend composition fusion, deliver to pump module 104 under pressure, passed filter ruffle 105, feed-line 106 arrives has the spinning plate 107 of panel 108.Glass sleeve 109 allows the fusion tow is observed.The molten fluoropolymer composition is extruded through one or more spinneret orifices of panel 108 in the spinning plate 107 and is formed continuous yarn, is conducted through elongated annealer 110 subsequently, and wherein this silk is subjected to shielding to prevent rapid cooling.Leave after the annealer, spun fiber passes draws thread guide 111, turns to thread guide 116, arrives finish roll 112 so that randomly oil, and arrives a pair of work beam 113 again, and a pair of drawing roller 114 is take up roll 115 at last.Can set up additional drawing-off, so relax rolls.
The fiber of the inventive method and device fabrication can be used for weaving.This kind textiles can be used for high-performance sportswear, for example socks.This kind fiber can be incorporated in the fabric with other fibers.The PTFE fiber can be used as industrial quality yarn and is used for filtering.The PTFE fiber also can shred and be used for dry-lubricated bearing.
Embodiment
In an embodiment, use following polymer (all by E.I.Du Pont Company (Wilmington DE) provides):
Teflon PFA 340, are the copolymers of a kind of TFE and perfluoro propyl vinyl ether
Teflon FEP 5100, the copolymer of TFE, hexafluoropropene and perfluoroethylvinyl ether
Zonyl MP-1300?PTFE
Teflon TE-6462?PTFE
Teflon PTFE TE-6472, granular molding powder
Teflon PTFE 62, lubricated pasty state extrusion molding resin
Zonyl MP-1600N，PTFE
Unless point out separately, used polymer all is Teflon PFA 340.
Example 1
Investigate the influence of spinning temperature, shear rate and spinneret draft coefficient (SSF) to spinning speed and fibre property.
Carried out spinning, wherein adopted 2.5cm (1.0 inches) diameter steel single screw extrusion machine, connected spinning pump block (module or pump seat) on it, the latter is connected to again on the spinning plate component adapter with following feature: replace Spinning pumps with bypass plate.Adopt a kind of elongated spinning plate, for example drawn in Fig. 2, wherein " h " equals 5cm (2.0 inches).With 762 μ m (30 mil), 39 hole spinning plate, 1 circle is only lined up in its all hole, cover low to medium shear rate, the shear rate interval of for example about 60/s～about 180/s, and in covering with 381 μ m (15 mil), 25 hole spinning plate to high-rate of shear, for example about 350/s～about 1, the 150/s interval.2.5cm (1 inch) is high, the spiral heater (industrial heaters company) of 3.18cm (1.25 inches) internal diameter is coiled in 2.5cm (1 inch) part of elongated spinning plate by the bottom, in order to the spinning plate part that comprises panel is heated separately.Tradition work beam and Leesona up-coiler are used.
Temperature curve before the spinning plate is: 350 ℃, and screw extruder; 380 ℃, be used to supply with between extruder and the spinning plate from the pump block to the component filter.Adopt Teflon PFA 340 has carried out spinning operation 3 times.The spinning plate temperature is set in 420 ℃, 460 ℃ or 500 ℃.
Under 420 ℃ situation, melt fracture (M.F.) occurs in the shear rate place of about 180/s.Under the shear rate of about 90/s, do not take place melt fracture, all intact the highest may spinning speeds be a shade below 219mpm.Fibre strength under this speed and shearing condition is 1.02gpd (gram/dawn).Under the shear rate of about 60/s, the high spinning speed during final fracture of wire (tow broken end) is 490mpm, and fibre strength is 1.68gpd at this moment, and filament denier is 4.0.
At 460 ℃, can spin shear rate and bring up to and be lower than 720/s slightly, just begin to occur melt fracture subsequently.Under the shear rate of 160/s, the high spinning speed during the first fracture of wire of mensuration is 435mpm, and the intensity of respective fiber is 1.13gpd.High spinning speed during final fracture of wire is 850mpm, also is under the shear rate of about 160/s.The highest fibre strength of spinning final fracture of wire is 1.61gpd, and corresponding spinning speed is 580mpm, and filament denier is 2.0.
Figure 11 represents the curve map of the shear rate of 500 ℃ of spinning plate samples to the spinneret draft coefficient.The blacking triangle is represented the data of first fracture of wire, and hollow triangle is the data of final fracture of wire.Under 500 ℃, can spin shear rate and be pulled to a shade below 1,150/s just begins melt fracture subsequently.Equal in shear rate under the condition of about 180/s, the high spinning speed of first fracture of wire is 933mpm, and the intensity of this fiber equals 1.04gpd.The high spinning speed of final fracture of wire is 930mpm, also is under 180/s, and the intensity under this speed is 1.15gpd.
So as can be seen, along with the spinning plate temperature is brought up to 500 ℃ from 420 ℃, accessibility spinning speed is brought up to the former 4.3 times.
Under the constant shear rate, temperature has positive-effect to the SSF of first fracture of wire, as shown in figure 12.Be coated with bullet and represent 420 ℃ SSF; Be coated with black box and represent 460 ℃ SSF; The blacking triangle is represented 500 ℃ SSF.SSF is higher to mean that work beam speed is higher in the spinning process under identical through-rate (that is, throughput) and given spinneret orifice size condition.
Unless point out separately, in the embodiment of remainder, spinning adopts equipment described above to carry out, and different is, adopt the corrosion-resistant single screw extrusion machine of 3.8cm (1.5 inches) diameter (KillionExtruders company (Cedar Grove, New Jersey) manufacturing).This extruder has 3 thermals treatment zone that separate, and is defined as " screw rod district 1,2 and 3 " in the temperature curve below.With clamping ring extruder is fixed on the thread adapter (screw shell), thereby the two is become one, then thread adapter is fixed on the spinning plate adapter.Clamping ring utilizes the heating of cylindrical bar insertion heater, and thread adapter and spinning plate adapter then utilize the heating of core formula heater.With strip heater heating and filtering cover.Unless point out separately, any feed-line, if exist, and the spinning panel, all adopt the heating of band shape or spiral heater.Adopt tradition to batch and winding apparatus, comprise the Leesona up-coiler.
Example 2
Spinning is carried out under following condition: through-rate, 1.3g/min/ hole; Adopt the elongated spinning plate in 762 μ m (30 mil) 30 holes; Effluxvelocity, 1.9mpm.The spinning temperature of equipment (℃) curve is:
The screw rod district clamps screw thread spinning plate assembly
123 ring adapter adapter filter spinning plate
350?350 350 380 353 480 480 500
Shear rate is 328/s, and the maximum spinning speed that reaches is 1, and the spinneret draft coefficient when 100mpm, first fracture of wire (FFB) is 580.Dawn number, intensity, elongation and the modulus that spins fiber is respectively 11d/0.76gpd/61%/5.6gpd.
Example 3
This spinning process is similar to example 2, and different is that 1.5m (5 feet) is high, and taper aluminum annealer joins on the upstream device of spinning plate, leaves the later fusion tow of spinning plate with shielding.Annealer has square cross-section, is that 30cm (12 inches) is square above, and the tapered bottom that extends to down is that 2.5cm (1.0 inches) is square.Adopt the temperature curve identical with example 2, different is: thread adapter, 380 ℃; The spinning plate adapter, 470 ℃; Component filter, 470 ℃.Shear rate is 328/s.Under the elongated spinning plate condition of through-rate and employing same 762 μ m (30 mil) 30 holes that adopts the 1.3g/min/ hole identical with example 2, maximum spinning speed improves 35%, or from 385mpm to 1,485mpm, wherein the SSF at FFB (first fracture of wire) is 782.Dawn number, intensity, elongation and the modulus that spins fiber is respectively 9.4/0.72gpd/76%/5.1gpd.
Example 4
This spinning process is similar to example 2 and 3, and different is used annealer difference.In the spinning of this example, adopt the high self-supporting Lucete of 2m (6 feet 3 inches) Annealer has the square section of 30cm * 30cm (12 inches * 12 inches).Adopt the temperature curve identical with example 3.Shear rate is 328/s.Maximum spinning speed brings up to 1, and 756mpm is 924 at the SSF of FFB correspondingly.This spinning speed improves 60% than example 2, improves 18% than example 3.Dawn number, intensity, elongation and the modulus that spins fiber is respectively 6.0d/1.16gpd/28%/10gpd.
Example 5
This example uses the spinning plate assembly that for example is illustrated among Fig. 3, has the elongated spinning plate of short type.The distance of crossing between filter ruffle lower surface and the spinning plate panel is 3.18cm (1.25 inches).Use with example 4 in identical temperature curve and identical 2m (6 feet 3 inches) Lucite Annealer.Shear rate is 328/s.The maximum spinning speed that reaches is 1,860mpm, and equal 979 at the SSF of FFB.This high speed sample is not tested its fibre property, but under the same conditions, equal 342/s and spinning speed 1 in shear rate, the 701mpm fibre property (dawn number, intensity, elongation and modulus) of the another kind of sample of spinning down is respectively: 7.6d/1.01gpd/68%/6.2gpd.
Example 6
Spinning is carried out as example 5, and different is that the elongated spinning plate of this short type adopts the heating of eddy-current heating spiral conducting line, and has made following change on temperature: component filter, 440 ℃; Spinning plate, 522～531 ℃.Shear rate is 342/s.Maximum spinning speed during FFB is 1,860mpm.Dawn number, intensity, elongation and the modulus that spins fiber is respectively 9.6d/1.06gpd/49%/8.7gpd.
Example 7
Spinning is carried out as example 6, and different is, adopts the taper aluminum annealer identical with example 3.Increased the transparent Lucite of 30cm (12 inches) at the annealer top Box is so that observe strand.Shear rate is 342/s.Maximum spinning speed during FFB is 1,860mpm.Dawn number, intensity, elongation and the modulus that spins fiber is respectively 9.0d/1.02gpd/54%/7.7gpd.
Example 8
Spinning adopts as shown in Figure 4 spinning plate to carry out, and has core formula heater (industrial heaters company (Stratford, CT) supply), and the standard strip heater is arranged in the spinning plate outside at the center of spinning plate.Spinning plate length from mistake filter ruffle bottom to the spinning plate panel is 3.18cm (1.25 inches).The temperature curve that adopts is as follows:
Screw rod district clamping ring screw thread spinning suiting filament plate assembly is crossed the spinning plate spinning plate
123 orchestration adapter filter centers
350 350 350 380 380 411 410 496 500
Used spinning plate has 26 holes; But every hole throughput is then kept identical with example 2～7.So shear rate is roughly the same, that is, and 342/s.Maximum spinning speed is 1,976mpm, and correspondingly SSF equals 1,040.Spinning speed is compared with example 5 and is improved 6%, owing to heating more evenly along the spinning plate melt.Dawn number, intensity, elongation and the modulus that spins fiber is respectively 5.6d/1.09gpd/55%/7.0gpd.
Another is 400 ℃ at spinning plate adapter and component filter temperature, and the sample that spins under 500 ℃ of conditions of identical spinning plate temperature, and providing maximal rate is 1,920mpm, the result that corresponding SSF equals 1,010.Fibre strength is higher, and the dawn number of fiber, intensity, generation and modulus measurements value are as follows respectively: 5.6d/1.25gpd/54%/8.7gpd.
Example 9
Adopt spinning plate assembly for example shown in Figure 6, check the present embodiment in the validity that reaches aspect the high spinning speed.Adopt the disk spinning plate of 15 hole 2.5cm (1.0 inch diameter), 762 μ m (30 mil) diametric hole.Used annealer is 2m (the 6 feet 3 inches) Lucite that uses in the example 4 Annealer is with strip heater heating component filter.Transfer line length from mistake filter ruffle lower surface amount to the spinning plate disk is 7.938cm (3.125 inches).
Under screw speed 4.0rpm condition, total through-rate be 20.3g/min (2.7 pounds/h) or the 1.35g/min/ hole.This is the every hole through-rate identical with front embodiment basically.Spinning speed reaches 1,816mpm, and silks all under following condition is all excellent: the screw extruder temperature, 3 districts all are set in 350 ℃; Clamping ring and thread adapter are set in 380 ℃, 389 ℃ of corresponding melt temperature measured values; Spinning plate adapter and component filter are set in 430 ℃; Feed-line is set in 470 ℃; Spinning plate is set in 500 ℃.
Reduce the temperature of spinning plate adapter and component filter and improve the feed-line temperature, spinning speed is further improved:
Spinning plate adapter feed-line spinning plate maximal rate performance
With component filter dawn number/intensity/elongation/modulus
430℃ 474℃ 500℃ 1,816mpm 6.5/1.20/45％/10
420℃ 471℃ 500℃ 1,969mpm 5.5/1.24/24％/12
410℃ 471℃ 500℃ 1,965mpm 5.6/1.38/35％/13
400℃ 470℃ 500℃ 1,950mpm 5.8/1.27/32％/12
400℃ 480℃ 500℃ 1,994mpm 5.3/1.48/48％/12
Spinning speed reaches 1,994mpm, and than the spinning speed 1 of example 4,756mpm has improved 14%.Shear rate is 347/s.Fibre strength is brought up to 1.48gpd from 1.16gpd, improves 28%.The improvement of this kind on intensity owing to, except speed was higher, depolymerization was less or do not have.
1, collect some yarn samples under the 000mpm condition, to investigate the long-time stability of spinning process.The spinning continuity of tow is splendid, allows to reel to reach 60min and 105min, and all be to plan silk.Performances such as the dawn number/intensity/elongation of fiber and modulus are respectively: 11d/0.94～1.01gpd/68～80%/7.5gpd.
A kind of sample, 1, spinning and lasting 4min under the 500mpm, the silk character at dawn number/intensity/aspects such as elongation/modulus is respectively: 7.2d/1.20gpd/39%/11gpd.Another sample, 1, spinning under the 000mpm, 1.4 times of online, 280 ℃ of following drawing-offs, the silk character at dawn number/intensity/aspects such as elongation/modulus is respectively: 7.6d/1.41gpd/25%/14gpd.
To annealer outlet, above tow path heating work beam and the air sample of collecting above the take up roll mensuration of carrying out do not find the release of any gas.If there is the polymer thermal degradation will produce gas.In view of the gas that discharges also may be sheltered or be dissolved in the fiber, collect fiber with phial at interval at different time, and adopt infrared spectrometry, gas chromatograph art/mass spectrometry and their upper space of chromatography of ions art check, do not contain any release gas yet.In addition, fiber sample is heated to 200 ℃ so that discharge the possibility dissolved gases, but does not also detect.This result's confirmation, in the present invention, although the temperature of employing up to 500 ℃ to help high-rate of shear, high spinning speed and high SSF, still do not have depolymerization to take place.The PFA polymer is if will be easy to degraded being low to moderate the time that 425 ℃ of maintenances surpass 1.0min.
Example 10
This spinning is similar to example 9, and different is that about 0.3cm (1/8 inch) eddy-current heating lead loop is round spinning plate panel 2 circles.Temperature curve in the screw extruder of thread adapter remains on the level the same with example 9.Shear rate is 347/s.Maximal rate has been improved 3.6% (from 1,994mpm, example 9) and has been reached 2,065mpm, and correspondingly SSF equals 1,087 during FFB.During the performance of maximal rate and acquisition is provided in the table below:
Spinning plate adapter feed-line spinning plate maximal rate performance dawn number/intensity/elongation/mould
With the component filter amount
430℃ 470℃ 520℃ 1,910mpm 6.9/1.04/59％/6.5
400℃ 480℃ 525℃ 2.065mpm 5.6/1.21/32％/11
Spinning continuity proof is splendid, and this moment, sample carried out the spinning of 90min with 997mpm, and is to plan silk.
Fibre property at dawn number/intensity/aspects such as elongation/modulus is respectively: 10.3d/0.97gpd/68%/3.6gpd.
Example 11
Adopt spinning plate assembly as shown in Figure 8.The diameter of spinning plate face is 4.45cm (1.75 inches), 60 holes, every hole 762 μ m (30 mil) diameter.Every hole throughput is 1.35gpm, amounts to total throughput 81gpm or 10.7 pounds per hour (pph).On the basis of example 7, adopt the top to have 30cm (12 inches) cube Lucite The taper aluminum annealer of box.The temperature that adopts (℃) curve is:
Screw rod district clamping ring screw thread spinning suiting filament plate assembly is crossed the carrier pipe spinning plate
123 orchestration adapter filter lines
350 350 350 380 380 400 400 477 500
Maximum spinning speed is 1,359mpm.Shear rate is 347/s.Dawn number/intensity/fibre properties such as elongation/modulus are respectively: 8.0d/1.04gpd/67%/7.1gpd.
With 30 hole spinning plate, for example example 7, compare, and the reason that spinning speed reduces is that total throughput doubles to cause the heat retention in the annealer too high.Annealer is replaced by the Lucite of larger capacity 2m (6 feet 3 inches) Box annealer, so maximal rate brings up to 1,500mpm.Used temperature (℃) curve is:
Screw rod district clamping ring screw thread spinning suiting filament plate assembly is crossed the carrier pipe spinning plate
123 orchestration adapter filter lines
350 350 350 380 380 420 420 500 520
Dawn number/intensity/fibre properties such as elongation/modulus are respectively: 7.2d/1.20gpd/48%/9.4gpd.
In order to reduce the delay of too much heat in annealer, the annealer door longitudinally moves towards also almost to surround the annealer one side, is all opened and covers with gas-permeable nets, so that the steady air movement of not being with turbulent flow is provided.The employing that has this porous metals sheet of 0.24cm (3/32 inch) diametric hole, centre to centre spacing 0.48cm (3/16 inch) makes maximum spinning speed bring up to 1,623mpm, closing to compare with the annealer door and improving 8%, this example adopt different slightly temperature (℃) curve:
Screw rod district clamping ring screw thread spinning suiting filament plate assembly is crossed the carrier pipe spinning plate
123 orchestration adapter filter lines
350 350 350 380 380 400 400 500 520
Dawn number/intensity/fibre properties such as elongation/modulus are respectively: 7.5d/1.18gpd/50%/8.9gpd.
Covered by the porous metals sheet in the annealer of front, as mentioned above, observing air movement has to a certain degree heterogeneity, because diffused air is arranged into and out of the front, and other 3 faces do not have.The thermocouple displays temperature that is placed near the spinning panel fluctuates 22 ℃ of amplitudes of variation between 368 ℃～390 ℃.
Adopt big Lucite Annealer is of a size of 51cm * 61cm (20 inches * 24 inches) section, 181.6cm (71.5 inches) height, and open top connects spinning plate, and bottom opening is used to operate strand.Spinning duration excessive air occurred and moved up and down, and spinning speed has reduced.
Put into plug-in unit at the annealer top, so that it is square to make the 51cm * 61cm (20 inches * 24 inches) of opening reduce to 51cm (20 inches).These plug-in units are tapered down, so that make yarn fall to dropping out.The temperature fluctuation of measuring is still up to 25 ℃, but actual temperature significantly reduces, (note: from 240 ℃ to 265 ℃ though the temperature of measuring low than the little annealer, but more should not doing too accurately of absolute temperature understood between 2 kinds of annealers, because the position of thermocouple not necessarily is located just the samely.) air stability looks more tranquil.Under the uniform temp curve, maximum spinning speed makes moderate progress than the record of little annealer, and improves slightly: 1, and 680mpm.Dawn number/intensity/fibre properties such as elongation/modulus are respectively: 8.2d/0.84gpd/59%/5.9gpd.
Example 12
In the design of above annealer, reach from annealer bottom and yarn so that it is included in thread suction gun and the yarn repiece is reached up-coiler to pass all yarn machining paths, have certain difficulty.In addition, the slow cooling of molten filament does not have the means of control fully by natural convection air.Above-mentioned 2 problems are resolved in the design of the annealer shown in Figure 10 A and 10B.Use this annealer, be easy to yarn be sucted at its awl bottom outlet place.Between inner and outer pipe, be upward through which floor fine mesh net from the air flow of compressed air source,, enter the top then and radially brush the fusion tow to eliminate eddy current.Allow air enter from the annealer bottom, and by noticeable degree, measure air mass flow with flowmeter.Can be along the temperature in the interior pipe of top 15cm (6 inches) by 1 thermocouple monitoring being set every 2.5cm (1 inch).The height of air intlet air door is adjustable in 2.5cm (1.0 inches)～10.2cm (4.0 inches) scope between the inner and outer pipes.2.5cm (1.0 inches) high glass ring can provide the observation to molten filament and spinning panel.
Spinning is to adopt structure to carry out as spinning plate assembly Fig. 8,30 holes, 1000.8 μ m (39.4 mil) aperture, spinneret orifice draw ratio 3.0.Spinning be throughput 1.3gpm and below the temperature curve condition under carry out: screw extruder is to component filter, 350 ℃; Feed-line, 450 ℃; Spinning plate, 500 ℃.Temperature in the annealer: from spinning plate face 2.5cm (1.0 inches), 268 ℃; From spinning plate face 5cm (2.0 inches), 252 ℃; From spinning plate face 15cm (6.0 inches), 222 ℃.Temperature fluctuation can be ignored, and has only 2 ℃ because change, and but observes the variation up to 25 ℃ by contrast before this paper in the annealer of example.Shear rate is 151/s.The maximum spinning speed that reaches is 1,737mpm.Dawn number/intensity/fibre properties such as elongation/modulus are respectively: 4.2d/1.17gpd/57%/7.8gpd.
The stability of this spinning system is confirmed by following true institute: 240 ℃ by 702mpm work beam speed through 1.4 times of drawing-offs online, reach 1,005mpm carries out the spinning cake coiling of 3.5h, shows the spinning continuity of excellence.This yarn package (spinning cake) net weight surpasses 20 pounds, and it is thick on 15cm (6.0 inches) diameter bobbin to be 5cm (2.0 inches).Temperature (℃) curve is:
Screw rod district clamping ring screw thread spinning suiting filament plate assembly is crossed the carrier pipe spinning plate
123 orchestration adapter filter lines
350 350 350 350 350 350 350 448 500
Dawn number/intensity/fibre properties such as elongation/modulus are respectively: 12.6d/0.80gpd/92%/3.8gpd.
Example 13
Spinning is carried out as example 12, but adopts Teflon without PFA 340 FEP 5100 fluoropolymers.Temperature (℃) curve is:
Screw rod district clamping ring screw thread spinning suiting filament plate assembly is crossed the carrier pipe spinning plate
123 orchestration adapter filter lines
315 319 325 32?5 325 325 325 401 480
The temperature that this example adopts is lower than the PFA polymer, because FEP is stable not as PFA.Shear rate is 161/s.The maximum spinning speed that reaches is 1,290mpm.Dawn number/intensity/fibre properties such as elongation/modulus are respectively: 7.3d/1.04gpd/36%/10gpd.
Example 14
The purpose of this example spinning is to test the method for research and development in the example 13 to Teflon The stability of FEP 5100 polymer (spinning).Adopt the equipment style identical, show remarkable spinning continuity with example 12 and 13, with 12 pairs of PFA polymer phases of example with coiling speed 700mpm condition under obtain the spinning cake of 3.5h.This yarn carries out the off-line drawing-off for 1.4 times with identical draw ratio, but drawing temperature is lower, is 200 ℃, because the fusing point of FEP (260 ℃) is lower than the fusing point (305 ℃) of PFA 340.Yarn package (quality) is similar to PFA 340 polymer of spinning in the example 12.Used temperature (℃) curve is lower than in the example 13 and uses, that is:
Screw rod district clamping ring screw thread spinning suiting filament plate assembly is crossed the carrier pipe spinning plate
123 orchestration adapter filter lines
305 310 315 315 315 315 315 393 480
Shear rate is 163/s.Dawn number/intensity/drawn fiber character such as elongation/modulus are respectively: 12.2d/0.97gpd/45%/5.8gpd.
Example 15
PTFE homopolymers spinning: the Zonyl that adopts granulation MP-1300 PTFE.The pelletized form of this homopolymers is to adopt the comminutor that comprises 5cm (2.0 inches) thick formpiston and former to suppress by thin PTFE powder, and formpiston has the pin of inlaying of 1,013 0.653cm (0.257 inch) diameter.Originally density is pellet, diameter 0.71cm (0.28 inch), length 1.27cm (0.50 inch), density 1.58g/mL for the powder of about 0.36g/mL is compacted under 30 tons of pressure of press.Adopt equipment and the 30 hole spinning plate identical with example 14.Used temperature (℃) curve is:
Screw rod district clamping ring screw thread spinning suiting filament plate assembly is crossed the carrier pipe spinning plate
123 orchestration adapter filter lines
400 400 400 400 400 410 410 450 520
The fusion tow comes out to look from the spinning panel and is opaque and glittering, shows certain degraded has taken place.Yet tow but fails to come out from annealer with conitnuous forms, but one section one section ground.Throughput is changed to the 1.33g/min/ hole also fail to produce continuous tow from the 0.17g/min/ hole.
After MP-1300 pellet in feed hopper is used up, in hopper, add about 200g powder type PTFE homopolymers TE-6462, form long, continuous tow through extruding.The continuous filament yarn of this free-falling is ductile, and can stretch gently between finger and constantly.The mensuration dawn number of silk is 349.
Example 16
In order to spin Teflon PTFE TE-6472, with extruder and the spinning equipment that uses in the example 15, place following high temperature (℃) curve, and use PFA 340 earlier to avoid subsequently PTFE homopolymers because of motionless degraded of stagnation between the temperature raising period that reaches 2.5h:
Screw rod district clamping ring screw thread spinning suiting filament plate assembly is crossed the conveying spinning plate
123 orchestration adapter filter pipelines
470 470 470 470 470 470 470 450 510
Teflon The pressed powder pellet of PTFE TE-6472 is defined as granular molding powder, is added in the extruder after the charging of PFA pellet uses up, and allows screw rod rotate with 14.0rpm.Teflon 6min after PTFE TE-6472 adds finds that component pressure is elevated to rapidly above 1 by 204psi, and 000psi shows Teflon PTFE TE-6472 has arrived assembly.Continuous adjusting screw(rod) speed and the spinning plate temperature brought up to 550 ℃, so that make component pressure maintain 1,000psi.Extrude continuous, transparent fusion tow, but carry bubble secretly, show thermal degradation has taken place, be cured as white tow subsequently.Under 2.0rpm, the throughput measured value is 7.6gpd, yet predicted value is 10.5gpd.Although screw speed maintains 2.0rpm, find that still throughput constantly descends, be low to moderate 0.4gpm unexpectedly, and continuous tow begins to be broken for drop, middlely connecting by length (reaching 122cm (48 inches)) and very thin silk.These very thin silks look light that like the seemingly cobweb, their are light as can to waft aloft.The dawn of the silk between drop is counted measured value from the less than 0.6 to 18.This clearly illustrates that PTFE can arrive even very thin filament denier by melt spinning.
The reduction of throughput is that in fact this stoped the feeding of fluoropolymer pellet owing in extruder barrel import department the ring-type obstruction takes place.In order to remove obstruction, all polymer of vacuum sucking-off are until seeing screw rod.Add the PFA pellet then, and utilize the special rectangular slab of making will expect to release, rectangular slab is contained on the pole of 1.3cm (0.5 inch), and size is identical with the machine barrel opening size.Rotating screw bolt causes a small amount of PFA pellet that the PTFE compressing powder that adheres to is wiped off from screw surface.
Removed after ring-type obstruction and the refeed, added PTFE compressing powder pellet once more.Under the throughput 9.3gpm condition of screw speed 5.0rpm and mensuration, continuous tow spins from all 30 holes and is batched by the work beam of 30mpm, fabulous spinning continuity has continued about 15min, ring-type takes place subsequently once more stop up, and descends indicated as component pressure.This experiment clearly illustrates that homopolymers PTFE can melt spinning.Temperature (℃) curve is:
Screw rod district clamping ring screw thread spinning suiting filament plate assembly is crossed the carrier pipe spinning plate
123 orchestration adapter filter lines
420 440 480 485 485 485 485 495 500
The PTFE fiber sample is ductile, and can operate and brittle break does not take place, and can accept tensile test.
The sample title tow dawn is counted brute force (g) intensity (gpd)
Free-falling 686 36.0 0.05
Free-falling 1,042 71.8 0.0 7
30mpm 332 14.0 0.04
Example 17
To Teflon PTFE 62 carries out spinning, and this raw material is defined as lubricated pasty state extrusion molding resin.This powder in a similar manner under 50 tons of pressure compacting be pellet, its diameter, 0.71cm (0.28 inch); Long 1.32cm (0.52 inch); The about 1.6g/cc of density.
Adopt equipment and the driving program identical with example 16.Under the 3.8rpm screw speed, add Teflon PTFE 62 pellets.Feeding is all right at the beginning, and the throughput measured value is 9.9gpm, and predicted value is 20gpm.Screw speed is brought up to 7.7rpm.Find that component pressure constantly raises and be stabilized in 1 by reducing screw speed, 200psi shows that feeding is all right.The ring-type obstruction has appearred, so component pressure descends.Accelerate screw speed once more to 30rpm, make to stop up and become flexible, so component pressure rises heavily again.At 10rpm, component pressure climbs up to 2,150psi, and this moment, continuous tow was taken out silk with 55mpm.The spinning continuity has continued about 5min, occurs ring-type again and stops up.
Example 18
The fiber of spinning carries out hot drawing-off in the example 16 and 17 in the heating salt bath.Tow is cut to about 2.5cm (1 inch) length and is clamped between 2 tip tweezers, and drawing-off then meanwhile is immersed in the salt bath of short durationly.Drawing temperature is between 330 ℃～400 ℃.This fiber can't drawing-off in the time of 320 ℃.The fusing point of PTFE polymer is between 325 ℃～342 ℃, so fiber drawing-off under molten condition.This tow is easy to drawing-off to 5.0～8.0 times.Tow is by shinny no preferred orientation under cross polarization light, and becoming along a direction is navy blue, and is the redness of pinkish red tone perpendicular to its direction, shows that molecule is along the fiber axis preferred orientation.340 ℃ drawing temperature produces high-orientation.Measure the dawn number and equal the intensity that 7.7 drafted fibre provides 0.2gpd.
Example 19
The spinning plate assembly that is described in the example 9 and is shown in Fig. 6 is used to spin Teflon PFA 340, and with the spinning condition (see figure 1) that adopts usually in traditional spinning plate assembly style, wherein spinning plate can not heat separately, compares with the heat-insulating each other spinning condition of assembly filter with spinning plate.In the present embodiment, thermal insulation part ground is obtained by set up feed-line between component filter lower surface and spinning plate face.
Adopt identical spinning plate system but spinning plate maintains identical steady temperature, carry out check experiment.Adopt 10 holes, 762 μ m (30 mil) spinning plate.
The 1st contrast spinning by with temperature (℃) curve maintains 350 ℃ and finishes by as follows:
Screw rod district clamping ring screw thread spinning suiting filament plate assembly is crossed the carrier pipe spinning plate
123 orchestration adapter filter lines
350 350 350 350 350 350 350 350 350
Throughput improves constantly, and occurs slight melt fracture when observing in the 0.178gpm/ hole.Shear rate under this maximum throughput is 45.7/s, equals at effluxvelocity 0.26mpm and SSF under 223 the condition, and the maximum spinning speed that reaches is 58mpm.
The 2nd contrast spinning is to finish under 400 ℃ higher temperature curve as follows:
Screw rod district clamping ring screw thread spinning suiting filament plate assembly is crossed the carrier pipe spinning plate
123 orchestration adapter filter lines
350 350 350 350 350 350 400 400 400
400 ℃ higher temperature allow before melt fracture, to take 0.370gpm than high throughput.Before melt fracture, under the low throughput in 0.238mpm/ hole, reach the maximum spinning speed of 206mpm.In high throughput and melt fracture edge, the maximum spinning speed that reaches is 381mpm, and this moment, shear rate was 95/s, and effluxvelocity 0.54mpm, SSF are 704.
Adopt following temperature (℃) curve:
Screw rod district clamping ring screw thread spinning suiting filament plate assembly is crossed the carrier pipe spinning plate
123 orchestration adapter filter lines
325 330 335 335 335 335 335 450 500
Adopt this kind temperature curve, throughput can be increased to the hole up to 1.125gpm/, is equivalent to 3 times of same 400 ℃ Comparative Examples, and melt fracture still do not occur.The maximum spinning speed that is reached is 1, and 956mpm is equivalent to 5 times of same 400 ℃ reference examples, and this moment, shear rate was 289/s; Effluxvelocity, 1,645mpm; SSF, 1,189.
Do not simulate 500 ℃ reference examples situation, because under the situation of traditional spinning plate system, component filter also must be heated to 500 ℃ temperature equally.When component filter reaches 500 ℃, owing to overstand in component filter, reach 10.1min, polymer will severely degrade.When being in 425 ℃, polymer just will begin degraded in not enough 1.3min.
Example 20
Carried out following experiment, to determine that the fusion tow leaves the much distances of spinning plate face and just will solidify.Curing is just to judge to have occurred when the transparent fusion tow that detects by an unaided eye becomes opaque.Can see when accelerating to 200mpm from relying on freely falling body (by gravity) to opaque transition by transparent.The fusion tow extrude be have or not with the situation of slow cooling pipe under carry out.Under the situation that adopts the slow cooling pipe, adopted a kind of special clear glass slow cooling pipe, so that can examine with interior observing, its size is 8cm (3.0 an inches) diameter, 104cm (41 inches) is long.Used spinning plate has the hole of 30 762 μ m (30 mil) diameter.Use Teflon The FEP-5100 polymer.
What the result that Figure 13 draws represented is: middle null symbol, not with the data of annealer; The blacking symbol has annealer.Curve map demonstrates the freely falling body distance to be increased along with the increase of total throughput, all like this under 3 kinds of constant spinning plate temperature: 380 ℃ (triangle symbol), 430 ℃ (block symbol) and 480 ℃ (round dot symbol).Show that under constant spinning plate temperature, solidifying distance increases with total throughput.Show that also under identical throughput situation, solidifying distance increases along with the raising of spinning plate temperature.Also show in addition, when having the slow cooling pipe, solidify 2 times far away that distance is about when not being with the slow cooling pipe.
Another experiment shows tow tension has solidifying apart from the effect that is increased to about 38cm (15 inches) from about 15cm (6 inches), wherein is not with the slow cooling pipe, and coiling speed equals 200mpm.Therefore, the curing that provides of Figure 13 is apart from the shortest curing distance of representative.
Adopted following temperature (℃) curve:
Screw rod district clamping ring screw thread spinning suiting filament plate assembly is crossed the conveying spinning plate
123 orchestration adapter filter pipelines
275 285 295 315 315 315 315 380 380,430，
480
Example 21
PTFE homopolymers grade, Zonyl MP-1600N is through melt-processed and adopt spinning plate assembly shown in Figure 8 to be spun into fiber.Polymer powder utilizes the pin compacting less than 0.64cm (0.25 inch) diameter to be the thick disk of about 0.25cm (0.1 inch) in filling up the former that has 0.64cm (0.25 inch) diameter, the high hole of 1.3cm (0.5 inch) then.About 2 pounds of this kind thin discs pellets have been made.With hand pellet is fed in the screw extruder, extremely just fills up the screw flight section, thereby to prevent crushed and to cause adhering to screw rod and the ring-type obstruction.Adopted following temperature (℃) curve:
Screw rod district clamping ring screw thread spinning suiting filament plate assembly is crossed the carrier pipe spinning plate
123 orchestration adapter filter lines
380 385 390 390 390 390 390 450 500℃
Equal under the 1.94rpm condition at screw speed, throughput is 9.4g/m, component pressure 238～246psi, employing be 10 holes, 762 μ m (30 mil) aperture spinning plate.Shear rate is 242/s.Adopt example 12 used and be shown in annealer among Figure 10 A and the 10B.Do not run into the ring-type blockage problem.After pellet used up, spinning just was through with in advance.
Originally, pick up 10 rhizoids with hand, walk around work beam and twine one the circle after, with repiece repiece rifle yarn is directed on the Leesona up-coiler always.Initial spinning speed is 30mpm, and speed is increased to maximum 202mpm gradually then.3 kinds of strands are carried out tow dawn number to be measured: 33,36 and 41.Measuring the spun filament character (dawn number/intensity/extension at break/modulus) that obtains from 41 denier filaments is: 41 dawn/0.05gpd/1.3%/3.7gpd.
Teflon PTFE 62 spinning adopt chopping and thin discs pellet to stop up to avoid ring-type.Adopt following temperature (℃) curve:
Screw rod district clamping ring screw thread spinning suiting filament plate assembly is crossed the carrier pipe spinning plate
123 orchestration adapter filter lines
440 445 450 450 450 450 450 450 500℃
The feeding situation of chopping pellet is quite smooth, does not stop up.Yet the disk pellet finally leads to the ring-type blockage problem.Spinning occurs stopping up until 60mpm then, and the spinning duration shear rate is between 183/s～614/s.
Example 22
Be similar to example 21 ground and prepare Zonyl The pellet of MP-1600N PTFE homopolymers powder adopts identical spinning plate assembly.Under following temperature curve condition, by carry out the influence of spinning research annealer with or without annealer.Through-rate is 30 hole spinning plate of 8.4g/min/762 μ m (30 mil) diametric hole, and shear rate equals 72/s.
Screw rod district clamping ring screw thread spinning suiting filament plate assembly is crossed the carrier pipe spinning plate
123 orchestration adapter filter lines
315 330 340 340 340 340 340 400 400℃
Be not with annealer.These extrude the deadweight that tow central about 15% can not bear the vertical free-falling distance of itself 1.54m (5 feet 8 inches).And the tow of those inadequate energy spinning also can only adhere to spinning the only maximum spinning speed of 15mpm, just breaks end.
Have the long annealer of 122cm (48 inches): all tow all freely fall on the ground continuously.The spinning speed of first fracture of wire (FFB) is 50mpm; The maximum spinning speed (MSS) that reaches is 480mpm.By the temperature of feed-line and spinning plate is brought up to 500 ℃ from 450 ℃, FFB is improved to 85mpm, and MSS is in 250mpm.The visible tow of naked eyes has slightly to be had carefully.The homogeneity of yarn it is found that, utilizes through the annealer chuck and introduces air at room temperature and make moderate progress to the annealer top.Under 250cfh (cubic feet per hour) condition, the yarn homogeneous that becomes.Under this kind spinning condition, MSS is improved to 404mpm.Strand fibre property (dawn number/intensity/extension at break/modulus) is 5.8/0.16gpd/12%/8gpd.
Example 23
Teflon is adopted in this experiment FEP-5100 is as fluoro-containing copolymer composition, and demonstrates the heat-insulating superiority of spinning plate.The filament spinning component that adopts is as shown in Figure 8.With identical assembly but all each several parts are all kept identical temperature.The temperature that reference examples adopted (℃) curve is:
Screw rod district clamping ring screw thread spinning suiting filament plate assembly is crossed the carrier pipe spinning plate
123 orchestration adapter filter lines
275 300 350 350 350 350 350 350 350
275 350 400 400 400 400 400 400 400
275 350 400 400 450 450 450 450 450
Screw rod district 1 and 2 temperature curve maintain low-level, up to screw rod district 3 or clamping ring just reach test temperature.If screw rod district 1 and 2 places test temperature, the degraded situation can be even worse.The temperature that sample of the present invention adopted (℃) curve is:
Screw rod district clamping ring screw thread spinning suiting filament plate assembly is crossed the carrier pipe spinning plate
123 orchestration adapter filter lines
275 295 300 300 300 300 300 380 480
Shear rate is: during 10gpm, and 86/s; 27.2gpm, 232/s; 42gpm, 359/s; 45gpm, 385/s.As shown in figure 16, when spinning temperature is about 480 ℃, reached 1, the spinning speed of 900mpm and without any remarkable degraded.Yet reference examples just experiences slight thermal degradation when 400 ℃ of spinning plate temperature, reaches the spinning speed of about 600mpm in this temperature, serious thermal degradation occurs at about 450 ℃, and the spinning speed that reaches is 900mpm.

Claims (25)

1. a melt spinning method that contains the composition of highly fluorinated thermoplastic polymer or this type of blend polymer comprises the following steps:
Make the composition fusion that contains highly fluorinated thermoplastic polymer or this kind blend polymer, form fusion fluorinated polymers compositions;
Under pressure, described fusion fluorinated polymer delivery of composition is arrived the extrusion die of apparatus for melt spinning; And
Thereby the molten fluoropolymer composition extruded by this extrusion die form the fusion tow, described die head is at least 450 ℃ temperature, 100s at least -1Shear rate and the spinning speed of 500m/min at least.
2. the method for claim 1 also comprises tow is implemented shielding.
3. the method for claim 1 also is included in before described composition extrudes by extrusion die, allows the molten fluoropolymer composition be exposed to a certain medium temperature, and this temperature is between described composition melt temperature～be lower than between the temperature of extrusion die temperature.
4. the process of claim 1 wherein highly fluorinated polymers at 372 ℃ melt flow rate between 1～50g/10min.
5. the process of claim 1 wherein that fluorinated polymer is the copolymer of tetrafluoroethylene and perfluoroolefine.
6. the method for claim 5, wherein fluorinated polymer is the copolymer of tetrafluoroethylene and hexafluoropropene.
7. the method for claim 5, wherein fluorinated polymer is the copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether.
8. the method for claim 7, wherein perfluoroalkyl vinyl ether is that perfluoro methyl vinyl ether, perfluoroethylvinyl ether are or/and perfluoro propyl vinyl ether.
9. the process of claim 1 wherein that die head temperature is 500 ℃ at least.
10. the process of claim 1 wherein zone that other of extrusion die and equipment are equipped with fluoro-containing copolymer composition heat insulation each other.
11. the process of claim 1 wherein that spinning speed is 1000m/min at least.
12. the process of claim 1 wherein that shear rate is 500s at least -1
13. the method for claim 1 also comprises this fiber of drawing-off.
14. the method for claim 1 also comprises relax stage.
15. a fibers melt spinning equipment comprises:
The spinning plate assembly, comprising
The filtration means,
Spinning plate,
Elongated delivery pipeline, described feed-line are arranged in described filtration means and described spinning
Between the plate,
Heat described elongated delivery pipeline means,
Heat the means of described spinning plate; And
Elongated annealer, be arranged in described spinning plate assembly below.
16. the equipment of claim 15, wherein elongated annealer comprises interior pipe, and it is arranged in the outer tube, and described interior pipe is separated each other by annulus with described outer tube.
17. the equipment of claim 16 also comprises the mesh pipe, is arranged in and described inner tube wall position adjacent, extends along at least a portion of described interior length of tube down.
18. the equipment of claim 16 also comprises at least 1 porous plate, is arranged in the described annulus, along the radially extension with respect to described outer tube circumference, is connected on described outer wall of inner tube or the described outer tube wall, perhaps on these 2 pipes.
19. the equipment of claim 18 also comprises net, is placed at least 1 porous plate or near it.
20. the equipment of claim 15, wherein elongated annealer also comprise the means of measuring or controlling air rate.
21. the equipment of claim 15, wherein spinning plate is dismountable.
22. the equipment of claim 15, wherein feed-line is dismountable.
23. the equipment of claim 15, the means of wherein said heating spinning plate are conduction heaters, convection heater or induction heater.
24. the equipment of claim 15, wherein spinning plate has many holes, all is arranged on the circle.
25. the equipment of claim 15 also comprises the means that accumulate spun tow.
CNB008032327A 1999-01-29 2000-01-28 High speed melt spinning of fluoropolymer fibers Expired - Fee Related CN1190533C (en)

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