CN1617957A - Production of dimensionally stable polyester yarns - Google Patents
Production of dimensionally stable polyester yarns Download PDFInfo
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- CN1617957A CN1617957A CN 03802338 CN03802338A CN1617957A CN 1617957 A CN1617957 A CN 1617957A CN 03802338 CN03802338 CN 03802338 CN 03802338 A CN03802338 A CN 03802338A CN 1617957 A CN1617957 A CN 1617957A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
Abstract
The invention relates to a method for producing stretched multifilament polyester yarns that are suitable for use in technical applications such as tires, cord, conveyor belts and the like. According to the inventive method, chips or granules having a so-called textile grade are post-condensed in a special reactor to an intrinsic viscosity of > 0.9 dl/g and a carboxyl end group concentration of less than 15 mole/kg. The yarn is spun in a spinning duct that comprises three zones, namely a pre-heating zone, a cooling zone and a conditioning zone. The yarn is spun at a spinning speed of 2,500 to 3,400, then doubly stretched and wound up with a winding speed of at least 5,500 m.
Description
The present invention relates to the continuation method that a kind of preparation is suitable for commercial Application such as tire cord and is applicable to the multifilament polyester yarn of the dimensionally stable that strengthens conveyer belt etc., also relate to multifilament polyester yarn and its purposes in commercial Application.
The multifilament polyester yarn of dimensionally stable is especially with the intensity component of form of fabric as industrial product such as tire, conveyer belt and V-belt etc.High-modulus, low-shrinkage and high antifatigue are the requirements that the polyfilament yarn of this dimensionally stable must satisfy.
The yarn that fatigue resistance is high must have the inherent viscosity that is higher than 0.83dl/g.
The polymer that needs thus mainly is down by solid-state condensation reaction preparation solid-state.This method generally is about the polymer of 0.6dl/g from fabric viscosity.Before spinning, need section fusion, and in extruder, carry out fusion usually after-condensation.
General two kinds of different spinning and the stable multifilament polyester yarn of draft process preparation size used.Two kinds of spinning hauling speeds that technology all adopts to be higher than 2000m/min.The difference of two kinds of technologies is: with regard to two-step method, coiling spun filament during beginning is then with the independent drawing-off of the speed that is lower than 500m/min; And, carry out drawing-off and coiling with speed immediately after the spinning up to about 7000m/min for the one-step method that is called high speed spinning-drawing-off method.
These methods all have their merits and demerits:
For example, United States Patent (USP) 4,195,052 has described a kind of method of improving Polyester Filament for preparing.According to this list of references, the spinning speed that this method adopts is 500～3000m/min.Do not do any narration about performance and fracture of wire number.Do not narrate the spinning head below yet and use post-heater.This causes the nucleocapsid structure of spun filament and the degree of crystallinity of increase inevitably, and therefore causes tensility not enough.Thereby productive rate is low and mostly the fracture of wire number is inevitable.
EP 0 799 331 B1 have described a kind of method for preparing industrial filament yarn, and its winding speed that yarn is adopted is greater than 6000m/min.In the method, will be by the high viscosity of solid-state post condensation preparation (IV＞0.86dl/g) section fusion in extruder, and be conducted to device for spinning.
The shortcoming of solid-state post condensation be this polycondensation mode can cause in addition the viscosity in single section inhomogeneous.For example, average viscosity is that the section of 0.98dl/g will have the viscosity apparently higher than 1.2dl/g on its outer surface.
Full-bodied like this extruding needs about 300 ℃ temperature.These high melt temperatures can cause bigger viscosity to descend, this viscosity descend obviously greater than 0.06dl/g (according in the number of the spinning station that provides and the transmission line and the melt residence time that produces in the spinning system and decide).Viscosity descends relevant with the increase of spun filament middle-end carboxyl number.For a person skilled in the art, be the measuring of thermal instability of melt with increase that viscosity descend to increase relevant end carboxyl concentration, it can cause in spinning-drawing-off the more and fracture of wire of broken end to increase.The end carboxyl that increases in the polyfilament yarn of dimensionally stable can damage the heat endurance and the hydrolytic stability of this yarn when further finished yarn.
EP 0 526 740 B1 have described a kind of birefringence of wherein spun filament and the method that degree of crystallinity is controlled.This can along with the change of operating condition by with the aliphatic dicarboxylic acid with 5～10 carbon atoms altogether and/or its carbonyl bond angular turn or its virtue nuclear have the substituent aromatic carboxylic acid of modification polyethylene terephthalate carried out modification, and/or realize by carrying out modification with the alkanediol with 3～10 carbon atoms or cycloalkanes glycol, diethylene glycol (DEG) or triethylene glycol or polyethylene glycol.
The shortcoming of this method is that the polyethylene terephthalate of after-condensation can not commercially availablely obtain, but the polyethylene terephthalate of special chemical modification.The polyethylene terephthalate of this chemical modification is in solid-state down after-condensation, and extrudes the high viscosity section subsequently, descends significantly and holds carboxyl to increase considerably in this process medium viscosity.In addition, lack information, these relevant key characters that also therefore constituted the yarn of dimensionally stable with following process about the final modulus of end carboxyl number purpose specifying information and the relevant industrial yarn that makes.
EP 0,423 213 has described a kind of preparation method of drawing-off polyethylene terephthalate yarn.The performance data (productive rate, fracture of wire number) that the value (E 4.5+HAS 177 ℃＜13.5%) of the final modulus height＞20g/den of this yarn, the value of stable, fracture strength that lacks the end carboxyl and DIMENSIONAL STABILITY is lower, particularly lack technology shows that performance is not good with regard to described method.
Although known the complete method series of the multifilament polyethylene terephthalate yarn that preparation size is stable, still need to guarantee the improvement technology of necessary premium properties (promptly in big commercial scale broken end and fracture of wire seldom).
Therefore the purpose of this invention is to provide a kind of provide obtain by the commercially available fabric polyester slice that gets and particularly suitable make the method for yarn that has good mechanical properties all the time of the reinforcing material of tire, conveyer belt and V-belt, and in this method the productive rate of dimensionally stable yarn increase, the fracture of wire decreased number.
Another object of the present invention is a kind of method with following feature:
-can use the commercially available polyethylene terephthalate section that gets with fabric viscosity as raw material and
-carry out the melt after-condensation with the acquisition high viscosity,
-it makes the uniformity height of high-viscosity melt,
-the concentration of stabilized end carboxyl in melt after-condensation process wherein,
-amplitude wherein little in spinning system medium viscosity decline scope or that end carboxyl number increases is little,
-wherein can be for spun filament is provided with optimum structure,
-with and show the relevant LASE5 modulus, percent thermal shrinkage of good especially and homogeneous and final modulus the yarn physical characteristic and
-wherein broken wires are few.
This purpose realizes by the method that is suitable for industrial multifilament polyester yarn by the following steps preparation:
-with deviation＜± inherent viscosity of 0.02dl/g is that the polyethylene terephthalate section of 0.55～0.70dl/g and the reagent that reduces end carboxyl concentration infeed in the extruder with fusion therein together and mixes,
-then this melt is infeeded in the reactor to handle high-viscosity melt, wherein the melt after-condensation is to inherent viscosity＞0.9dl/g, and end carboxyl concentration is reduced to＜15mmol/kg, and the temperature in the reactor is 268～278 ℃,
-force the melt handled in the reactor with the shear rate at＞2300/ second nib wall place by the spinning nib, then by heat-treatment zone, cooling zone and regulatory region, the yarn that solidifies is finished spinning and by the spinning hauling speed v of draw-gear with 2500～3400m/min it is taken out, thereby the spun filament that obtains comprises the architectural feature Q that meets the following conditions:
-1.333×10
-3×v+8.03≤Q≤-1.333×10
-3×v+9.03
Wherein Q is 1000 times of birefringence of the spun filament merchants with degree of crystallinity, makes that in the spun filament of 2 this structures of draw zone drawing-off total stretch ratio is 1.7/1～2.6/1, and HEAT SETTING is lax then, reels with the winding speed of＞5500m/min.
According to the favourable embodiment of the inventive method as described in the claim 2～5.
The present invention also provides the drawing-off polyethylene terephthalate multifilament according to claim 6.Claim 7～9 has related to the particularly advantageous embodiment of drawing-off polyethylene terephthalate multifilament of the present invention.
The present invention also provides multifilament polyester yarn according to the present invention strengthening the particularly purposes in the preferred automobile tyre of tire, conveyer belt and the V-belt etc. of industrial product.
The starting point of the method according to this invention is the polyethylene terephthalate section that the commercially available fabric viscosity that gets is 0.55～0.70dl/g.The viscosity deviation range of this section usually＜± 0.02dl/g.In extruder, make this section fusion.The reagent metering that will reduce the end carboxyl in addition infeeds the extruder inlet, and in extruder itself and PET melt is mixed together evenly.The temperature of the melt that comes out from extruder should be less than 275 ℃, preferably less than 272 ℃.
This melt is fed in the reactor by Melt Pump, preferred gear pump metering subsequently, and the melt after-condensation is to viscosity＞0.90dl/g there, and the end carboxyl concentration of PET melt is adjusted to less than 15mmol/kg simultaneously.
The reactor that is used to handle high-viscosity melt can be any reactor with following characteristics: guarantee the control of good mixing fully and even temperature, particularly wherein pending condensation polymer can not located deposition at the dead angle of wall, the dead angle of agitating device etc.Introduce suitable reactor among DE 3743051 A1, incorporated its disclosure into this paper by reference especially here.
Preferably advantageously use alkylene carbonates and allyl three phenyl phosphonium bromides that the end carboxyl concentration of high-viscosity polyester melt is set with the amount of 4000 to 16000ppm (are benchmark with the polyester).In DE19526405 A1, introduce the method that is fit to, incorporated its disclosure into this paper by reference especially here.
Reaction temperature in the reactor is preferably 268～278 ℃, and adopts vacuum so that final viscosity to be set in reactor; Described vacuum, promptly pressure is preferably 0.3～1.2mbar.The deviation range of final viscosity≤± 0.0075dl/g.
Subsequently the Melt Pump of after-condensation in the reactor is sent in the transmission line that leads to each filament spinning component that Spinning pumps wherein is installed.
Melt in the transmission line remains on＜285 ℃ temperature under.This temperature is starkly lower than in the accessible temperature of extruder medium-high viscosity PET slice spinning (being higher than 295 ℃).In spinning system according to the inventive method, the viscosity decline＜0.06dl/g in the transmission line, thereby compare half less than its drop-out value with traditional extruding spinning.
Preferably Spinning pumps is heated separately, and Spinning pumps forces described melt to pass through die assembly.Die assembly comprises filter, preferred nonwoven metallic filter, can leach any impurity thus from melt.Die pressure is preferably 200～600bar, and can adjust according to the melt throughput.
Described melt is pressed through the nib in the spinning head then under 300～315 ℃ spinning temperature, the diameter of selecting hole and number make the shear rate in the die channel be in the preferable range per second 2500～7500, and it calculates according to following formula:
γ＝4F/πr
3
Wherein F is with m
3/ s meter pass through flow rate capillaceous, r is the capillary radius in m.
The spinning head port of export is directly followed in the heat-treatment zone, and the length of heat-treatment zone is 100～500mm and is set to 270～370 ℃.The effect that melt solidifies that postpones is played in this district.Then the heat-treatment zone is that length is the cooling zone of 150～700mm, and it is preferably with the radially form operation of cooling axle.Be suitable for the laterally cooling axle that also has of doing the cooling zone in principle.
Use 10～40 standard cubic meters air-flow/kg polymer to come cooling yarn.Cooling blast is preferably 15～40 ℃.Then the cooling zone is a regulatory region, and wherein yarn stops 50～150 * 10
-3Second.The inner wall temperature of regulatory region is lower than 60 ℃.After leaving regulatory region, the silk thread that makes is finished spinning, and with the spinning hauling speed of 2500～3400m/min it is drawn.On the 4-double-roll type machine in 2 draw zones this silk thread is carried out drawing-off subsequently, HEAT SETTING is lax then, reels with the speed greater than 5500m/min.
Surprisingly only when satisfying following Q value condition for 2500m/min≤v≤3400m/min drawing-off operate and could prepare the high yarn of DIMENSIONAL STABILITY satisfactorily:
-1.333×10
-3×v+8.03≤Q≤-1.333×10
-3×v+9.03。
Here Q is used to measure purpose, the process transfer behind first pair of roller and 1000 times of the birefringence of the spun filament of the coming merchants with degree of crystallinity.V is the spinning hauling speed, and it equals the superficial velocity of first pair of roller.
Those of ordinary skills can be arranged on the Q value in the predetermined scope by regulating following condition: the time of staying in the flow rate/speed of the length of spinning temperature, die throat diameter, heat-treatment zone and temperature, cooling blast and temperature, the regulatory region.In principle, high Q value can cause improved tensility, promptly causes higher productive rate and less fracture of wire.High-crystallinity in the as-spun fibre can make drawing-off difficulty more, but it is to make the drawing-off yarn have the prerequisite of necessity of required DIMENSIONAL STABILITY.
In addition, the deviation range of polymer viscosity≤± 0.0075dl/g is the prerequisite of premium properties.
The combination that the multifilament polyester yarn that obtains shows following chemical property and physical property and operational characteristic:
Viscosity: 〉=0.84dl/g
End carboxyl :≤21mmol/kg
Fracture strength:＞69cN/tex
DIMENSIONAL STABILITY DS:＞10cN/dtex
*%
HAS under DS=Lase5/160 ℃
Final modulus:＜160cN/tex
Fracture of wire/10km :≤7
Broken end/t :≤8
Especially can be used as the reinforcing material of tire, conveyer belt and V-belt according to yarn of the present invention.
The characteristic value of reporting among aforementioned content and the back embodiment is measured in accordance with the following methods:
Inherent viscosity be 25 ℃ down with the 0.5g polyester in 3: 2 (w/w) phenol/1 in milliliter, the solution in the 2-dichloro-benzenes is measured.
End carboxyl concentration is by the ethanolic solution with 0.05N potassium hydroxide the bromthymol blue in 70: 30 (w/w) orthoresol/chloroformic solutions of polyethylene terephthalate to be carried out photometric titration to measure.
The birefringence of spun filament is to adopt wedge-formed incision to measure by the petrographic microscope that is equipped with gradient compensation device and green filter (540nm).What record is when linearly polarized photon optical path difference between ordinary light and the extraordinary ray when the silk thread.Birefringence is the merchant of optical path difference and silk thread diameter.In spinning-drawing-off operation, below the traction godet roller with spun remove fibers.
The degree of crystallinity of drawn fiber is not determined by the density of this fiber.Density is to measure in the gradient column that is being filled with normal heptane/carbon tetrachloride under 23 ℃.According to ASTM D1505-68 standard fabrication and calibration gradient column.
Calculate degree of crystallinity according to following formula then:
Ds-is in the sample in measurement density of g/ccm
The solid density of da-100% amorphous phase (1.335g/ccm)
The solid density of dc-100% crystalline phase (1.529g/ccm)
Strength character is that the extension speed with 200mm/min obtains the yarn mensuration that applies the 50 commentaries on classics/rice twists on it on 250mm length.Corresponding percentage elongation is that 5% o'clock power is known as Lase5 divided by line density in power-extension curve.
By elongation at break in fracture strength and the power-extension curve is that the difference of 2.4% o'clock intensity is calculated final modulus divided by 0.024.
Hot blast shrinkage factor (HAS) is to be 0.05cN/dtex, processing time to be to measure under the situation of 4min by shrinking measuring instrument (from Testrite/USA) 160 ℃ of following predrafts.
The present invention will be described in more detail for reference example:
Comparative example 1-3
Inherent viscosity is that 0.98dl/g, end carboxy CO OH are PETP section fusion in the 7E of German Barmag extruder that 16mmol/kg and wet amount are 25ppm.Under 160 crust, force the polymer of fusion to pass through static mixer, and it is conducted to 40cm
3Melt metering pump.Spinning pumps is controlled to be temperature 298 ℃ described melt Conveying to Zimmer BN 52 spinning systems, the system is characterized in that rectangular spinnerets assembly and the rectangular spinnerets with different spinneret orifice geometries.The throughput of melt is set so that 300 rhizoid lines have the finished product density of 1100dtex.Die pressure is 300bar.Laterally cooling off spun polyfilament yarn in the cooling system, finish spinning by the yarn oiler, and at room temperature it is conducted to the two rollers of first seal wire.Speed according to this first pair of roller of definition equals the spinning hauling speed.Nascent yarn is guided to coiler device to be provided for measuring the sample of birefringence and degree of crystallinity along first pair of roller.For the stable yarn of preparation size, guide described yarn from the seal wire pair rollers of first pair of roller, and at last it is reeled through other three heating.Between the first pair of roller and the 3rd pair of roller, yarn is carried out two step drawing-offs, simultaneously on the 3rd pair of roller with its HEAT SETTING, and between the 3rd pair of roller and up-coiler, make it lax.Two rollers of described three heating have following temperature:
Two roller 2:85 ℃
Two roller 3:240 ℃
Two roller 4:150 ℃
In all cases, the lax ratio between two rollers 4 and the two roller 3 is 0.995.Other is provided with shown in form.The technological parameter of spinning operation is identical in all three embodiment.
Inventive embodiments 4～6
PET section with following characteristic:
Inherent viscosity (IV): 0.60dl/g
End carboxyl: 22mmol/kg
Antimony content: 310ppm
Phosphorus content: 12ppm
Wet amount: 27ppm
With fusion in the 7E10 extruder of Barmag, and the Spinning pumps of this melt by 40ccm be conducted under 271 ℃ melt temperature in the high viscosity automatically cleaning polycondensation reactor (HVSR), described in DE3743051A1.
Enter the mouth end carboxyl concentration is set by under 75 ℃, the mixture metering of the ethylene carbonate of 6000ppm and allyl three phenyl phosphonium bromides (mixing ratio: 100: 8) infeeded extruder by gear pump.
After-condensation in the high viscosity self-cleaning reactor was carried out under the time of staying of the vacuum of 272 ℃ melt temperature, 0.8mbar and 160 minutes.The pumping from described reactor of highly condensed melt is come out, and be sent in the Spinning pumps.Pressure in the transmission line is reduced to 135bar.The time of staying in the transmission line between reactor discharging pump and Spinning pumps is 12 minutes.2 static mixers are installed in the transmission line.Heat this circuit to 280 ℃ with Diphyl (Diphyl).
Spinning pumps with described melt Conveying to Zimmer BN 110 spinning systems with circular spinneret assembly and annular spinning head.The melt throughput is set makes final line density be ... dtex.Radially cooling off spun polyfilament yarn from outside and inside in the cooling system, finish spinning by the yarn oiler, and at room temperature it is conducted to the two rollers of first seal wire.Distance between spinning head and the yarn oiler is 4250mm.Speed according to this first pair of roller of definition equals the spinning hauling speed.Nascent yarn is guided to coiler device to be provided for measuring the sample of birefringence and degree of crystallinity along first pair of roller.For the stable yarn of preparation size, guide described yarn from the seal wire pair rollers of first pair of roller, and at last it is reeled through other three heating.Between the first pair of roller and the 3rd pair of roller, yarn is carried out drawing-off, simultaneously on the 3rd pair of roller with its HEAT SETTING, and between the 3rd pair of roller and up-coiler, make it lax.Two rollers of described three heating have following temperature:
Two roller 2:85 ℃
Two roller 3:240 ℃
Two roller 4:140 ℃
In all cases, the lax ratio between two rollers 4 and the two roller 3 is 0.995.The different technological parameter of other setting and spinning operation is shown in form.
Form
| The embodiment sequence number | ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | |
| Invention | Invention | Invention | |||||
| The PET raw material, IV | ????dl/g | ????0.98 | ????0.98 | ????0.98 | ????0.6 | ????0.6 | ????0.6 |
| Extruding spinning when not having HVSR | Be | Be | Be | Not | Not | Not | |
| Direct fabrics when HVSR is arranged | Not | Not | Not | Be | Be | Be | |
| IV behind the HVSR | ????dl/g | ????- | ????- | ????- | ????0.94 | ????0.94 | ????0.94 |
| End carboxyl behind the HVSR | ????mmol/g | ????- | ????- | ????- | ????14 | ????14 | ????14 |
| Spinning temperature | ????℃ | ????310 | ????310 | ????310 | ????310 | ????310 | ????310 |
| The post-heater temperature | ????℃ | ????330 | ????330 | ????330 | ????330 | ????330 | ????330 |
| Rectangular spinnerets with horizontal cooling | ????℃ | Be | Be | Be | Not | Not | Not |
| The cooling blast temperature | ????℃ | ????16 | ????16 | ????16 | ????20 | ????20 | ????20 |
| The cooling shaft length | ????mm | ????300 | ????300 | ????300 | |||
| Cooling velocity | ????m/sec | ????0.6 | ????0.6 | ????0.6 | |||
| Has the radially annular spinning head of cooling | Not | Not | Not | Be | Be | Be | |
| Cooling blast speed | ????Nm3kg/PETP | ????28 | ????28 | ????28 | |||
| The cooling shaft length | ????mm | ????1500 | ????1500 | ????1500 | |||
| The time of staying in the regulatory region | ????msec | Do not have | Do not have | Do not have | ????72 | ????60 | ????54 |
| The spinning hauling speed | ????m/min | ????2500 | ????3000 | ????3250 | ????2500 | ????3000 | ????3250 |
| Q | ????3.8 | ????3.1 | ????3 | ????5.1 | ????4.8 | ????4.2 | |
| First draw ratio | ????1∶ | ????1.6 | ????1.45 | ????1.3 | ????1.6 | ????1.45 | ????1.3 |
| Total stretch ratio | ????1∶ | ????2.45 | ????2.1 | ????1.9 | ????2.45 | ????2.1 | ????1.95 |
| Total relaxation ratio | ????1∶ | ????0.974 | ????0.976 | ????0.985 | ????0.975 | ????0.977 | ????0.982 |
| Winding speed | ????m/min | ????5965 | ????6150 | ????6080 | ????5970 | ????6155 | ????6220 |
| Yarn viscosity | ????dl/g | ????0.86 | ????0.86 | ????0.86 | ????0.88 | ????0.88 | ????0.88 |
| IV | ????dl/g | ||||||
| End carboxyl in the yarn | ????mmol/kg | ????26 | ????26 | ????25 | ????20 | ????19 | ????19 |
| Fracture strength | ????cN/tex | ????70.5 | ????69 | ????65 | ????71.6 | ????70.5 | ????70.2 |
| DIMENSIONAL STABILITY | ????cN/tex％ | ????9.4 | ????10.3 | ????12.1 | ????10.3 | ????11.3 | ????13.2 |
| Shrinkage factor under 160 ℃ | ????％ | ????3.5 | ????3.4 | ????22.9 | ????3.4 | ????3.1 | ????2.6 |
| LASE5 | ????cN/tex | ????33 | ????35 | ????35 | ????35 | ????35 | ????37 |
| Final modulus | ????cN/tex | ????230 | ????247 | ????274 | ????106 | ????115 | ????132 |
| Broken end/t | ????n | ????8 | ????10 | ????11 | ????5 | ????6 | ????6 |
| Fracture of wire | ????n/10km | ????10 | ????14 | ????21 | ????3 | ????5 | ????6 |
Q=1000 * birefringence/degree of crystallinity
Shrinkage factor under DIMENSIONAL STABILITY=Lase5/160 ℃
Claims (12)
1. method that is suitable for industrial multifilament polyester yarn by following steps preparations:
-with deviation＜± inherent viscosity of 0.02dl/g is that the polyethylene terephthalate section of 0.55～0.70dl/g and the reagent that reduces end carboxyl concentration infeed in the extruder with fusion therein together and mixes,
-then this melt is infeeded in the reactor to handle high-viscosity melt, wherein the melt after-condensation is to inherent viscosity＞0.9dl/g, and end carboxyl concentration is reduced to＜15mmol/kg, and the temperature in the reactor is 268～278 ℃,
-force the melt of handling in the reactor to pass through spinning head with the shear rate at＞2300/ second nib wall place, then by heat-treatment zone, cooling zone and regulatory region, the yarn that solidifies is finished spinning and by the spinning hauling speed v of draw-gear with 2500～3400m/min it is drawn, thereby the spun filament that obtains comprises the architectural feature Q that meets the following conditions:
-1.333×10
-3×v+8.03≤Q≤-1.333×10
-3×v+9.03
Wherein Q is 1000 times of birefringence of the spun filament merchants with degree of crystallinity, makes that in the spun filament of 2 this structures of draw zone drawing-off total stretch ratio is 1.7/1～2.6/1, and HEAT SETTING is lax then, reels with the winding speed of＞5500m/min.
2. method according to claim 1 is characterized in that the processing in the reactor is carried out under 270～275 ℃.
3. method according to claim 1 and 2 is characterized in that with melt after-condensation to viscosity be 0.92～1.00.
4. according to each described method in the claim 1 to 3, it is characterized in that adopting the mixture of alkylene carbonates and allyl three phenyl phosphonium bromides to reduce the end carboxyl.
5. according to each described method in the claim 1 to 4, it is characterized in that adopting the reactor of DE 3 743 051 A1 instruction.
6. drawing-off polyethylene terephthalate multifilament with following combination property:
Viscosity: 〉=0.84dl/g
End carboxyl :≤21mmol/kg
Fracture strength:＞69cN/tex
DIMENSIONAL STABILITY DS:＞10cN/dtex*%
HAS under DS=Lase5/160 ℃
Final modulus:＜160cN/tex
Fracture of wire/10km :≤7
7. drawing-off polyethylene terephthalate multifilament according to claim 6 is characterized in that the viscosity that has is 0.85～0.90dl/g.
8. according to claim 6 or 7 described drawing-off polyethylene terephthalate multifilament, it is characterized in that the end carboxyl concentration that has is 17～21mmol/kg.
9. according to each described drawing-off polyethylene terephthalate multifilament in the claim 6 to 8, it is characterized in that the DIMENSIONAL STABILITY that has is 11～14.
In the claim 6 to 9 each polyester multifilament yarn described or that obtain by each method in the claim 1 to 5 in tire as the purposes of reinforcing material.
11. in the claim 6 to 9 each polyester multifilament yarn described or that obtain by each method in the claim 1 to 5 in conveyer belt as the purposes of reinforcing material.
12. in the claim 6 to 9 each polyester multifilament yarn described or that obtain by each method in the claim 1 to 5 in the V-belt as the purposes of reinforcing material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10201834.0 | 2002-01-18 | ||
| DE2002101834 DE10201834B4 (en) | 2002-01-18 | 2002-01-18 | Production of dimensionally stable polyester threads |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1617957A true CN1617957A (en) | 2005-05-18 |
| CN1308506C CN1308506C (en) | 2007-04-04 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038023385A Expired - Fee Related CN1308506C (en) | 2002-01-18 | 2003-01-07 | Production of dimensionally stable polyester yarns |
Country Status (6)
| Country | Link |
|---|---|
| CN (1) | CN1308506C (en) |
| AU (1) | AU2003210150A1 (en) |
| DE (1) | DE10201834B4 (en) |
| EA (1) | EA006140B1 (en) |
| TW (1) | TWI247828B (en) |
| WO (1) | WO2003060206A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102154728A (en) * | 2011-03-09 | 2011-08-17 | 宁波大发化纤有限公司 | Preparation method of deoiled hard short fibers |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634858A (en) * | 2012-04-24 | 2012-08-15 | 可隆（南京）特种纺织品有限公司 | Manufacture method of polyethylene terephthalate drawn wire, tyre cord fabric and manufacture method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4195052A (en) * | 1976-10-26 | 1980-03-25 | Celanese Corporation | Production of improved polyester filaments of high strength possessing an unusually stable internal structure |
| AU634484B2 (en) * | 1988-07-05 | 1993-02-25 | Performance Fibers, Inc. | Dimensionally stable polyester yarn for high tenacity treated cords |
| US5242645A (en) * | 1989-11-15 | 1993-09-07 | Toray Industries, Inc. | Rubber-reinforcing polyester fiber and process for preparation thereof |
| EP0526740B1 (en) * | 1991-07-05 | 1998-03-25 | Hoechst Aktiengesellschaft | High strength polyester yarn and method for its production |
| DE69518988T2 (en) * | 1994-12-23 | 2001-04-05 | Akzo Nobel Nv | METHOD FOR PRODUCING A CONTINUOUS POLYESTER FILM YARN, USE OF THE FILAMENT YARN AND CORD PRODUCED THEREOF |
| DE19526405B4 (en) * | 1995-07-19 | 2006-03-30 | Zimmer Ag | Process for reducing the carboxyl end groups of linear polyesters |
| ATE259435T1 (en) * | 1999-12-03 | 2004-02-15 | Rhodia Industrial Yarns Ag | METHOD FOR PRODUCING HYDROLYSIS STABILIZED MONOFILAMENTS FROM POLYESTER AND THEIR USE |
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2002
- 2002-01-18 DE DE2002101834 patent/DE10201834B4/en not_active Expired - Fee Related
- 2002-12-19 TW TW91136751A patent/TWI247828B/en not_active IP Right Cessation
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- 2003-01-07 AU AU2003210150A patent/AU2003210150A1/en not_active Abandoned
- 2003-01-07 EA EA200400960A patent/EA006140B1/en not_active IP Right Cessation
- 2003-01-07 CN CNB038023385A patent/CN1308506C/en not_active Expired - Fee Related
- 2003-01-07 WO PCT/EP2003/000050 patent/WO2003060206A1/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102154728A (en) * | 2011-03-09 | 2011-08-17 | 宁波大发化纤有限公司 | Preparation method of deoiled hard short fibers |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200302300A (en) | 2003-08-01 |
| TWI247828B (en) | 2006-01-21 |
| DE10201834B4 (en) | 2006-12-07 |
| AU2003210150A1 (en) | 2003-07-30 |
| EA200400960A1 (en) | 2004-12-30 |
| DE10201834A1 (en) | 2003-07-31 |
| WO2003060206A1 (en) | 2003-07-24 |
| EA006140B1 (en) | 2005-10-27 |
| CN1308506C (en) | 2007-04-04 |
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