CN1098148A - Low denier polybenzazole fibers and preparation thereof - Google Patents
Low denier polybenzazole fibers and preparation thereof Download PDFInfo
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- CN1098148A CN1098148A CN93121671A CN93121671A CN1098148A CN 1098148 A CN1098148 A CN 1098148A CN 93121671 A CN93121671 A CN 93121671A CN 93121671 A CN93121671 A CN 93121671A CN 1098148 A CN1098148 A CN 1098148A
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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
- D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
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Abstract
The method that herein disclosed is low denier polybenzazole fibers and make these low denier polybenzazole fibers.This method is to spin fiber by pore (0.0051 centimetre to 0.018 centimetre) with the spin-drawing rate between 12 to 60 from the low concentration spinning solution, does not have this fiber of at least 750 kms of reeling then damagedly.
Description
The present invention relates to poly-indoles (" PBZ ") fiber and manufacture method thereof.
Polybenzazole fiber comprises polybenzothiozole (" PBT ") fiber or polybenzoxazole (" PBO ") fiber.These PBZ fibers are high performance fibers, and they have good chemical resistance, heat endurance and mechanical performance.These characteristics make them become one of preferred material that is used for high-performance fiber goods and integrated application.
From PBZ the solution of all kinds of solvents polybenzazole fiber (see polymer science and technology encyclopedia, the 11st volume, 601-635) nominal diameter that has of the fiber that is produced is 16 to 20 microns.Is useful in order to make fiber in some final use, preferably makes the diameter of PBZ fiber less than 12 microns.Up to now, people also do not know to spin how equably diameter less than 12 microns PBZ fiber.
Another common methods of describing minor diameter is to be referred to as low dawn fiber.Dawn is any 9000 meters long stapled grammes per square metre numbers.Dawn is a direct computing system, wherein represents less size than low number and higher number is represented bigger size.Because the unit at dawn is the weight of every segment length, and diameter is a long measure, thus directly during comparative figures dawn and diameter be not interchangeable unit.Their relational equation is for density is 1.58 polybenzoxazole:
Fibre diameter (μ m)=(square root/long filament at dawn) * 9.4625
When generically referring to minor diameter, very thin fiber, term dawn and diameter but have interchangeability.
One aspect of the invention is the method for making the minor diameter polybenzazole fiber, it comprises:
(1) aperture by a spinning plate spins the poly-indoles spinning solution of the lyotropic liquid crystal that comprises polybenzazole polymers and a kind of solvent and produces the spinning solution fiber, and wherein the aperture of said aperture is 0.018 centimetre or littler.
(2) with the spin-drawing rate of 12-60 by one 40.6 centimetres or the narrower air gap above-mentioned spinning solution fiber that stretches.
(3) by being contacted with a kind of non-solvent, fiber removes most of solvent.
(4) coiling at least 750 kms do not have failed fibers.
Second aspect of the present invention is the indoles fiber of a kind of diameter between 4 to 12 microns.
Poly-indoles is a kind of rigid rod polymer, as described in polymer science and technology macropaedia the 11st volume 601 pages-635 pages.
The present invention uses the fiber that comprises polybenzoxazole or polybenzothiozole.Polybenzoxazole, polybenzothiozole and their random copolymer ordered copolymer and block copolymer have description in following document: people's such as Wolfe " composition of liquid crystal polymer, technology and product ", United States Patent (USP) 4,703,103(1987 October 27); People's such as Wolfe " composition of liquid crystal polymer, technology and product ", United States Patent (USP) 4,533,692(1985 August 6); " composition of poly-(the 2.6-benzothiazole) of liquid crystal, technology and products thereof " of people such as Wolfe, United States Patent (USP) 4,533,724(1985 August 6); " composition of liquid crystal polymer, technology and products thereof " of Wolfe, United States Patent (USP) 4,533,693(1985 August 6); " thermal oxide stable connect p-benzo-dioxazole and p-benzo double thiazole polymer " of Evers, United States Patent (USP) 4,359,567(1982 November 16); People's such as Tsai the method for block copolymer " make heterocycle ", United States Patent (USP) 4,578,432(1986 March 25); " polybenzothiozole and polybenzoxazole " in 11 polymer science and the engineering macropaedia, 601 pages (J, Wiley and Sons1988) and W, W, people's such as Adams " material science of rigid rod polymer and engineering " (investigation of materials association 1988).
This polymer may contain the AB-matrix, suc as formula 1(a) shown in, and/or the AA/BB matrix, suc as formula 1(b) shown in
Wherein:
Each Ar represents an aryl.This aryl may be heterocycle, as inferior pyridine radicals, but its carbocyclic ring preferably.Aryl can be a polycyclic system that condense or non-condensed, but 6 Yuans rings of a list preferably.Size is unimportant, but the carbon number that aryl comprises is advisable to be no more than 18, be no more than 12 better, be no more than 6 best.The example of the aryl that is fit to comprises the phenylene residue, tolylene residue, biphenylene residue and biphenylene ether residue.Ar ' in the AA/BB-matrix preferably 1,2,4,5-phenylene residue or its analog, the Ar in the AB-matrix preferably 1,3,4-phenylene residue or its analog.
Each Z is independently an oxygen atom or a sulphur atom.
Each DM is organic residue of a key or a divalence, and it does not interfere the synthetic of polymer, makes and use.Organic residue of this divalence can comprise an aliphatic group that preferably is no more than 12 carbon atoms, but the organic residue of this divalence preferably an aforesaid aryl (Ar), be desirably one 1 most, 4-phenylene residue or its analog.
Nitrogen-atoms on each pyrrole ring and Z part all combines with carbon atom in the adjacent aryl, so just formed one with aryl-fused 5 Yuans pyrrole rings.
Pyrrole ring in the AA/BB-matrix may be in cis or trans position mutually.Just as above-mentioned 11 polymer science and engineering macropaedia, 602 pages described.
This polymer is made up of better the poly-indoles matrix of AA/BB basically substantially to be consisted of by in the two one of the poly-indoles matrix of AB-or the poly-indoles matrix of AA/BB.The molecular structure of polymer can be rigid rod, a semi-rigid rod or a flexible ball of string.Rigid rod is comparatively desirable under the situation of AA/BB-polybenzazole polymers, and is comparatively desirable at second rigid rod of situation of AB-polybenzazole polymers.The Zui Hao Wei of pyrrole ring in polymer oxazole ring (Z=O).Preferred matrix is suc as formula 2(a)-(h) shown in:
The cis polybenzoxazole
Poly-[benzo (1,2-d:5,4-d ') Shuan oxazole-2,6-two bases-1,4-phenylene]
Trans-polybenzoxazole
Poly-[benzo (1,2-d:4,5-d ') Shuan oxazole-2,6-two bases-1,4-phenylene]
Trans-polybenzothiozole
This polymer is more satisfactory to be substantially by 2(a)-matrix shown in (h) forms, preferably substantially by the 2(a of some)-same a kind of matrix in (c) forms.
Each polymer is on average to contain at least 25 matrixes for well, and at least 50 matrixes are better, and at least 100 matrixes are the most desirable.Rigidity AA/BB-polybenzazole polymers logarithmic viscosity number in methanesulfonic acid in the time of 25 ℃ is preferably approximately at least 10 deciliter/gram (dl/g), betterly is 15dL/g approximately at least, is desirably 20dL/g approximately at least most.For some purpose, approximately perhaps the logarithmic viscosity number of 25dL/g or 30dL/g is best at least.60dL/g or higher logarithmic viscosity number are possible, but logarithmic viscosity number preferably is not more than about 45dL/g.The logarithmic viscosity number of semi-rigid AB-polybenzazole polymers is more satisfactory to be 5dL/g approximately at least, betterly is 10dL/g approximately at least, is desirably 15dL/g approximately at least most.
By spinning or extrusion spinning liquid, this polymer can be made fiber and film.Carry out spinning or extruding if can not obtain the polymer or the copolymer of new system, then polymer or the copolymer of making in the past can be dissolved in a kind of solvent to form a kind of solution or spinning solution.Some polybenzoxazoles and polybenzothiozole polymer dissolve in cresols, but preferably a kind of acid of dissolving this polymer of solvent.This acid is preferably non-oxidizing.The example of suitable acid comprises polyphosphoric acid, methanesulfonic acid and sulfuric acid and these sour mixtures.For well, polyphosphoric acid is better with polyphosphoric acid and/or methanesulfonic acid in this acid.
The concentration of the polymer that this spinning solution is contained should be enough high, so that a kind of solid-state product of formation that condenses, can't not handle to viscosity but this concentration is high spinning solution.When polymer when being rigidity or semirigid, the polymer concentration in the spinning solution preferably is high enough to provide a kind of fiber spinning from crystalline state liquid.The concentration of polymer is preferably and is approximately 7% of weight at least, more preferably is approximately 10% of weight at least, preferably is approximately 14% of weight at least.Cmax is mainly limited by practical factor, for example the viscosity of the solubility of polymer and the spinning solution narrated.Because these limiting factors are arranged, the concentration of polymer seldom surpasses 30% percentage by weight, generally is no more than about 20% percentage by weight.
Suitable polymer or copolymer and spinning solution can synthesize by known method, comprise such as people such as Wolfe at United States Patent (USP) 4,533,693(1985 August 6) in; People such as Sybert are at United States Patent (USP) 4,772,678(1988 September 20) in; Harris is at United States Patent (USP) 4,847,350(1989 July 11) in; And people such as Ledbetter is in " a kind of full experiment chamber method that is prepared rigid rod fibers by monomer ", rigid rod polymer material science and technology, 253-64(investigation of materials association, 1989 years) described method.Generally speaking, suitable monomer (AA-monomer and BB-monomer or AB-monomer) is reacted violent in addition stirring and high-intensity shearing in non-oxide environment in a kind of solution of non-oxidizable dehydracetic acid; Temperature increases in mode gradually or the slope, is increased to approximately at least 190 ℃ final temperature from the initial temperature that approximately is no more than 120 ℃.The example of the AA-monomer that is fit to comprises terephthalic acids and analog thereof.The example of the BB-monomer that is fit to comprises 4, the 6-diamino resorcin, and 2,5-diaminourea hydroquinones, 2, the 5-diaminostilbene, 4-two thio phenyls and analog thereof, they generally store with the form of acid salt.The example of the AB-monomer that is fit to comprises 3-amino-4-hydroxy benzoic acid, 3-hydroxyl-4-aminobenzoic acid, 3-amino-4-thiobenzoate, 3-sulfydryl-4-aminobenzoic acid and analog thereof.They generally store with the form of acid salt.
Spin pbo fiber
The preparation of PBO " spinning solution "
The PBO spinning solution is the solution of PBO polymer in a kind of solvent.Polybenzoxazoles only is only in as methanesulfonic acid or polyphosphoric acid soluble in very strong proton type acid solvent.Preferred solvent is polyphosphoric acid (PPA).The optium concentration of PBO in polyphosphoric acid is approximately 14% percentage by weight.The inherent viscosity of PBO/PPA should be the methanesulfonic acid solution of 0.05g/dL in 22-45dL/g(concentration when measuring 25 ℃) scope in.
Fiber can be spun by monofilament or multifilament threads.A kind of useful monfil spins and show (seeing " polybenzothiozole and polybenzoxazole ", polymer science and engineering macropaedia, second edition, 601 pages to 635 pages of the 11st volumes) in 625 page of the survey article of J.f.Wolfe.Spinning equipment preferably comprises one and has one or more pores and a spinning plate that forces spinning solution to pass through the device of these pores.When spinning plate had a plurality of pore, this equipment preferably also comprised a spinning mould so that with about identical pressure and flow velocity spinning solution is taken to each pore.The device that promotes spinning solution can be the extruder of a pump, piston or single screw rod or multiscrew.Spinning plate and spinning mould are called spinning plate together.Each part of this spinning plate all must be able to be handled high viscosity, corrosive polymer dope solution.
The spinning solution fiber
In case spinning solution is placed in the spinning plate, it just is heated to and reaches spinning temperature.Spinning temperature can be between 135 ℃ to 180 ℃, and the spinning temperature scope is 140 ℃ to 170 ℃ preferably, and best spinning temperature scope is 150 ℃ to 160 ℃.
Polymer dope by pore by spinning, from 0.0051 to 0.018 centimetre of pore size (2 to 7 mil), better scope is 0.0076 to 0.015 centimetre (3 to 6 mil), optimum diameter is 0.013 centimetre.
When spinning solution left spinning plate, its shearing rate was at 300 to 4000 seconds
-1Scope in, the better scope of shearing rate is 500 to 3000 seconds
-1, shearing rate is preferably 1500 seconds
-1
Along with PBO spins by spinning plate, the spinning solution fiber has just formed.These spinning solution fibers leave spinning plate and enter the space of a what is called " air gap ", and this space is present between the outlet side and coagulating bath of spinning plate.Gas in " air gap " can be air, but can be another gas also, such as nitrogen, and carbon dioxide, helium or argon gas.Temperature in the air gap to be to be advisable between 150 ℃ at 0 ℃, better then between 0 ℃ to 100 ℃, is preferably between 50 ℃ to 100 ℃.Air gap in the scope of 1.3 to 15 centimetres more fortunately (0.5 inches to 6 inches), is preferably in the scope of 2.5 to 10 centimetres (1 to 4 inches) in the scope of 0.64 to 41 centimetre (0.25 to 16 inch).
The spin-drawing rate is the ratio of fiber winding speed divided by the extruded velocity of spinning solution.Extruded velocity or by the rate of volume flow decision of spinning solution in extruder, or decided at the free dropleting speed beyond the spinning head by spinning spinning solution.For this operation, spun the free dropleting speed of spinning solution outside spinning head once to be used to determine the spin-drawing rate.The spin-drawing rate of this spinning once was maintained between 12 to 60, and scope is between 13 to 25 preferably, and best spin-drawing rate is about 15.
Solidify/cleaner bath or run into to and solidify/clean shower nozzle in case the spinning solution fiber leaves air gap and enters, remain in solvent (polyphosphoric acid) beginning in the fiber and separate with PBO polymer phase in the fiber and be diffused in the coagulating agent.This phase separation is called as and solidifies.Any use solidify or cleaner bath/shower nozzle all can moisture or water/acid blend, and preferred acid is that concentration is 30% or smaller phosphoric acid.Other coagulating agent or cleaning fluid can comprise organic solvent such as acetone, methyl alcohol or acetonitrile.
The cleaning of fiber, drying and heat setting
After being cleaned, fiber to carry out drying and heat setting to it.This fiber at first is dried to remove remaining surface water.In case after fiber is dried, just they are heat-treated.Preferably allow heat treatment be undertaken by a stove that inert gas such as nitrogen are housed.When fiber during, just be coupled with tension force on the fiber by the heat treatment element.Heat treatment can be carried out under the arbitrary temperature between 300 ℃ to 650 ℃, and temperature range is 400 ℃ to 650 ℃ and optimum temperature is 600 ℃ preferably.The heat treated holdup time is depended on temperature, and the time that hot more temperature needs is few more, and the heat treatment period scope is second to one minute.Preferred time span is between 3 seconds to 45 seconds, and better the heat treatment time scope is between 5 to 20 seconds, and best time range is between 8 to 15 seconds.Fiber all is under the tension force effect in heat treatment process.
When according to treatment conditions of the present invention, might in the long time, spin fiber and the fibre beakage that the unstability owing to spinning process produces does not take place.Spinning operation is started and the THE MEASUREMENT OF TIME of non-cracking can be expressed as the collected km number that does not have broken fibre.For the present invention, the unabroken fiber that can collect is at least 500 kms approximately.Betterly be about at least 600 kms, be desirably about 800 kms most.
The physical characteristic of the low dawn fiber produced by method of the present invention has been done detection.It is found that the scope by the tensile strength after the heat treatment of the low dawn fiber of this method manufacturing is to 6.07 capital handkerchiefs (625 kip/inches from 4.31 capital handkerchiefs
2To 880 kip/inches
2), and the scope of the tensile modulus of firm spun fiber is that 172.4 capital handkerchiefs are to (25,000,000 pounds/inch of 310.2 capital handkerchiefs
2To 45,000,000 pounds/inch
2).
The low dawn fiber of these polybenzoxazoles will use the anti-solvent of high-performance at those, is useful under the occasion of anti-cutting and fire-retardant fiber.And the feature of its tensile strength and modulus makes them be suitable for being used in the composite.
The embodiment that below provides is that conduct is to specific explanations of the present invention.Yet it should be understood that the present invention is not limited among the concrete statement among these embodiment.
The spinning of embodiment 1-monofilament
By polymerization PBO in PPA prepare that percentage by weight is 14%, inherent viscosity (" IV ") is 0.05g/dL with 25 ℃ of concentration 22 to 40dL/g(methanesulfonic acid serves as that the basis is determined) PBO/PPA spinning solution in the scope.Then these polymer dopes are used to spin fiber.Fibre spinning is to finish with the spinning plate in one four hole.In each spinning stroke, the diameter of hole that fiber passes through or pore (its professional address) all is specific.Fiber spins with 150 ℃ cylinder temperature.The spinning solution fiber leaves spinning head and passes through one 20 millimeters air gap, is wound on to soak with various winding speeds then to be located on 15 ℃ of reels in the water.Fiber washed in flowing water 48 hours.Air drying 24 hours, vacuumize 4 hours.They are heat-treated to 450 ℃ under the tension force effect then.Spinning condition and fibre diameter are listed in following table.Sample 1-7 is by the preparation of PBO spinning solution, its IV=19dL/g.
Table 1
The size in sample number hole (centimetre) spinning/extensibility fibre diameter (micron)
1 .0039 30-50 17-26
2 .0028 30-40 16-20
3 .0024 13 18-20
3α .0024 25-35 13-16
4 .0020 25-30 10-15
5 .0016 20-38 ≤12
6 .0012 15-30 12
7 .0008 15-30 ≤12
8* .0024 25-60 ≤12
9* .0020 20-40 ≤12
10* .0016 20-35 ≤12
11* .0012 15-35 ≤12
12* .0008 15-35 ≤12
The IV of * this PBO spinning solution is 26dL/g
Embodiment 2-spinning under the small-bore
To prepare percentage by weight be 14% IV is 0.05dL/g with 25 ℃ of concentration 22 to 40dL/g(methanesulfonic acid serves as that the basis is determined with the method identical with embodiment 1) PBO/PPA spinning solution in the scope.
Fibre spinning is by using the spinning plate that have 4 holes identical with embodiment 1 to finish.The spinning solution processing method is identical with embodiment 1.
Fiber spins under 150 ℃ cylinder temperature, and the spinning solution fiber leaves spinning plate, and the air gap by a 20mm also is collected into one and soaks on the reel of reeling with various speed in the water that is located at 15 ℃.Fiber washed in flowing water 48 hours, air drying 24 hours, vacuumize 4 hours.They are heat-treated to 450 ℃ under the effect of tension force then.
5.1 the single fiber of centimetre (2 inches) full-length strain rate with 0.01/ minute on an Instron Tensile testing machine stretches.Result of the test is that " kip per square inch " or msi are that " million poundages per square inch " are represented with ksi.1ksi=6.895 MPa (writing a Chinese character in simplified form MPa), 1msi=6.895 gpa (capital handkerchief).The result of the test of fibre spinning and tensile strength and modulus is listed in the table 2.
Table 2
The size spinning in sample number hole/fibre diameter heat treatment tension heat treatment tension
(centimetre) extensibility (micron) intensity (ksi) modulus (msi)
13 .01 12 8-9 686±59 34±5.0
14 .01 23 7-8 747±97 50±15
15 .01 31 5-6 738±105 51±17
The mean value of 12 to 19 samples is used for heat treatment tensile strength and heat treatment tensile modulus number.
The multifilament spinning of the low dawn pbo fiber of embodiment 3-
Prepare the PBO spinning solution by polymerization PBO in PPA.The such spinning solution of about 1000 grams is spun into fiber by a multifilament fiber spinning equipment.The multifilament fiber spinning equipment comprises a blend spinning liquid and make its uniform mixing arrangement under vacuum, comprises an acceptance, filters and carry the spinning plate of spinning solution to 36 holes (pore) weaving mould.One is equipped with 2 or the water tank of lining up the free moving runner of row more therein and is placed in below the spinning mould to receive spinning solution and the spinning solution fiber is solidified in water.The PBO spinning solution is added in the spinning equipment and mixed 4 hours at least, is transported to spinning plate then, and this spinning solution spins the spinning mould at 160 ℃ of quilts then.The size of pore is approximately 0.01 centimetre (4 mil) on the spinning plate.The spinning solution fiber that leaves by about 7.62 centimetres (3 inches) air gap and be immersed in the water, drawn around godet roller by fiber roll then by the distance of about 91.4 centimetres (3 inches) by wheel guiding.Then, fiber is sent on the coiler.
Then firm spun fiber was washed in flowing water 48 hours, in a chamber of crossing with purging with nitrogen gas, it is stored and drying again.Some fibers that tried are by heat treated under tension force.The just spun and dry pbo fiber of crossing all is used for carrying out microexamination and mechanical test.The full-length of tension test is 25.4 centimetres (10 inches), and the yarn coefficient of torsion is 6.Test result is that " kip number per square inch " or msi are that " million poundages per square inch " represent 1ksi=6.895 MPa (writing a Chinese character in simplified form MPa), 1msi=6.895 gpa (GPa) with Ksi.Test result is listed in table 3.
Table 3
Sample number pore size spinning/extensibility fibre diameter heat treatment tension heat treatment tension
(centimetre) (micron) intensity (ksi) modulus (msi)
16 .01 14 9.87 716.4±25.7 27.9±1.0
16* .01 14 9.87 *746.9±20.7 *40.1±1.4
17 .01 14 10.4 751.9±37.3 26.7±2.1
17a** .01 14 19.4** 744.8±41.3 **43.3±2.5
18 .01 14 9.2 771.3±48.8 31.0±1.6
18a** .01 14 9.2** 789.2±41.8 **43.7±1.4
19
x.05 200 14.9 524.5±76.4 21.3±4.3
19a
x** .05 200 14.9 577.4±39.9 **39.8±2.8
* fiber is 500 ℃ of heat treatments
The * fiber is 630 ℃ of heat treatments
X sample 19 and 19a are not embodiments of the invention.
These embodiment show from the mould of 0.01 centimetre of (4 mil) hole dimension spun 10 microns or more the fiber of minor diameter than from the 0.05(20 mil) tensile characteristics of the fiber made the mould of hole dimension has greatly improved, it is many 50% just to have spun the tensile modulus of small diameter fibers of state, tensile strength many 20%.
Claims (10)
1, a kind of method for preparing the poly-indoles of minor diameter, the step that comprises is:
(a), be that the hole of 0.018 centimetre or littler spinning plate is spun a kind of poly-indoles spinning solution of lyotropic liquid crystal that contains polybenzazole polymers and a kind of solvent and produced the spinning solution fiber by diameter;
(b), adopt the spin-drawing rate between 12 to 60, said spinning solution fiber is stretched by one 40.6 centimetres or littler air gap;
(c), by it being contacted with non-solvent to remove the most of solvent on the fiber;
(d), coiling at least 750 kms do not have failed fibers.
2, the method for claim 1 also comprises cleaning, the step of drying and heat treatment of fibre.
3, the method for claim 1, the aperture that it is characterized in that said pore is greater than 0.0051 centimetre, less than 0.018 centimetre.
4, the method for claim 1 is characterized in that the minor diameter polybenzazole fiber is a polybenzoxazole fibers.
5, the polybenzazole fiber of a kind of diameter between 4 to 12 microns.
6, polybenzazole fiber as claimed in claim 5 is characterized in that poly-indoles is a polybenzoxazole.
7, polybenzazole fiber as claimed in claim 5 is characterized in that poly-indoles is a polybenzothiozole.
8, polybenzazole fiber as claimed in claim 5 is characterized in that the length of failed fibers is not at least 500 kms.
9, polybenzazole fiber as claimed in claim 5 is characterized in that the length of failed fibers is not at least 600 kms.
10, polybenzazole fiber as claimed in claim 5 is characterized in that the length of failed fibers is not at least 750 kms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US98482892A | 1992-12-03 | 1992-12-03 | |
| US07/984,828 | 1992-12-03 |
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|---|---|
| CN1098148A true CN1098148A (en) | 1995-02-01 |
| CN1051341C CN1051341C (en) | 2000-04-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93121671A Expired - Fee Related CN1051341C (en) | 1992-12-03 | 1993-12-03 | Low denier polybenzazole fibers and the preparation thereof |
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|---|---|
| JP (1) | JP3265579B2 (en) |
| KR (1) | KR950704548A (en) |
| CN (1) | CN1051341C (en) |
| AU (1) | AU5682594A (en) |
| IL (1) | IL107735A0 (en) |
| MX (1) | MX9307665A (en) |
| TW (1) | TW257798B (en) |
| WO (1) | WO1994012700A1 (en) |
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| CN101258272B (en) * | 2005-03-28 | 2010-12-29 | 纳幕尔杜邦公司 | Hot surface hydrolysis of polyphosphoric acid in spun yarns |
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| US5773025A (en) | 1993-09-09 | 1998-06-30 | Edward Mendell Co., Inc. | Sustained release heterodisperse hydrogel systems--amorphous drugs |
| US5756040A (en) * | 1994-08-03 | 1998-05-26 | Toyobo Co., Ltd. | Process of making polybenzazole nonwoven fabric |
| US5756031A (en) * | 1994-08-12 | 1998-05-26 | Toyobo Co., Ltd. | Process for preparing polybenzazole filaments and fiber |
| US5525638A (en) * | 1994-09-30 | 1996-06-11 | The Dow Chemical Company | Process for the preparation of polybenzazole filaments and fibers |
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| US4533693A (en) * | 1982-09-17 | 1985-08-06 | Sri International | Liquid crystalline polymer compositions, process, and products |
| DE3330160A1 (en) * | 1983-08-20 | 1985-03-07 | Boehringer Ingelheim KG, 6507 Ingelheim | MONOCLONAL ANTIBODY WITH HIGH AFFINITY TO DIGOXIN |
| JPS6128015A (en) * | 1984-07-10 | 1986-02-07 | Asahi Chem Ind Co Ltd | Production of poly(p-phenylenebenzo-bis-thiazole fiber |
| JPH0284509A (en) * | 1988-09-20 | 1990-03-26 | Mitsui Petrochem Ind Ltd | Production of polybenzthizaole fiber, polybenzoxazole fiber or polybenzimidazole fiber |
| JPH0284511A (en) * | 1988-09-20 | 1990-03-26 | Mitsui Petrochem Ind Ltd | Production of polybenzthiazole drawn fiber, polybenzoxazole drawn fiber or polybenzimidazole drawn fiber |
| JPH0284510A (en) * | 1988-09-20 | 1990-03-26 | Mitsui Petrochem Ind Ltd | Production of polybenzthiazole fiber, polybenzoxazole fiber or polybenzimidazole fiber |
| JPH03104920A (en) * | 1989-09-14 | 1991-05-01 | Mitsui Petrochem Ind Ltd | Production of fiber of polybenzothiazoles, polybenzoxazoles or polybenzimidazoles |
| JPH03104921A (en) * | 1989-09-14 | 1991-05-01 | Mitsui Petrochem Ind Ltd | Production of fiber of polybenzothiazoles, polybenzoxazoles or polybenzimidazoles |
| CA2044407A1 (en) * | 1990-06-15 | 1991-12-16 | William C. Uy | Anisotropic spin dopes of reduced viscosity |
| JPH04194022A (en) * | 1990-11-28 | 1992-07-14 | Mitsui Petrochem Ind Ltd | Production of fiber of polybenzothiazoles, polybenzoxazoles or polybenzimidazoles |
| JPH04202257A (en) * | 1990-11-29 | 1992-07-23 | Mitsui Petrochem Ind Ltd | Wholly aromatic heterocyclic polymer compostion, fiber and film produced therefrom, and production thereof |
-
1993
- 1993-11-24 IL IL10773593A patent/IL107735A0/en unknown
- 1993-11-24 TW TW082109914A patent/TW257798B/zh active
- 1993-11-30 KR KR1019950702233A patent/KR950704548A/en not_active Application Discontinuation
- 1993-11-30 WO PCT/US1993/011587 patent/WO1994012700A1/en active Application Filing
- 1993-11-30 AU AU56825/94A patent/AU5682594A/en not_active Abandoned
- 1993-11-30 JP JP51344794A patent/JP3265579B2/en not_active Expired - Lifetime
- 1993-12-03 CN CN93121671A patent/CN1051341C/en not_active Expired - Fee Related
- 1993-12-03 MX MX9307665A patent/MX9307665A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101258272B (en) * | 2005-03-28 | 2010-12-29 | 纳幕尔杜邦公司 | Hot surface hydrolysis of polyphosphoric acid in spun yarns |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08504007A (en) | 1996-04-30 |
| IL107735A0 (en) | 1994-02-27 |
| AU5682594A (en) | 1994-06-22 |
| MX9307665A (en) | 1994-07-29 |
| WO1994012700A1 (en) | 1994-06-09 |
| CN1051341C (en) | 2000-04-12 |
| TW257798B (en) | 1995-09-21 |
| KR950704548A (en) | 1995-11-20 |
| JP3265579B2 (en) | 2002-03-11 |
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