CN1241223A - Dispersion spinning process for poly(tetrafluoroethylene) and related polymers - Google Patents
Dispersion spinning process for poly(tetrafluoroethylene) and related polymers Download PDFInfo
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Abstract
A process for preparing a dispersion spun fluorinated polymer fiber wherein the intermediate fiber structure, immediately before sintering, contains primarily ions characterized as fugitive ions.
Description
The present invention relates to be used for will poly-(tetrafluoroethylene) or the dispersion spinning of related polymer become fiber or this kind dispersion be configured as the method for molded article, wherein the fluorinated polymer structure of this sintering does not contain technology salt, acid and other impurity substantially.
Background of invention
Poly-(tetrafluoroethylene) and related polymer be to the excellent stability of light, heat, solvent, chemical etching and electric stress, makes this base polymer and to be used for various purposes by the goods of this base polymer manufacturing rather well received.Yet, because the complexity that this base polymer relates in fusion and solution processing is difficult to by conventional method their spinning or shaping.
A kind of method that is used to gather the shaping or the spinning of (tetrafluoroethylene) and related polymer thereof, it is mixture by this polymer beads aqueous dispersion and viscose glue, be shaped or spin this polymer, wherein cellulose xanthate is the soluble form of matrix polymer, for example can be seen in United States Patent (USP) 3,655,853; 3,114,672; And 2,772,444.
Although viscose glue with cause poly-(tetrafluoroethylene) and related polymer shaped fibers, is adopted viscose glue to exist some important disadvantages by generally.
Though known had some replacement scheme to the viscose glue forming process, still, adopt this class matrix polymer still will relate to organic solvent, surfactant or use that the two has concurrently mostly, for example can be seen in United States Patent (USP) 3,147,323; 3,118,846 and 2,951,047.
Produce the qualified sintering fluorinated olefin polymer goods or the method for fiber, usually require cautiously to select matrix polymer not contain ion or impurity to guarantee the intermediate fiber.The present invention allows to adopt various structure and chemical type, far-ranging matrix polymer, and it can also produce solid sintered fiber and goods simultaneously.
In dispersion spinning or shaping, the ion-transfer in the coagulating bath is in intermediate structure.These ions, for example hydrogen, sodium, sulfate ion can cause serious problem in the process that is converted into final sintering (coalescent) fluorinated olefin polymer fiber by the intermediate fibre structure.
The typical coagulating bath of using during dispersion is shaped is the acid bath that comprises sulfuric acid and sodium sulphate.Can under the temperature conditions of the coalescent requirement of fluorinated polymer, cause the degraded of intermediate fibre structure from the residual acid of sulfuric acid.The existence of salt can be accumulated to the 25wt% up to fibre structure sometimes, often makes the fiber of producing defective in mechanical properties.As a rule, the salt of intermediate fibre structure middle and high concentration even can hinder the formation of sintered fiber, this be because, make the intermediate fibre structure generation sintering that comprises salt residue, impossible also be unusual difficulty even if be not.
The inventor finds that high-purity, solid sintering fluorinated polymers fibres can be produced by carrying basic intermediate structure for fugitive ion (fugitiveion).Perhaps in other words, the invention provides a kind of intermediate structure that is substantially free of non-fugitive ion residue.
Summary of the invention
The invention provides the method for the fluorinated olefin polymer fiber of making dispersion spinning, it may further comprise the steps:
(a) produce the mixture of a fluorinated olefin polymer pellet moisture prose style free from parallelism and the matrix polymer aqueous solution;
(b) this mixture is expressed into contains in the coagulating bath of ion that finite concentration makes matrix polymer cohesion, thereby be configured as the intermediate fibre structure that carries ion species (ionic species); And
(c) with intermediate fibre structure sintering, so that matrix polymer decomposes and makes the fluorinated olefin polymer particles coalesce,
Wherein before facing sintering, this ion species is fugitive ion substantially, so-called fugitive ion is the such ion or the compound of partial ionization, it is when being heated to above 25 ℃ temperature but being lower than the temperature that causes the fluorinated olefin polymer particles coalesce, just volatilization or decomposition, thus volatile materials or carbonaceous residue only generated.
A kind of enforcement pattern of the present invention is by matrix polymer solidifying in mainly the comprising fugitive ion solution intermediate fibre structure that is shaped.
In implementing another kind of pattern of the present invention, a kind of intermediate fibre structure that only carries fugitive ion basically is shaped, in this pattern, make in the solution after matrix polymer solidifies comprising solidifying of the ion species that is selected from non-fugitive, fugitive or the two mixture, yet before sintering, the intermediate fibre structure contacts with the ion exchange solution that mainly comprises fugitive ion.
The inventive method can be used to be shaped multifilament, monofilament, film, tape and other molded articles.
Detailed Description Of The Invention
Term as used herein poly-(tetrafluoroethylene) and related polymer are meant poly-(tetrafluoroethylene) and the polymer that is referred to as fluorinated olefin polymer, the copolymer of tetrafluoroethylene and hexafluoropropene (FEP) for example, the copolymer of tetrafluoroethylene and perfluoroalkyl-vinyl ethers such as perfluoro propyl-vinyl ethers (PFA) and perfluor ethyl-vinyl ethers, the fluorinated olefins terpolymer that comprises the above various monomers of enumerating, so other are based copolymers with the tetrafluoroethylene.
Term as used herein PTFE is meant poly-(tetrafluoroethylene).
The term as used herein aqueous dispersion is meant the dispersion that particle forms in water, it can comprise various surfactant additives and be adjusting pH and the additive of keeping dispersion.
The term as used herein dispersion is shaped and is meant a kind of like this process, wherein the dispersion of insoluble polymer particle and dissolvable matrix polymer solution are mixed with each other, then, by the solution that solidifies of dissolved state contacts with making matrix polymer solution change into not with this mixture, this mixture is condensed.
Dispersion is shaped, and is referred to as the dispersion spinning of fibre usually, is making in the molded article very useful by fluorinated polymer.This base polymer melt extrudes or solvent spinning is shaped though be difficult to adopt, and can successfully be spun into silk with suitable matrix polymer solution through mixing the mixture that forms by the fluoropolymer particles aqueous dispersion.When this mixture when suitable coagulating bath contacts, just generate a kind of intermediate structure.Though intermediate structure mechanically is solid, still needing usually is enough to make the temperature of fluorinated polymer particles coalesce to make it to be configured as final sintering structure by intermediate structure is heated to.Through oversintering, matrix polymer just decomposes, and becomes escaping gas and remaining carbonaceous residue.
Intermediate structure of the present invention only comprises that class ion that characterizes with this speech of fugitive ion basically.The fugitive ion of term defined herein is meant the such ion or the compound of partial ionization, it is being heated to above 25 ℃ but be lower than the temperature that can cause poly-(tetrafluoroethylene) or related polymer particles coalesce, just volatilizees or is decomposed into the material of volatile or carbonaceous.Preferred low volatilization or decomposition temperature are about 100 ℃.
Method of the present invention adopts one of following 2 kinds of methods to be shaped and only carries the intermediate structure of fugitive ion basically: matrix polymer is not solidified in not containing non-fugitive ion solution substantially; Perhaps, after solidifying but before sintering, be fugitive ion by making the intermediate structure non-fugitive ion exchange that intermediate structure is entrained that contacts with ion exchange solution.
Ion species with regard to the object of the invention, can be divided into 2 classes.This 2 class is respectively fugitive with non-fugitive.The compound of any ion or part ion all can be included into 1 class in this 2 class.For example, sodium and the fugitive ion of sulfate ion right and wrong; Ammonium, and acetate ion and acetic acid are the examples of fugitive ion.This paper will call fugitive ion salt to the salt that is made of fugitive ion below, and be called fugitive ionic acid by the acid that the acid of fugitive ion or partial ionization constitutes.
Term carries or is carried, and when being used in reference to the intermediate fibre structure, is meant to be absorbed by intermediate structure or adsorb from the teeth outwards, perhaps is attached to inside.
In order to obtain useful coalescent fluorinated olefin polymer fiber, crucial is, the intermediate fibre structure must not contain fiber sintering and/or additive and/or dispersant that the harmful ion that absorbs from coagulating bath of final coalescent fluorinated polymer fibre property and other impurity are for example existed original fluorinated polymer dispersion before facing sintering.The invention provides a kind of dispersion manufacturing process of making goods, particularly fiber by poly-(tetrafluoroethylene) that do not contain the ion that disturbs sintering or reduce the sintered fiber serviceability and related polymer thereof.
The present invention produces the intermediate fibre structure that does not contain harmful ion substantially, and it is to realize for fugitive ion in sintering step by employing is a kind of in coagulating bath or in ion exchange solution.The compound of these ions or part ion will volatilize or be decomposed into, or volatile as water vapour and carbon dioxide, or carbonaceous and material that do not damage the general serviceability of sintered fiber.By the fugitive ionogenic carbonaceous material of the inventive method, as decomposing the carbonaceous material that produces by matrix polymer, can be by from sintered fiber, being removed by " bleaching ".
Though the selection of fugitive ion is somewhat dependent upon the fusing point of fluorinated olefin polymer, usually, to be those be higher than 25 ℃ and be lower than the ion that about 250～350 ℃ temperature is decomposed into volatility or carbonaceous material to fugitive ion.For example, the fusing point of FEP is about 253 ℃～282 ℃; PFA's is about 306 ℃; PTFE's is about 335～345 ℃.When enforcement was of the present invention, the boiling point or the decomposition temperature that are used for the fugitive ion of FEP should be lower than the analog value that is used for PFA or PTFE.Certainly, perhaps the fugitive ion that can be used for FEP can be used for PFA or PTFE equally.
Fugitive ion comprises by hydrogen, carbon, oxygen and/or nitrogen and constitutes and be higher than 25 ℃ but the organic acid and the organic acid ammonium salts that are lower than about 350 ℃ of volatilizations or decompose.The preferred upper limit of volatilization/decomposition temperature scope begins low about 20～30 ℃ of coalescent temperature than fluorinated polymers fibres.The example of fugitive ionic compound comprises oxalic acid, acetic acid, citric acid, formic acid, propionic acid, malic acid, butyric acid, acrylic acid, ammonium oxalate, ammonium acetate, ammonium formate, propionic acid ammonium, malic acid ammonium, butyric acid ammonium, ammonium acrylate, ammoniacal liquor and composition thereof, and other compounds that possess requirement volatility or decomposability.When fugitive ion is when being selected from the fugitive ion that just decomposes below 100 ℃, care should be used to when selecting matrix polymer must be avoided the situation that the dissolubility to matrix polymer has a negative impact that loses of ion species.
Be included as the fugitive ion that the enough concentration that matrix polymer solidifies required pH and salinity is provided according to the coagulating bath of the inventive method.Coagulating bath can comprise one of fugitive ion salt or acid separately, perhaps fugitive ion salt and sour mixture.
Preferred coagulating bath is the aqueous solution, though, solidify also and can in the coagulating bath of the mixture that comprises water and a small amount of solubility organic compound, realize.
In some cases, may preferably allow matrix polymer in the coagulating bath that comprises non-fugitive ion, solidify.In this case, this method still can have benefit of the present invention, only needs after coagulation step but before sintering step, sets up ion exchange and bathes to remove and to use fugitive ion to replace non-fugitive ion.The contact time in ion exchange solution and the concentration of fugitive ion can be adjusted to, the level that makes whole basically entrained non-fugitive ions of intermediate fibre structure all be removed or replace.
Preferred ion exchange solution is the aqueous solution of fugitive ion, though the small amounts of water soluble organic solvent also can be present in this solution.The actual composition of this wash solution and solidifies the same of solution, and also adjustable being fitted on makes the intensity of intermediate fibre structure reach optimization.Ion exchange solution is not strict with and is contained non-fugitive ion anything but.Said as the front, only importantly, the entrained non-fugitive ion concentration of intermediate fibre strength should be hanged down is enough to make the degree that qualified mechanical performance can be provided behind the fiber sintering.Qualified mechanical performance is represented with the sintered fiber TENSILE STRENGTH, measures according to ASTM methods of test D2256-90, should be greater than about 0.5g/dtex.
For example, in the methods of the invention, if use the sulfate ion coagulating bath, then the fibre structure that solidifies of sulfate ion can place and for example comprise that the ion exchange solution of acetic acid and ammonium acetate washs.Fugitive ion concentration wherein can be adjusted to the non-fugitive ion that makes in the fibre structure and obtains displacement, does not make the intensity of intermediate fiber that significantly loss takes place simultaneously, is removed from fiber until sulfate ion.
Abundant degree and the cleaning solution ion concentration of intermediate fibre structure and ion exchange wash solution contact time, the existence of remaining non-fugitive ion that can be by measuring the fibre structure sample is optimized.For example, trace element analysis is the known instrumental methods of those skilled in the art as Atomic Absorption or atomic emissions or other, can be used to determine whether there are these elements in the fibre structure.
The inventor's experience shows that the entrained non-fugitive ion of intermediate fiber can be replaced at an easy rate.The inventor observes, and sodium in the intermediate fiber and sulfate ion concentration can be reduced to so low by the ion exchange washing, so that the concentration of these ions in the technology sample is low unexpectedly to below the sensitivity of some trace metal analysis technology.For implementing purpose of the present invention, facing the preceding non-fugitive ion concentration of sintering may not need so low.Generally speaking, only need will non-fugitive ion concentration be reduced to about 0.2wt% less than the intermediate fibre structure that wets.
It is about 5 or above condition that strong non-fugitive acid concentration in the methods of the invention must satisfy the pH that makes the intermediate fibre structure.
But whether a kind of very effectively non-fugitive ion of so accurate check is replaced into the method for fugitive ion fully, sees exactly smoothly whether the intermediate fiber carries out in sintering step.The intermediate fiber when non-fugitive ion concentration is too high, can shows and be clamminess and have bigger fracture tendency.One is to place ion exchange solution to wash fiber for reaching the actual practice that non-fugitive ion concentration fully replaces, and can waltz through sintering step until fiber.In case the intermediate fiber can pass through smoothly, just available chemistry and instrument analytical method are checked non-fugitive ion concentration, to determine processing and needed concentration of final serviceability and wash time.
Can adopt common chemical test to come testing fiber to wash the existence of non-fugitive ion in the solution that uses.For example, under the situation of sulfate ion, a used wash solution can be joined in the barium chloride weak solution.The existence of sulfate radical will be indicated by the precipitation of barium sulfate.Such chemical operation program also can be applicable to the sample of intermediate fibre structure, only needs this moment the intermediate fibre structure is dissolved in the medium that does not disturb the chemical test that is used to refer to one or more non-fugitive ions existence of being studied.
In case it is abundant to determine ion exchange washing, just can find out and make that intermediate and sintered fiber can the quantity-produced processing conditions, only require whether fully monitoring regularly to ion exchange.
Can the composition of fugitive ion coagulating bath or ion exchange wash solution be optimized, so that the fibre structure of suitable strength to be provided, optimization can realize so that the intermediate fiber that can accept intensity to be provided by the concentration of regulating acid and salt.
Matrix polymer of the present invention can be such polymer that only comprises hydrogen, carbon, oxygen and nitrogen, and it may be dissolved in the aqueous solution, but can solidify or be precipitated out by adding salt or changing pH.The preferred cellulose polymer, because this base polymer is being lower than most of fluorinated olefin polymer melt temperature not fusion of scope or softening, and when sintering, this polymer just is decomposed into carbonaceous material.For example, this kind cellulosic polymer is methylcellulose, hydroxyethylcellulose, methylhydroxypropylcellulose, hydroxypropyl methylcellulose, hydroxypropyl cellulose, ethyl cellulose and carboxymethyl cellulose.Particularly, the polymer such as carboxymethyl cellulose, solubility in water is excessive usually for it, so that can not form the intermediate structure that can remove harmful substance by washing, can be used as matrix polymer in the methods of the invention.The present invention also not only is confined to those at the matrix polymer that solidifies in fugitive ion coagulating bath, because undesirable solable matter can be removed and replace to the ion exchange wash solution also.
The matrix solution of any matrix polymer of the present invention or its mixture all can prepare by specific matrix polymer is dissolved in the water or in acidity or the alkaline solution as required.
The temperature of coagulating bath and ion exchange wash solution can be adjusted to the level that the intermediate of requirement fibre structure performance can be provided, but coagulating bath is mostly in the operation of 25 ℃～90 ℃ temperature range, and preferred temperature range then is about 40 ℃～about 60 ℃.
Employed spinning or forming composition in the inventive method are to be mixed and made into mutually with matrix polymer solution by the aqueous dispersion with fluorinated polymers composition granule of the present invention.The aqueous dispersion of fluorinated olefin polymer particle, for example technical known those all can be used in the inventive method.The concentration of preferred solution mesostroma polymer is 3～10wt%.Subsequently, these components are mixed, mixed proportion should make the ratio of the weight of polymer beads in the intermediate fibre structure and matrix polymer weight about 3: 1～about 20: 1 scope, is preferably about 9: 1.
Though in most of the cases, matrix polymer solution of the present invention is stable, and gelling can not appear along with useful life, but preferably, matrix polymer solution mixes before facing use with the fluorinated polymer dispersion again, with homogeneity that guarantees this mixture and the precipitation of avoiding occurring the fluorinated polymer dispersion granule.
Test method
Polymer viscosity
Polymer solution viscosity is measured by the following method:
Treat the liquor sample of viscosimetric, after filtering, be placed in the vacuum chamber and maintain under the vacuum until no longer including visible trace bubble.The sample of q.s is transferred in the 600ml beaker, makes beaker pour into the degree of depth to 10cm.Subsequently, this sample is placed in that the temperature until whole sample becomes unanimity in the water bath with thermostatic control that is set in 25 ℃.
Adopt Brookfield HB-T type viscometer determining viscosity.The beaker that above-mentioned 600ml is filled sample is placed on below the viscosimeter, and No. 2 rotors are installed on viscosimeter.Regulate the height of viscosimeter, touch flow surface until the breach of armature spindle, the position of adjusting beaker makes sample be in the center.Start viscosimeter so that make rotor begin rotation, note viscosity reading and temperature then.
The Brookfield reading of record, the Brookfield coefficient table that utilizes suitable ISO 9002 to authenticate according to rotor number, RPM number and Brookfield reading, is scaled viscosity.
Embodiment
Example 1
The formulations prepared from solutions process is: it is that about 0.30 carboxymethyl cellulose (CMC) places the about 1.0 ℃ soft water of 17.7 liters to make slurry that 1.58kg is contained wet 6.2wt%, substitution value.After CMC is soaked, under 4.5 ℃, in water/CMC mixture, add the 12.3kg23% sodium hydroxide solution.The mixture that forms stirs 1h down in vacuum (about 29mm mercury column), then, is filled in the film degasser of operating under about 29mm mercury column vacuum through 50 μ m polypropylene mat bag type filters.The solution that is obtained is 3516mPas 25 ℃ viscosity.
Above-mentioned flow of solution and TEF 3311 poly-(tetrafluoroethylene) be dispersion (E.I.Du Pont Company (PTFE), Wilmington, DE provides) the stream merging, control relative discharge therebetween, make that the weight ratio of PTFE and CMC is 8.1, merge stream and in online static mixer, mix.Subsequently, the mixture that is obtained is crossed spinning head by pump pressure, and spinning head has 120 holes (every bore dia 7 mils) and is immersed in below the coagulating bath liquid level.Coagulating bath solution is 5% sulfuric acid and 18% sodium sulphate.Bathe temperature and maintain 52 ℃ ± 2 ℃.
Subsequently, the intermediate fiber of gained passes and maintains 44 ℃ 0.4% acetic acid washing bath, then on one group of rotation hot-rolling.The surface temperature of these hot-rollings maintains 250 ℃ ± 5 ℃, thereby makes the intermediate fiber drying.
Yarn is then around to another group rotation hot-rolling.The surface temperature of this group hot-rolling maintains 375 ℃ ± 5 ℃, thereby makes fiber sintering.
This yarn and then on one group of " draw roll " that does not heat, and twine multi-turn thereon.Set the speed difference between second group of hot-rolling and " draw roll ", make yarn be stretched to 8.08 times.Here it is so-called draw ratio.Come out from draw roll, yarn is wound up on the paper bobbin.
The sintering yarn linear density that obtains is 757dtex.Its intensity is 1.63g/dtex.
Example 2
Fibre spinning is substantially according to example 1, and just draw ratio is set at 7.73.
The line density of the yarn that obtains is 770dtex.Its intensity is 1.67g/dtex.
Example 3
Fibre spinning is substantially according to example 1, and just draw ratio is set at 6.31.
The line density of the yarn that obtains is 882dtex.Its intensity is 1.48g/dtex.
After the ion exchange washing, with the sodium amount that contains of analysis of emission spectrography intermediate fibrous structure sample, as the method for na concn in the fibre structure of measuring dry and sintering.The sodium content measured value is 570ppm.
Example 4
Fibre spinning is substantially according to example 1, and just draw ratio is set at 5.05.
The yarn linear density that obtains is 1187.7dtex.Its intensity is 1.21g/dtex.
Example 5
Fibre spinning is substantially according to example 1, and just draw ratio is set at 4.29.
The yarn linear density that obtains is 1187.7dtex.Its intensity is 1.19g/dtex.
Example 6
The formulations prepared from solutions process is: place the about 80 ℃ soft water of 30.3 liters to make slurry the methylcellulose (MC) of 1.26kg (containing wet 3.3wt%).After MC is soaked, temperature is reduced to about 25 ℃.The mixture that forms stirs 1h down in vacuum (about 29mm mercury column), then, is filled in the film degasser of operating under about 29mm mercury column vacuum through 10 μ m polypropylene mat bag type filters.The solution that is obtained is about 5000mPas 25 ℃ viscosity.
Above-mentioned flow of solution and the TEF of Du Pont 3311 poly-(tetrafluoroethylene) (PTFE) stream of dispersion merge, and control relative discharge therebetween, make that PTFE and the ratio of MC are 7.9, and mix in online static mixer.Subsequently, the mixture that is obtained is crossed spinning head by pump pressure, and spinning head has 180 holes (6 mil diameter) and is immersed in below the coagulating bath liquid level.Coagulation bath composition is 40% ammonium acetate.Bathe temperature and maintain 65 ℃ ± 5 ℃.Subsequently, the fiber that is obtained forwards on one group of rotation hot-rolling.The surface temperature of these hot-rollings maintains 200 ℃ ± 5 ℃, thereby makes fiber drying.
Yarn forwards on another group rotation hot-rolling.The surface temperature of this group hot-rolling maintains 360 ℃ ± 5 ℃, thereby makes fiber sintering.
This yarn forwards on one group of " draw roll " that does not heat, and twines multi-turn thereon.Set the speed difference between second group of hot-rolling and " draw roll ", make yarn be stretched to 4.3 times.Here it is so-called draw ratio.Come out from draw roll, yarn is wound up on the paper bobbin.
The yarn linear density that obtains is 731dtex.Its intensity is 0.891g/dtex.
Example 7
Fibre spinning is substantially according to example 6, and just draw ratio is set at 5.1.
The yarn linear density that obtains is 460dtex.Its intensity is 0.981g/dtex.
Example 8
Fibre spinning is substantially according to example 6, and just draw ratio is set at 6.22.
The yarn linear density that obtains is 413dtex.Its intensity is 1.44g/dtex.
Example 9
Fibre spinning is substantially according to example 6, and just draw ratio is set at 7.07.
The yarn linear density that obtains is 616dtex.Its intensity is 1.42g/dtex.
Claims (6)
1. method of making the fluorinated olefin polymer fiber of dispersion spinning, it may further comprise the steps:
(a) produce the aqueous dispersion of fluorinated olefin polymer particle and the mixture of the matrix polymer aqueous solution;
(b) this mixture is expressed into contains in the coagulating bath of ion that finite concentration makes matrix polymer cohesion, thereby be configured as the intermediate fibre structure that carries ion species; And
(c) with intermediate fibre structure sintering, so that matrix polymer decomposes and makes the fluorinated olefin polymer particles coalesce,
Wherein before facing sintering, this ion species is fugitive ion basically, wherein fugitive ion is the such ion or the compound of partial ionization, it is when being heated to above 25 ℃ temperature but being lower than the temperature that causes the fluorinated olefin polymer particles coalesce, just volatilization or decomposition, thus volatile materials or carbonaceous residue only generated.
2. the process of claim 1 wherein that the intermediate fibre structure solidifies in the aqueous solution that comprises fugitive ion basically.
3. the method for claim 1, wherein comprising after solidifying of the ion species that is selected from non-fugitive, fugitive or its mixture solidify in the solution when matrix polymer, but before sintering, this intermediate fibre structure contacts with the ion exchange solution that comprises fugitive ion basically.
4. the process of claim 1 wherein that fluorinated polymer is selected from the copolymer of copolymer, tetrafluoroethylene and perfluoroalkyl-vinyl ethers of poly-(tetrafluoroethylene), tetrafluoroethylene and hexafluoropropene and the fluorinated olefins terpolymer of these monomers.
5. the process of claim 1 wherein that this matrix polymer is selected from methylcellulose, hydroxyethylcellulose, methylhydroxypropylcellulose, hydroxypropyl methylcellulose, hydroxypropyl cellulose, ethyl cellulose and carboxymethyl cellulose.
6. the process of claim 1 wherein that fugitive ion is selected from oxalic acid, acetic acid, citric acid, formic acid, propionic acid, malic acid, butyric acid, acrylic acid, ammonium oxalate, ammonium acetate, ammonium formate, propionic acid ammonium, malic acid ammonium, butyric acid ammonium, ammonium acrylate, ammoniacal liquor and composition thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97180874 CN1241223A (en) | 1996-12-20 | 1997-12-16 | Dispersion spinning process for poly(tetrafluoroethylene) and related polymers |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/770,531 | 1996-12-20 | ||
| CN 97180874 CN1241223A (en) | 1996-12-20 | 1997-12-16 | Dispersion spinning process for poly(tetrafluoroethylene) and related polymers |
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| CN1241223A true CN1241223A (en) | 2000-01-12 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100529204C (en) * | 2003-12-31 | 2009-08-19 | 纳幕尔杜邦公司 | Dispersion spinning core-shell fluoropolymers |
| CN109913969A (en) * | 2013-07-29 | 2019-06-21 | 东丽含氟纤维（美国）公司 | Wear improved polytetrafluoroethylene (PTFE) (PTFE) fiber and its manufacturing method |
-
1997
- 1997-12-16 CN CN 97180874 patent/CN1241223A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100529204C (en) * | 2003-12-31 | 2009-08-19 | 纳幕尔杜邦公司 | Dispersion spinning core-shell fluoropolymers |
| CN109913969A (en) * | 2013-07-29 | 2019-06-21 | 东丽含氟纤维（美国）公司 | Wear improved polytetrafluoroethylene (PTFE) (PTFE) fiber and its manufacturing method |
| CN109913969B (en) * | 2013-07-29 | 2021-10-08 | 东丽含氟纤维（美国）公司 | Abrasion modified Polytetrafluoroethylene (PTFE) fibers and methods of making same |
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