CA1335745C

CA1335745C - Polyphenylene sulfone fibers and a method for production thereof

Info

Publication number: CA1335745C
Application number: CA000552830A
Authority: CA
Inventors: Masao Umezawa; Toshio Tsubota; Shiro Imai
Original assignee: Toray Industries Inc
Current assignee: Ticona GmbH
Priority date: 1986-09-26
Filing date: 1987-11-26
Publication date: 1995-05-30
Anticipated expiration: 2012-05-30

Abstract

Disclosed are polyphenylene sulfone fibers mainly con-sisting of a structural unit represented by the general formula (wherein x is 0 or 1 or 2, ?, the average value of x is 1.0 to 2.0 and the bond attached to the benzene ring is in the para- or meta-position with respect to the SOx group). The fibers can be obtained by oxidizing polyphenylene sulfide fibers mainly consisting of a structural unit represented by the formula

Description

SPECIFICATION
.

POLYPHENYLENE SULFONE FIBERS AND A
METHOD FOR PRODUCTION T~EREOF

Technological Field The present invention relates to polyphenylene sulfone fibers having excellent heat resistance and chemical resistance and a method for production thereof.

Background Technology As polyarylene sulfone fibers, porous fibers consisting of the structural units containing ether bondings in their main chains are known. However, these so-called polyethersulfones containing ether bonds in their main chains dissolve in amide type organic solvents and although their heat resistance and chemical resistance are excellent, there is a limitation.
On the other hand, crystalline polyparaphenylene sulfone powder whose melting point is higher than 500.C
and having heat resistance has been known, but it is practically impossible to carry out melt-molding or solution-molding thereof. There are however some examples cf film-forming in Japanese Laid-Open Patent Publication 92828/1985 and 92829/1985.

A

Moreover, in Japanese Patent Publication 35370/1984, it is proposed that the surface of polyphenylene sulfide fibers are treated with hydrogen peroxide or sodium hypochlorite and so on to make the fibers infusible. However, fibers obtained by this method are very brittle and have low strength. Moreover, there are such defects that cracks often occur and fibrillation occurs on the (treated) surface layers of the fibers.
Disclosure of the Invention The present invention provides polyphenylene sulfone fibers mainly consisting of a structural unit represented by a general formula ~ Sx ? (where x is 0 or 1 or 2, x, the average value of x, is 1.0 to 2.0 and the bond attached to the benzene ring is in para- or meta-position with respect to the Sx group).
Another aspect of the invention provides a method for production of the polyphenylene sulfone fibers by oxidizing poly-phenylene sulfide fibers mainly consisting of a constituting unit represented by a general formula ~ S __L- (wherein the bond attached to the benzene ring is in para- or meta-position with respect to the S atom) with an organic peroxide to poly-phenylene sulfone fibers represented by a main constituting unit ~Sx ) .
A further aspect of the invention provides a woven, knitted or non-woven sheet or fabric made of the polyphenylene sulfone fiber.

13357~5 66623-186 New fibers having a distinctively excellent chemical resistance against acids such as sulfuric acid and so on and bases such as sodium hydroxide aqueous solution and so on as well as an excellent heat stability at a temperature higher than 200C can be obtained according to the present invention.
More details will be explained below.
When x is less than 1.0, the distinctively excellent heat resistance cannot be obtained. The average value x is preferably more than 1.4. Moreover, the ratio of SO2/SOx ~namely the ratio of the sulfur atoms in the sulfone form (SO2) to the total sulfur atoms in the sulfide (S), sulfine (SO) and sulfone (SO2) forms) is more than 0.3, preferably more than 0.5 and more preferably more than 0.7. The ratio of SO2/SO is preferably more than 1.0, more preferably more than 2.0 and especially more preferably more than 3Ø Almost perfectly polysulfonated products wherein oxidized ratio of sulfur atoms in the polymer is more than 0.9 and the ratio of SO2/SO is ~3 is expecially preferable because ultrahigh heat resistance can be obtained. In this case, the formation of so-called three dimensional structure wherein main chains are partially bonded with oxygen atoms and so on can be observed.
The bonds between the benzene ring and the sulfur atom in the main chain are in para-or meta-position, but the para bonding is preferable beOEause a higher crystallinity can be obtained.
It is especially preferable that para bondings are more than 90 mole %. If the para bonding is les than 90 mole %, crystallinity and transition temperature of the polymer obtained decrease, namely, heat resistance and chemical resistance might not be sufficient. On the other hand, less than 10 mole %, of other bondings such as, an ether bonding, a biphenyl bonding, a naphthyl bonding, a substituted phenyl sulfide bonding and so on can be contained.
The hydrogen atoms on the benzene ring in the above described structural unit formula may partly be substituted by a hydroxyl group, an oxygen atom and so on.
As the fine structure of the fiber of the present inven--tion, it is preferable that the degree of orientation, value calculated from the strength distribution obtained by scanning the peak observed at the equatorial line scanning 20 = 16 to 17 in the circular direction is more than 60%.
If the degree of orientation is less than 60%, fibers of low knot strength and being brittle are often obtained. At least 80% is preferable and especially, if the value is more than 90%, fibers high knot strength and heat resistance can be obtained. It is preferable that the size of fine crystalline as the size observed at 2~ = 16 to 17 ismore than 20A, and more than 30A is more preferable. Meanwhile, in the polysulfide fibers having ordinary denier and wherein only the surface layer is A _4_ polysulfonated, crystallinity of the polymer is deteriorated and the size of the crystalline is small probably due to mixing of various constituting units and thereby only low crystallinity and low strength can be obtained.
On the other hand, the fiber period in the fiber axis direction is preferably 9.5 to 10.5A and more preferably 9.5 to 10.OA As the long period of the crystalline lamella, more than 100A is preferable.
Polyphenylene sulfone (hereinafter abbreviated as PPSO) fibers can be easily prepared from ultrafine fibers or porous fibers having large surface area. As the ultrafine fibers, less than 0.5 denier of the monofilament denier is preferable and less than 0.1 denier is especially preferable. The reason is that when the fiber diameter is small, (1) fibers having high strength can be obtained, (2) fibrillation hardly occurs, (3) fibers rich in flexibility (bending resistance) can be obtained, (4) dense and inter-entangled sheet-like products can be obtained, (5) especially when these fibers used for filters, much smaller dust can be removed. On the other hand, as the porous fibers or porous films, it is preferable that the specific surface area is more than 0.4 m2/g. More than 2.4 m2/g is more preferable and more than 10 m /g is especially preferable. Where fiber-like ~ 133574~ 66623-l86 products twoven, knitted products, non-woven fabrics and so on) are prepared from the porous fibers, (1) the amount of air layer kept in the fiber-like products is large and excellent heat insulating property can be thereby obtainedl or (2) as the porosity is high, excellent liquid keeping property for various liquids such as various solutions and electrolytes can be obtained.
Here, the specific surface area means the surface area per 1 g of the fiber and can be measured by means of the so-called BET
(Brunauer-Emmet-Teller) method.
PPSO fibers of the present invention can be obtained by oxidizing polyphenylene sulfide (hereinafter abbreviated as PPS), more preferably highly oriented PPS, especially preferably highly oriented polyparaphenylene sulfide thereinafter abbreviated as PPPS) fibers wherein para-bonding is more than 90%, with an organic peracid.
PPS can be obtained for example by reacting an alkali metal sulfide with a para-dihalogenated benzene in a polar solvent at a high temperature and a high pressure. It is especially preferable that sodium sulfide is reacted with para-dichlorobenzene in an amide type polar solvent having a high boiling point such as N-methyl-pyrrolidone and the like.

A

As for the methods for producing ultrafine fibers especially suitable for the purpose of the present invention, previously known methods such as meltblow1ng, superdrawing, removing a sea component from the islands-in-a-sea type composite fibers or the blend spun fibers, and making peel-off type composite fibers ultrafine by means of a physical or chemical treatment cansbe used with no special limitation. When ultrafine fiber producing type fibers such as islands-in-a-sea type composite fibers and so on are used, polymer substances having fiber form-ability such as pol~styrene, polyethylene, polypropylene, poly-ethylene terephthalate, polyamide and so on can be used without any limitation as a binding component or a component to be -~removed by dissolution but polymers having high melting point and being hardly thermally-decomposable are preferable because PPS has a high melting point (about 280C). From the point of easiness of spinning and removing solvent, preferred is a copoly-merized polyethylene terephthalate easily dissolvable in alkali solution. By the way, although the spinning temperature of PPS
is high, polyestyrene type polymers can be co-melt-extruded with PPS. It is surprising fact that PPS can depress thermal decomposition of polystyrene type polymers, especially ~ 66623-186 thermal decomposition in the molten state a nd polystyrene type polymers prevent occurrence of finer filame nts and nozzle blocking by PPS. This behaviour is observed not only with respect to polystyrene but styrene copolymers. Copolym ers of styrene with a higher alcohol ester of acrylic acid and/
or a higher alcohol ester of methacrylic acid are preferable an d those polymers of higher viscosity are more preferable among them. Moreover, acrylonitrile-butadiene-styrene copolymers (ABS), acrylonitrile-styrene copolymers (AS), butadiene/styrene copolymers (BS), halogenated polystyrene and so on also show the same effect.
Hereinafter these polymers are generally ca lled PST.
Undrawn fibers thus obtained are then drawn and heat-treated, and preferably highly oriented. A
drawing ratio of more than 2 times is preferable when the taking-up is carried out at an ordinary spinning speed (300 to 1,500 m/min) and it is desirable that drawing of more than 2.5 tim es, more preferably more than 3 times is carried out. By;doing so, PPS fibers whose degree of orientation is more than 60% can be obtained. It is also possible to carry out the spinning at high speed higher than 4,000 m/min to highly orient the fiber s. It is surprising that a co-melt-extrusion with another polym er gives better form-ability than a single spinning of PPS. The reason is not clear but such troubles as A

occurrence of finer filaments and nozzle blocking decrease when molten PPS does not directly contact with the nozzle.
Ultrafine fiber producing type fibers obtained are converted into the state of ultrafine fibers by using an appropriate solvent. Of course, a sheet consisting of ultrafine fibers can be obtained by solvent treatment after fibrous sheet-like materials such as woven fabrics, knitted fabrics, non-woven fabrics and so on are formed by using these fibers. By doing so, ultrafine highly oriented PPS fibers can be obtained.
As the methods for producing porous fibers which are one more preferable example of the present invention, conventional well known technologies can be widely applied. Namely, the method wherein the island component is removed from the islands-in-a-sea type fibers whose sea component is PPS and the method for producing the fibers by a dry, wet or dry-wet coagulation spinning of PPS
solution can be used. Moreover, making porous can be done by drawing the fibers at a temperature below the glass.
In case of wet or dry spinning, because PPS is hardly dissolved at lower temperature and therefore it is necessary to heat the spinning solution above 200C, wet or dry spinning is not preferable method. On the other hand, when porous fibers are prepared from islands-in-a-sea type fibers, as the island component or the component _ g _ removable by dissolution, polymeric substances having fiber formability and being durable at the melt spinning temperature of PPS such as polystyrene, polyethylene, polypropylene, polyethylene terephthalate, polyamide and so on can be used without any limitation in the same way as the case of producing ultrafine fibers. From the point of easiness of spinning and removing solvent, polystyrene, copolymerized polyethylene terephthalate being easily dissolvable in alkali solution and copolymers of styrene with a higher alcohol ester of acrylic acid and/or a higher alcohol ester of methacrylic acid are preferable and those polymers of high viscosity are more preferable among them.
Porous fiber forming type fibers thus obtained are converted into the porous state by using an appro-priate solvent. Of course, sheet-like products consisting of porous fibers can be obtained by solvent treatment after fibrous sheet-like materials such as filters, non woven fabrics and so on are formed.
Thereafter, the present invention can be achieved by reacting PPS ultrafine fibers or porous fibers with a sulfonating reagent below described to convert PPS
into PPSO.
As the sulfonating reagents used in the present invention, oxidizing agents used for ordinary oxidation of '-chemicals can be used (but sulfuric acid and nitric acid are excluded) and peracetic acid, perbenzoic acid, performic acid, perpropionic acid, perbutylic acid, m-chloro-perbenzoic acid, pertrichloroacetic acid, pertrifluoroacetic acid and perphthalic acid are prefer-able among them. The treating conditions with said sulfonating reagents depend on the denier of ultrafine fibers, the specific surface area of porous fibers, the reaction velocity of the reagents and so on and therefore are not generally specified. In case of peracetic acid for ultrafine fibers of less than 0.5 denier and porous fibers and porous films of more than 0.4 m2/g, high rate of making PPSO can be achieved even at room temperature.
Moreover, these organic peracids are explosive chemicals and therefore, ultrafine fibers and porous fibers and films by using which high rate making PPSO can be easily achieved are especially preferable. Organic peracids can be prepared by oxidation in an aldehyde in the presence of a catalyst (for example, AMP method for peracetic acid), a vapor phase partial oxidation method, a syntheses using hydrogen peroxide and carboxylic acid anhydride or chloride and reaction of diaroyl peroxide with sodium methaoxide.
It is preferable that the PPS fibers consist of polyparaphenylene sulfide (hereinafter abbreviated as 13~57~5 PPPS) and especially preferable that more than 95% thereof consist of PPPS. If it is less that 90 mole %, crystal-linity, transition temperature and so on of the polymers obtained decrease and it is therefore difficult to obtain fibers having excellent heat resistance and chemical resistance. In the other components of less than 10 mole % besides the above described main component of 90 mole %, ether, biphenyl, naphthyl, substituted phenyl sulfide and so on bondings can be contained. Moreover, cross-linking can be partly contained.
As the fine structure of the fiber of the present invention, especially the degree of orientation, it is preferable that the value calculated from the strength distribution obtained by scanning the peak observed at the equatorial line scanning 2~ = 19 to 21 in the circular direction is more than 60%. If the degree of orientation is less than 60%, fibers of low knot strength and being brittle are often obtained. The degree of orientation is more preferably more than 80% and especially, if the value is more than 90% and the fibers are highly oriented, fibers having high strength and excellent heat resistance can be obtained.
Moreover, it is preferable that the size of fine crystalline as the size observed at 2~ = 19 to 21 is more than 20A.

13~5745 On the other hand, the fiber period of the crystalline in the fiber axis direction is preferably 10 to llA. PPS having such a fine structure has high strength, excellent heat resistance and excellent chemical resistance.
There is a merit that if the denier of PPS
fibers is less than 0.5 denier, sulfonation reaction easily occurs and polysulfonation can be carried out in a short time. Moreover, the degree of orientation of PPSO
fibers becomes very high and the physical properties of PPSO fibers thereby can becomes very high. For example, there is even an example that the degree of orientation is improved more than 10% by making an ultrafine PPS to PPSO.
There is even another large merit that coloring of PPS
fibers themselves can be reduced because ultrafine fibers can dispersed the light.
Moreover, PPS ultrafine fibers have such characteristics that (1) they have high strength, (2) fibrillation hardly occurs, (3) fibers are rich in flexi-bility (bending resistance), (4) dense and inter-entangled sheet-like products can be obtained, (5) especially they are durable against high pH.
Moreover, fiber-like products (woven, knitted products, non-woven fabrics and so on) prepared of said fibers bring such large effects that the amount of air 133574~

layer kept in these fiber-like products increases and excellent heat insulating property can be thereby obtained and that as the porosity is high, excellent liquid keeping property for various liquids such as various solvents and electrolytes can be obtained.
Because these characteristics exhibit their effects the finer the denier of the fibers, it is preferable that the PPS fibers are finer and less than 0.3 denier (hereinafter abbreviated as d) is especially preferable, and less than 0.1 d is more especially preferable.
Moreover, as described above, PPS also have the effect improving the heat resistance of PST. The effect largely depends upon the kinds, compositions, applications and processing conditions of PST to be used. Although the amount of PPS to be added is not generally determined but it is necessary to determine the amount to be added by testing it properly in advance.
However, in general, based on 100 weight parts of polystyrene component in PST, more than 0.01 weight parts (hereinafter called part unless otherwise described) of PPS are preferable, more than 0.5 parts are more preferable and more than 3 parts are especially preferable. If the amount of PPS to be added is less than 0.01 part, the thermal decomposition resistance of PST is '-little improved. When mixing PST with PPS is carried out in powder form, it is enough to add more than 0.5 parts of PPS because both components can be very easily mixed together. But either when both components are in the form of chips or when only PPS is in powder form and PST is in the form of chips, such a problem that mixing is not smoothly done occurs and more than 3 parts of the amount to be added are therefore preferable.
The present invention will be hereinafter described in more detail in connection with the examples.
Example 1 50 parts of PPS prepared by reacting sodium with para-dichlorobenzene is N-methyl-2-pyrrolidone in the presence of sodium benzoate under high temperature and high pressure and whose apparent viscosity was 3,700 poises at 300C as the island component and 50 parts of polystyrene of high viscosity as the sea component were used for preparing islands-in-a-sea type composite fibers having 36 island components in a filament under such spinning conditions that the spinning temperature and the take-up velocity were 320C and 900 m/minute respectively.
The spun filaments were thereafter drawn by 3.7 times to obtain filaments of 72 deniers/24 filaments. Said fila-ments were cut by 10 cm in length and polystyrene as the sea component was extracted and removed in trichloro-~ 1335'1 ~S

ethylene, and the fibers were then dried. PPPS ultrafinefibers obtained whose monofilament denier was 0.04 denier have tensile strength of 3.8 gjd elongation of 29.2%. The degree of orientation of the fibers calculated from X-ray measurement was 80% and the size of crystalline at 20.2 and the fiber period were 27 and 10.3A respectively.
This ultrafine fibers were treated in a peracetic acid solution (9% concentration in acetic acid) at room temperature at one hour and thereafter washed, neutralized, washed and dried. The ultrafine fibers thus obtained showed the weight increase of 26% and the mono-filament denier was 0.05 denier. Tensile strength, elongation and knot strength of the fibers were 3.1 g/d, 22% and 2.2 g/d respectively.
Said fibers were immersed in concentrated nitric acid solution whose specific gravity was 1.42 overnight and the rate of tenacity retention was measured after taking them out. It was found that the rate of tenacity retention for said fibers was 95%, which was very high.
As the heat resistance, the rate of tenacity retention after the exposure in air at a high temperature such as 300!C for 24 hours was 100%, which was very excellent.
Said fibers were analized by means of solid state high resolution NMR and ESCA (Electron Spectroscopy for Chemical Analysis) and it was found that the structural units of said fibers consisted of 83 mole % of ~ S2 ) ,13 mole % of ~ SO ) and 4 mole % of ~ S -~- and the degree of orientation at 20 = 16.3 determined by means of wide angle X-ray diffraction was 91%.
Example 2 Mutually arranged polymeric fibers having seven island components in a filament and moreover a number of ultrafine fiber components in each island component and consisting of 35 parts of PPPS which is the same as in example 1 as the ultrafine fiber component and 65 parts of a copolymer of acrylic acid and styrene as the binding component were spun in 1,200 m/minute, drawn by 3.5 times, crimped and staple fibers prepared of mutually arranged polymeric fibers whose fiber length and denier were 51 mm and 4.0 denier respectively can be obtained. The average denier of the ultrafine fiber components was 0.002 denier.
A web was prepared by treating said staple fibers through a carding and a crosswrapper and then needle-punched to prepare a non-woven fabrics whose weight and apparent density were 200 g/m2 and 0.17 g/cm2 respectively. Thereafter, high speed liquid flows were blasted on both sides of said non woven fabrics under the pressure of 100 kg/m2 through nozzle arranged in a line in a pitch of 1.5 mm whose hole diameters were 0.20 mm while 133S~45 the nozzles were being vibrated to inter-entangle the fiber densely. Thereafter, mutually arranged polymeric fibers wholly becames to ultrafine fibers by almost completely extracting the above described copolymer component in trichloroethylene.
Next, sulfonating treatment of the fibers was carried out in the same way as example 1. The non-woven fabrics obtained had a fiber structure where ultrafine fibers of polyphenylene sulfone densely entangled each other (the rate of sulfonation was 95~ by means of ESCA
measurement. The degree of orientation was measured by using a sample prepared by bundling drawn filaments before crimping, cutting them by 10 cm and removing the sea component and by means of X-ray analysis. The value was 90% and it was therefore confirmed that the fibers were highly oriented.), and was a sheet having an effective dimensional stability although no binder existed between fibers. Moreover after keeping the fabrics in air at such a high temperature as 290C for 24 hours, almost no coloring was observed and enough tenacity was kept.
Example 3 Islands-in-a-sea type composite fibers consist-ing of 50 parts of the same PPPS as the example 1 as the sea component and 50 parts of polystyrene of high viscosity as the island component and having 36 islands in '-~

a filament were spun under the conditions that the spinning temperature was 320C and the take-up velocity was 900 m/minute and thereafter was drawn by 3.7 times at 100C and was heat-set at 220C to obtained a filament yarn of 72 denier/24 filaments. Said filament yarns were cut by 5 cm in length and polystyrene of the island component was extracted and removed in trichloroethylene and the resultant fibers were dried. PPPS porous hollow fibers thus obtained whose specific surface area was 1.6 m2/g was treated in a paracetic acid solution (the concentration was 9% in acetic acid) for 3 hours, washed, neutralized, washed and dried.
The weight of the porous hollow fibers thus obtained increased by 29~ and the specific surface area was 1.24 m2/g.
Said fibers did not fall into pieces any more in a concentrated nitric acid solution.
The rate of sulfonation of said fibers was analyzed by means of ESCA and was found 98%.
Example 4 60 parts of PPPS being the same as the example 1 and 30 parts of polystyrene of high viscosity were melted and blended at 320C and were extruded from a nozzle having 100 holes, spun by take-up velocity of 900 m/minute, drawn by 3.5 times at 100C, heat-set at 220C

s-to obtain composite fibers whose monofilament denier was 3 d. The fibers were thereafter cut by 51 mm in length and a web was formed thereof by means of a carding machine. A non-woven fabric whose weight was 500 g/m2 was obtained by needle-punching the web.
The non-woven fabric thus obtained was thereafter immersed in trichloroethylene and polystyrene was thereby almost completely extracted and removed.
Thereafter, said non-woven fabric was treated with 9~
peracetic acid in acetic acid solution at 50C for 1 hour and, washed, neutralized, washed and dried.
The non-woven sheet thus obtained was a sheet consisting of porous fibers mainly consisting of PPSO
(whose rate of sulfonation was 95% measured by ESCA) and whose specific surface area was 16 m2/g. The non-woven sheet had excellent warming property, did not melt and fuse at such a high temperature as 300C and had distinguished heat resistance.
Example 5 PPPS pellets being the same as the one of example 1 were spun under spinning conditions that the same spinning temperature and the take-up velocity were 330C and 450 m/minute respectively. The filaments obtained were thereafter drawn by 4.0 times under such drawing conditions that the hot roller temperature and the ~ 133S1 4S

hot plate temperature were 90 and 200C respectively to obtain filaments of 75 denier/24 filaments. Tensile strength of PPPS fibers obtained was 3.5 g/d.
Next, this ultrafine fibers were treated in a commercially available peracetic acid solution (9%
concentration in acetic acid) at room temperature (30C) for 2 weeks and thereafter washed, neutralized, washed and dried. The ultrafine fibers thus obtained showed the weight increase of 24% in comparison with the original PPS
fibers and the tensile strength and the breaking strength were 2.6 g/d and 18% respectively. Said fibers were kept in air at such a high temperature as 290C for 24 hours and the tensile strength and elongation of the fibers before and after the test were measured. No change was observed on the strength-elongation characteristics and it meant that the fibers had very excellent heat resistance.
Said fibers were analized by means of solid state high resolution NMR and ESCA and it was found that the structural units of said fibers consisted of 75 mole %

of ~ S2 ) , 16 mole % of ~ SO t and 9 mole % of ~ S -~-. It was also found that the degree of orientation at 2~ = 16.5 determined by means of wide angle X-ray diffraction was 91.3% and the size of fine crystalline in said direction was 35A. It was thereby confirmed that said fibers had a highly oriented crystalline structure.
Comparison examples 1 and 2 Instead of the treatment with peracetic acid in example S, treatments in sodium hypochlorite 9% solution (1 mole of H2SO4 was contained against 2 mole of NaOCl) at room temperature for one day (comparison example 1) and at 90C for one hour (comparison example 2) were carried out.
The fibers obtained in comparison example 1 showed the weight increase of 4%, while the fibers in comparison example 2 fell in pieces during the treatment and changed to pieces having no fibrous shape any more.
The fibers obtained in comparison example 1 were put on a slide glass and heated from the bottom with the fire of an alcohol lamp, but they did not melt any more even when the surface temperature becames to 500C and it was thereby confirmed that the fiber surface had been unfusible. However, the fiber strength of the fiber obtained in comparison example 1 decreased to 16 kg/mm2, 36% of the original strength, by the treatment with sodium hypochlorite and the breaking elongation became 3~, too.
It meant that the fibers had been changed to very brittle fibers. The rate of heat resistant tenacity retention measured in the same way as example 1 was 32%, which was very low.

~' .

~ 13357 45 Said fibers of comparison example 1 were analyzed by means of NMR, ESCA, IR and it was found that besides 60 mole % of the original structural unit ~ S ) , 7 mole % ~ SO ) and 15 mole %
of ~ S2 ) , total 19 mole % of -SO4 and -SO3 had been prepared and the ratio of sulfur atoms to carbon atoms decreased from 0.27 to 0.18. It was thereby confirmed that fairly large amount of main chain cuttings occurred.
Reference example 1 PPPS being the same as the one in example 1 and polystyrene (Type 679 manufactured by Asahi Chemical Industries Co., Ltd.) were separately melted and then joined together in a spining nozzle pack to obtain composite fibers whose sheath and core were PST and PPPS
respectively. The preparing conditions were as follows.
(1) Sheath component/core component (weight ratio) (2) Melter temperature of PST = 280C

(3) Melter temperature of PPPS = 315C

(4) Temperature of the spinning nozzle pack part where PST and PPPS were joined together = 315C

(5) Spinning velocity = 1,000 m/minute (6) Drawing ratio = 3.2 times (7) Drawing temperature = 95C

13~5745 (8) Denier X numbers of the fibers obtained = 150 denier x 50 filaments Both spinning and drawing can be smoothly carried out without any special trouble. By treating said drawn filaments with trichlene, good PPS fibers whose strength, elongation and degree of orientation measured by means of X-ray were 4 g/d, 30% and 89% respectively were obtained. It was surprising that less filaments cutting occurred and better spinning can be carried out in composite spinning of PST and PPPS in comparison with the spinning of PPPS alone. Namely, numbers of filament cutting (in spinning and drawing all together) were 3 times/t in the case of PPPS alone and 0.7 times/t in the case of PST and PPPS composite fibers.
Reference example 2 3 parts of fine powder of PPS manufactured by Phillips Petroleum Co., Ltd. in U.S.A. was added to and mixed with 100 parts of polystyrene (Type 679 manufactured by Asahi Chemical Industries Co., Ltd.) and the mixture was put into a Petri dish and stirred at 300C to prepare a mixture of PST and PPS. The said mixture was heated in air at 330C for one hour to carry out a thermal decom-position test and it was found that the rate of weight decrease was 7.1%. The amount of decomposed gas generated by mixing at 300C was very little by observation with naked eyes.
The same test was carried out on the composition without PPS in the same manner and it was found that the rate of weight decrease of PST was 18.7%. Moreover, when only PST was stirred at 300C, large amount of decomposed gas occurred. Extremely large amount of decomposed gas occurred at 330C and it was afraid that even ignition might occur.
Polyphenylene sulfone fibers of the present invention do not deteriorate with concentrated sulfuric acid and nitric acid and have excellent heat resistance and chemical resistance.
Therefore, they can be favorably applied for filters for refining concentrated sulfuric acid and nitric acid to which demands have been recently growing, various filters for desulfuration and denitration apparatus of chimney gas, and filters, sheet-like materials and so on used in the fields where distinguished heat resistance and chemical resistance are required, for example, battery separators and fused membrane and the like.

Claims

1. A polyphenylene sulfone fiber mainly consisting of a structural unit represented by the general formula wherein (a) x is 0, 1 or 2, (b) ?, the average value of x, is 1.0 to 2.0, (c) the bond attached to the benzene ring is in the para- or meta-position with respect to the SOx group, (d) the molar ratio of SO2/SOx, namely, the molar ratio of the sulfur atoms in the sulfone form (SO2) to the total sulfur atoms in the sulfide (S), sulfine (SO) and sulfone (SO2) forms, is more than 0.3, and wherein the fiber has a degree of orientation of more than 60%.

2. The polyphenylene sulfone fiber as claimed in claim 1, wherein ? is 1.4 to 2Ø

3. The polyphenylene sulfone fiber as claimed in claim 1, which has a specific surface of more than 0.4 m2/g.

4. The polyphenylene sulfone fiber as claimed in claim 1, which is porous.

5. The polyphenylene sulfone fiber as claimed in claim 1, 2, 3 or 4, wherein a molar ratio of SO2/SO is at least 3.

6. The polyphenylene sulfone fiber as claimed in claim 5, wherein more than 90 mole % of the bond attached to the benzene ring is in the para-position with respect to the SOx group.

7. A polyphenylene sulfone fiber mainly consisting of a structural unit represented by the general formula:

[wherein (a) x is 0, 1 or 2, (b) ?, the average value of x is 1.0 to 2.0, (c) the bond attached to the benzene ring is in the para- or meta-position with respect to the SOx group, provided that more than 90 mole % thereof is in the para-position and (d) the molar ratio of SO2/SOx, namely the molar ratio of the sulfur atoms in the sulfone form (SO2) to the total sulfur atoms in the sulfide (S), sulfine (SO) and sulfone (SO2) forms, is more than 0.3], wherein the fiber has a specific surface of more than 0.4 m2/g and a degree of orientation of more than 60%.

8. The polyphenylene sulfone fiber as claimed in claim 7, wherein ? is 1.4 to 2Ø

9. The polyphenylene sulfone fiber as claimed in claim 7, wherein the SO2/SOx molar ratio is more than 0.7.

10. The polyphenylene sulfone fiber as claimed in claim 7, wherein a SO2/SO molar ratio is at least 3Ø

11. The polyphenylene sulfone fiber as claimed in claim 7, wherein the degree of orientation is at least 80%.

12. The polyphenylene sulfone fiber as claimed in claim 7, which is a porous hollow and has a surface of more than 10 m2/g.

13. The polyphenylene sulfone fiber as claimed in claim 9, which is an ultrafine fiber having a fineness of 0.002 to 0.1 denier.

-27a-

14. The polyphenylene sulfone fiber as claimed in claim 9, which is a porous hollow fiber and has a specific surface of more than 10 m2/g.

15. The polyphenylene sulfone fiber as claimed in claim 7, which has a fine crystalline size of more than 20.ANG..

16. The polyphenylene sulfone fiber as claimed in claim 7, 8 or 9, which has a fineness of less than 0.5 denier.

17. The polyphenylene sulfone fiber as claimed in claim 10, 11 or 12, which has a fineness of less than 0.5 denier.

18. The polyphenylene sulfone fiber as claimed in claim 7, 8 or 9, which has a fineness of less than 0.1 denier.

19. The polyphenylene sulfone fiber as claimed in claim 10, 11 or 12, which has a fineness of less than 0.1 denier.

20. A woven, knitted or non-woven sheet or fabric made of the fiber as defined in claim 1, 2 or 4.

21. A woven, knitted or non-woven sheet or fabric made of the fiber as defined in claim 7, 8 or 9.

22. A filter for refining concentrated sulfuric acid or nitric acid, which is made of the fiber as defined in claim 7, 8 or 9.

23. A filter for refining concentrated sulfuric acid or nitric acid, which is made of the fiber as defined in claim 10, 11 or 12.

24. A filter for refining concentrated sulfuric acid or nitric acid, which is made of the fiber as defined in claim 13, 14 or 15.

25. A method for production of the polyphenylene sulfone fiber as defined in claim 1, which comprises:
oxidizing a polyphenylene sulfide fiber mainly consist-ing of a structure unit represented by the formula:

(wherein the bond attached to the benzene ring is in the para-or meta-position with respect to the S atom) with an organic per-acid.

26. A method for production of the polyphenylene sulfone fiber as defined in claim 7, which comprises oxidizing a poly-phenylene sulfide fiber which has a specific surface area of more than 0.4 m2/g and a degree of orientation of more than 60% and mainly consists of a constituting unit represented by a general formula (wherein the bond attached to the benzene ring is in the para- or meta-position, provided that more than 90 mole % thereof is in the para-position) with an organic peracid to the polyphenylene sulfone fiber.

27. The method as claimed in claim 26, wherein the organic peroxide is at least one selected from the group consisting of peracetic acid, perbenzoic acid, performic acid, perpropionic acid, perbutyric acid, m-chloroperbenzoic acid, pertrichloroacetic acid, pertrifluoroacetic acid and perphthalic acid.

28. The method as claimed in claim 27, wherein the poly-phenylene sulfide fiber is prepared by a co-melt-extrusion of the polyphenylene sulfide polymer as the island component and a polystyrene polymer as the sea component in the form of an islands-in-a-sea type composite fiber and then carrying out a combination of a drawing process and a removing process of the sea component.

29. Ultrafine poly-p-phenylene sulfide fibers which has a fineness of less than 0.5 denier and a degree of orientation of more than 60%.

30. The ultrafine poly-p-phenylene sulfide fibers as claimed in claim 29, which have a specific surface of more than 0.4 m2/g

31. The ultrafine poly-p-phenylene sulfide fibers as claimed in claim 29, which have a specific surface of more than 10 m2/g.

32. The ultrafine poly-p-phenylene sulfide fibers as claimed in claim 29, 30 or 31, which have a fineness of from 0.002 to 0.1 denier.

33. The ultrafine poly-p-phenylene sulfide fibers as claimed in claim 29, 30 or 31, which have a fineness of 0.002 to 0.1 denier and are in a non-woven fabric form.

34. A method of production of the ultrafine poly-p-phenylene sulfide fibers as defined in claim 29, 30 or 31, which comprises:

a co-melt-extrusion of an islands-in-a-sea type composite fiber composed of poly-p-phenylene sulfide polymer as the island component and another polymer as the sea component, the said other polymer having fiber formability and being capable of being removed after the co-melt-extrusion by a solvent which does not dissolve the poly-p-phenylene sulfide polymer;
drawing the composite fiber; and removing the sea component polymer by dissolving with the said solvent.

35. The method as claimed in claim 34, wherein the other polymer constituting the sea component is polystyrene or a copolymer of styrene and a higher alcohol ester of acrylic or methacrylic acid.

36. The method as claimed in claim 34, which further comprises:
forming the fibers into a non-woven fabric form either before or after the sea component removing step.