CN113481626A - Preparation method of polyphenylene sulfide sulfone ketone fiber - Google Patents
Preparation method of polyphenylene sulfide sulfone ketone fiber Download PDFInfo
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
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- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention discloses a preparation method of polyphenylene sulfide sulfone ketone fiber, which comprises the following steps of firstly, taking metal oxide as a catalyst, and preparing ketone-containing PPS tows by carrying out screw extrusion reaction on PPS resin, the metal oxide and dicarboxylic acid or polycarboxylic acid; then placing the ketone-containing PPS tows in an oxidation system, and carrying out oxidation reaction under the action of an oxidation catalyst to obtain polyphenylene sulfide sulfone ketone nascent fibers; and removing impurities from the polyphenylene sulfide sulfone ketone nascent fiber, and drying to obtain the polyphenylene sulfide sulfone ketone fiber. The invention realizes the Friedel-crafts acylation crosslinking reaction among PPS molecular chains in a molten state, realizes the intermolecular crosslinking or intermolecular chain extension of the PPS, and introduces ketone groups into PPS molecules; and oxidizing the PPS fiber with the crosslinked or chain-extended ketone group to realize the controllable oxidation of S atoms and the introduction of sulfone groups and sulfoxide groups, thereby obtaining the PPS modified fiber containing ketone and sulfone or ketone and sulfoxide, which has high temperature resistance, solvent resistance, creep resistance, molten drop resistance, oxidation resistance, high toughness and high strength.
Description
Technical Field
The invention relates to the technical field of PPS modification, in particular to a preparation method of polyphenylene sulfide sulfone ketone fiber.
Background
Polyphenylene Sulfide (PPS) is a thermoplastic resin with a molecular main chain containing a phenylthio group, and has the characteristics of excellent high temperature resistance, corrosion resistance, radiation resistance, flame retardance and the like, so that the PPS can be widely applied to high-temperature severe environments. However, since the PPS fiber is easily shrunk by creep, has a dripping phenomenon, is not resistant to oxidation and has low temperature resistance, and is limited to be used in an environment of 180 ℃ or higher. Although the research and development are actively carried out at home and abroad, a certain production capacity (ZL201510631820.5 and ZL201510350644.8) of the PPS fiber or the modified fiber is initially formed, the PPS-derived fiber product still has the problems of poor toughness, low strength, ultraviolet ray resistance, few high-function products and the like.
At present, PPS is generally used as special engineering plastic after being filled and modified, then PPS composite fiber is spun, but the properties of oxidation resistance, high temperature resistance and the like of the PPS fiber cannot be effectively improved by adding a modification technology, while the oxidation resistance and the temperature resistance of the fiber can be greatly improved by a PPS oxidation modification technology, but the mechanical property of the fiber is greatly reduced due to the oxidation of pure PPS fiber, and the strength and the toughness of the modified fiber cannot be effectively improved.
Currently, mainly developed structurally modified PPS resins are polyphenylene sulfide ketone (PPSK), polyphenylene sulfide sulfone, polyphenylene sulfide amide, and polyphenylene nitrile sulfide. The PPS derivatives are mainly introduced by the copolymerization of a third monomer containing a special functional group, so that the introduction of the special modified group into a PPS molecular chain is realized, but the monomer copolymerization cost is high, and the introduction of the third monomer greatly reduces the average molecular weight of a target compound. Although polyphenylene sulfide sulfone has excellent high temperature resistance, its solvent resistance is slightly inferior to that of a crystalline polyarylene sulfide resin. Polyphenylene sulfide ketone is also a high temperature and corrosion resistant material, and has high strength, high modulus crystallinity and high temperature resistance thermoplastic resin at high temperature. Compared with the former two, the polyphenylene sulfide sulfone ketone combines the advantages of polyphenylene sulfide sulfone and polyphenylene sulfide ketone, compared with PPS, the polyphenylene sulfide sulfone ketone has better mechanical property, high temperature resistance and solvent resistance, the thermal deformation temperature of the polyphenylene sulfide sulfone ketone can reach more than 300 ℃, and the polyphenylene sulfide sulfone ketone has huge potential application value in related industries such as automobile, chemical industry, electronics, electrical appliances, precision machinery, aviation and the like.
At present, the preparation of the polyphenylene sulfide sulfone ketone resin only has one mode: the sodium sulfide, 4 '-dichlorodiphenyl sulfone and 4,4' -dichlorobenzophenone are taken as raw materials, N-methyl pyrrolidone solvent, sodium hydroxide is taken as an auxiliary agent, and sodium benzoate is taken as a catalyst, and the sodium sulfide is directly polymerized (the invention of application number 201610753506.9). However, the modification method has the disadvantages of complex process, difficult control of polymerization, low average molecular weight of a polymerization product and relatively high polymerization cost, so that the industrialization of high-quality products is difficult.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to solve the technical problem of providing a preparation method of polyphenylene sulfide sulfone ketone fiber.
The technical scheme for solving the technical problems is to provide a preparation method of polyphenylene sulfide sulfone ketone fiber, which is characterized by comprising the following steps:
(1) taking metal oxide as a catalyst, and carrying out in-situ spinning on PPS resin, the metal oxide and carboxylic acid by a screw extrusion reaction blending melting one-step method to prepare ketone-containing PPS tows; or extruding PPS resin, metal oxide and carboxylic acid by using a screw to react, blending, melting and granulating to prepare ketone-containing PPS particles, and then carrying out particle melt spinning by using the ketone-containing PPS particles as a raw material to prepare ketone-containing PPS tows; the carboxylic acid is dicarboxylic acid or polycarboxylic acid;
(2) placing the ketone-containing PPS tows prepared in the step (1) in an oxidation system, and carrying out oxidation reaction under the action of an oxidation catalyst to obtain polyphenylene sulfide sulfone ketone nascent fibers;
(3) and (3) removing impurities from the polyphenylene sulfide sulfone ketone nascent fiber prepared in the step (2), and drying to obtain the polyphenylene sulfide sulfone ketone fiber.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method takes PPS resin as a raw material, utilizes carboxylic acid as a modifier, and adds nano-micron metal oxide as a Friedel-crafts acylation catalyst to realize the Friedel-crafts acylation crosslinking reaction (namely screw extrusion reaction) among PPS molecular chains in a molten state, realize the intermolecular crosslinking or intermolecular chain extension of the PPS, and introduce ketone groups into PPS molecules; and oxidizing the PPS fiber with the crosslinked or chain-extended ketone group to realize the controllable oxidation of S atoms and the introduction of sulfone groups and sulfoxide groups, thereby obtaining the PPS modified fiber containing ketone and sulfone or ketone and sulfoxide, which has high temperature resistance, solvent resistance, creep resistance, molten drop resistance, oxidation resistance, high toughness and high strength.
(2) Through carrying out the keto modification on PPS, the flexibility of molecular chains is effectively improved, the interaction force among the molecular chains is increased, and the mechanical properties such as the tensile strength, the tensile toughness and the cohesive force among fibers of PPS fibers or resin are greatly improved. Meanwhile, the oxidative fracture of PPS molecular chains can be greatly inhibited, and the mechanical property of the ketone-containing PPS tows can be kept well in the catalytic oxidation process.
(3) Selective oxidation of sulfur atoms (S) to Sulfones (SO) in PPS by an oxidation process2) Or Sulfoxide (SO), regulating and controlling catalytic oxidation conditions, regulating and controlling oxidant types and catalyst types, and preparing the ketone-containing sulfone-containing modified PPS fiber in a targeted manner.
(4) The addition of carboxylic acid and metal oxide improves the comprehensive performance of the fiber, reduces the influence of high-temperature volatile components on spinning (residual volatile components such as N-methylpyrrolidone and ethylene glycol in PPS), and greatly improves the fiber forming rate of the fiber.
(5) The existence of the metal oxide can catalyze the Friedel-crafts acylation reaction of the organic acid and PPS molecules, improve the ultraviolet resistance of the modified fiber and improve the mechanical property of the fiber.
(6) The polyphenylene sulfide sulfone ketone fiber prepared by the method has high glass transition temperature (more than 150 ℃, even no glass transition temperature, and the PPS glass transition temperature is about 93 ℃), and the polyphenylene sulfide sulfone ketone fiber has no molten drop and no creep phenomenon at high temperature, so that the defects of low glass transition temperature, low temperature resistance, poor oxidation resistance, poor toughness, high brittleness, easy generation of static electricity, poor cohesion among monofilaments, loose strands, high friction coefficient and difficult post-processing of the PPS are overcome.
The polyphenylene sulfide sulfone ketone fiber prepared by the method has the characteristics of excellent creep resistance, molten drop resistance, shrinkage resistance, oxidation resistance and ultraviolet resistance, and particularly has excellent mechanical properties. And the corresponding fiber oiling agent is utilized to improve the surface performance of the polyphenylene sulfide sulfone ketone fiber, improve the wettability and high-temperature cohesiveness of the polyphenylene sulfide sulfone ketone fiber and improve the conductivity of the polyphenylene sulfide sulfone ketone fiber, so that the phenomena of broken filaments, broken ends and the like of the fiber in the processing process are reduced, the tensile property and the post-treatment property of the fiber are improved, and the fiber can smoothly pass through each processing procedure.
The polyphenylene sulfide sulfone ketone fiber prepared by the method has large polymer molecular weight and good controllability of the fiber structure, and is beneficial to large-scale industrial production. Can be used for protective articles, such as fire-fighting clothing, stokehole work clothes, electric welding work clothes, special military clothes, fire-proof curtains, fire-proof felts, fire-proof gloves and the like. Can be used for high-end filter materials, such as high-temperature flue dust removal filter bags, chemical filter cloth and the like.
Drawings
FIG. 1 is an XPS plot of the sulfur element of polyphenylene sulfide sulfone ketone fiber prepared in example 1 of the present invention;
FIG. 2 is a comparison graph of the corrosion resistance and high temperature resistance tests of the PPS fibers and the PPS fibers prepared in example 1 of the present invention;
FIG. 3 is a comparative graph of the combustion test of the PPS fibers and the PPS fibers prepared in example 1 of the present invention;
FIG. 4 is a DSC of the polyphenylene sulfide sulfone ketone fiber prepared in example 1 of the present invention;
FIG. 5 is a graph showing the results of a UV resistance test of PPS fibers;
FIG. 6 is a graph showing the UV resistance test results of the PPS sulfone ketone fiber prepared in example 1 of the present invention;
FIG. 7 is a thermogravimetric plot of polyphenylene sulfide sulfone ketone fibers prepared in examples 2-7 of the present invention;
FIG. 8 is an XPS elemental test chart of polyphenylene sulfide sulfone ketone fibers prepared in examples 2 to 7 of the present invention;
FIG. 9 is an SEM topography 1000 times the surface of the polyphenylene sulfide sulfone ketone fiber prepared in example 9 of the present invention;
FIG. 10 is an SEM topography of 2000 times the surface of the polyphenylene sulfide sulfone ketone fiber prepared in example 9 of the present invention.
Detailed Description
Specific examples of the present invention are given below. The specific examples are only intended to illustrate the invention in further detail and do not limit the scope of protection of the claims of the present application.
The invention provides a preparation method (a method for short) of polyphenylene sulfide sulfone ketone fiber, which is characterized by comprising the following steps:
(1) ketonized PPS: taking metal oxide as a catalyst, and carrying out blending melting one-step method in-situ spinning on fiber-grade PPS resin, the metal oxide and carboxylic acid in a screw extruder by using screw extrusion reaction to prepare ketone-containing PPS tows; or the fiber grade PPS resin, the metal oxide and the carboxylic acid are mixed and melted in a screw extruder for granulation by screw extrusion reaction to prepare the ketone-containing PPS particles, and then the ketone-containing PPS particles are used as raw materials to carry out particle melt spinning to prepare the ketone-containing PPS tows; the carboxylic acid is dicarboxylic acid or polycarboxylic acid;
preferably, in the step (1), the dicarboxylic acid is terephthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid or biphenyldicarboxylic acid; the polybasic carboxylic acid is benzene ring-containing tricarboxylic acid, preferably trimesic acid and biphenyl tricarboxylic acid; the metal oxide is TiO2、SiO2、ZrO2、ZnO、SnO2、Al2O3、MoO3、WO3、CdO、GeO2Or Ga2O3At least one of;
preferably, in the step (1), the mass of the carboxylic acid is 0.01 to 10 wt%, preferably 0.01 to 2 wt%, more preferably 0.1 to 2 wt% of the total mass of the PPS resin, the metal oxide and the carboxylic acid; the mass of the metal oxide is 0.01-5 wt%, preferably 0.01-1 wt% of the total mass of the PPS resin, the metal oxide and the carboxylic acid;
preferably, in the step (1), the one-step in-situ spinning process of blending melting is as follows: mixing or not mixing, melting by a screw extruder, metering by a melt pump, forcibly filtering, spinning by a spinning assembly, primarily spinning, thermally stretching, and preparing the ketone-containing PPS tows, specifically, directly feeding PPS powder or granules, carboxylic acid and metal oxide into a double-screw extruder or a single-screw extruder through a feeding machine, or fully mixing the PPS powder or granules, the carboxylic acid and the metal oxide in the mixing machine to form a mixed material, and then feeding the mixed material into the double-screw extruder or the single-screw extruder through the feeding machine; then the materials react at high temperature in the screw extrusion process to form a target substance; the temperature of a feeding port (namely a first zone) is 265-310 ℃, the temperature of an intermediate zone is 300-335 ℃, and the temperature of a die head is 295-320 ℃; and (2) forcibly filtering gel or large-size metal oxide in the melt by using a metal mesh under the action of a melt metering pump, controllably spinning the filtered melt by using a spinning assembly to form primary yarns, and performing a hot stretching process to obtain the ketone-containing PPS (polyphenylene sulfide) tows.
Preferably, in the step (1), the blending, melting and granulating process comprises the following steps: mixing or not mixing, melting by a screw extruder, melting by a melt metering pump, forcibly filtering, wire drawing and granulating, and feeding PPS powder or granules, carboxylic acid and metal oxide into a double-screw extruder or a single-screw extruder directly through a feeder, or fully mixing the PPS powder or granules, the carboxylic acid and the metal oxide in the mixer to form a mixed material, and then feeding the mixed material into the double-screw extruder or the single-screw extruder through the feeder; then the materials react at high temperature in the screw extrusion process to form a target substance; the temperature of a feeding port (namely a first zone) is 250-295 ℃, the temperature of an intermediate zone is 290-340 ℃, and the temperature of a die head is 280-320 ℃; and (3) forcibly filtering gel or large-size metal oxide in the melt by using a metal mesh under the action of a melt metering pump, and drawing and granulating the filtered melt to obtain the ketone-containing PPS particles.
Preferably, in step (1), the process of melt spinning the particles is: drying the ketone-containing PPS particles, melting by a screw extruder, metering a melt pump, forcibly filtering, spinning a spinning pack, primarily spinning, thermally stretching, and feeding the ketone-containing PPS particles into a double-screw extruder or a single-screw extruder by a feeder; then the materials react at high temperature in the screw extrusion process to form a target substance; the temperature of a feeding port is 270-310 ℃, the temperature of a middle area is 290-340 ℃ (290-330 ℃ in a second area, 315-340 ℃ in a third area and 320-340 ℃ in a fourth area), and the temperature of a die head is 300-320 ℃; and (2) forcibly filtering gel or large-size metal oxide in the melt by using a metal mesh under the action of a melt metering pump, controllably spinning the filtered melt by using a spinning assembly to form primary yarns, and performing a hot stretching process to obtain the ketone-containing PPS (polyphenylene sulfide) tows.
Preferably, in the step (1), the hot stretching process is carried out at a hot stretching temperature of 90-200 ℃ and a stretching ratio of 2-10 times; preferably, hot stretching is carried out in steam at 70-100 ℃, and the stretching multiple is 3-8 times, so that the crystallinity of the ketone-containing PPS tows is 80-96%.
(2) In-situ or post-oxidation of ketone-containing PPS tows: placing the ketone-containing PPS tows prepared in the step (1) in an oxidation system, and carrying out oxidation reaction under the action of an oxidation catalyst to obtain polyphenylene sulfide sulfone ketone nascent fibers;
preferably, in the step (2), the mass of the ketone-containing PPS tows accounts for 0.1-40 wt% (preferably 5-15 wt%) of the total mass of the ketone-containing PPS tows and the oxidation system; the mass concentration of the oxidation catalyst in the oxidation system is 0.1-40 wt% (preferably 1-20 wt%);
preferably, in the step (2), the fineness of the ketone-containing PPS tows is 1D-3D;
preferably, in step (2), the oxidation catalyst is an inorganic acid and/or an organic acid; the inorganic acid is sulfuric acid, hydrochloric acid, carbonic acid, heteropolyacid, boric acid, phosphoric acid, nitric acid, molybdic acid, tungstic acid or acidic molecular sieve; the organic acid is selected from fatty acid and aromatic acid such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, capric acid, benzoic acid, naphthoic acid, benzenesulfonic acid, naphthalenesulfonic acid, oxalic acid, malonic acid, succinic acid, adipic acid and pimelic acid. The oxidation catalyst has the function of placing the pH value of an oxidation system in an interval of 1-8 (preferably 4-8) so as to facilitate the oxidation reaction.
Preferably, in the step (2), the oxidation system is an oxidant solution, an electrolyte, an oxygen-saturated solution of water or an aqueous ozone solution;
when an oxidant solution is adopted, soaking the ketone-containing PPS tows prepared in the step (1) in the oxidant solution, and oxidizing for 0.1 min-24 h (preferably 1 min-6 h, more preferably 0.5-2 h) at 0-140 ℃ (preferably 35-90 ℃) under the action of an oxidation catalyst to obtain the polyphenylene sulfide sulfone ketone nascent fibers; the oxidant solution is formed by dissolving or dispersing an oxidant in a solvent, and the mass concentration of the oxidant solution is 0.1-40 wt% (preferably 0.5-40 wt%, more preferably 5-15 wt%); the oxidant is H2O2、Na2O2、NaClO、KClO、HClO、KMnO4、K2Cr2O7、MnO2、FeCl3、NO2、HNO3Peracetic acid, performic acid, dicumyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, perylenel peroxideOxidizing at least one of cyclohexanone, t-butanol peroxide, or perbenzoic acid; the solvent is at least one of water, benzene, toluene, ketone compounds, organic alcohol, amide compounds, dimethyl sulfoxide, tetrahydrofuran, diethyl ether, dimethyl ether, cyclohexane, n-hexane, organic acid or halogenated hydrocarbon.
When an electrolyte is adopted, the ketone-containing PPS tows prepared in the step (1) are soaked in the electrolyte of an electrolytic oxidation device, the initial pH of the electrolytic oxidation reaction is 4-7, an anode and a cathode are inert electrodes, the voltage is 2-380V, and the current density is 10-1000A/m2(preferably 300 to 400A/m)2) The electrolytic oxidation time is 0.1 min-10 h (preferably 5-7 h), and the polyphenylene sulfide sulfone ketone nascent fiber is obtained by oxidation under the action of an oxidation catalyst; the electrolyte is a potassium hydrogen sulfate solution; the oxidation capacity is regulated and controlled by adjusting the current intensity and the voltage of the electrolytic oxidation device, and the online controllable oxidation is realized. The active oxygen generated by electrolysis is hydroxyl free radical, superoxide, peroxy or oxygen free radical, etc.
When the oxygen saturated solution of water is adopted, oxygen or air is continuously introduced into deionized water, and meanwhile, aryl alcohol compounds are used as oxidation auxiliary agents and added into the deionized water to obtain the oxygen saturated solution of water; soaking the ketone-containing PPS tows prepared in the step (1) in an oxygen saturated solution of water, and carrying out oxidation reaction with air or oxygen for 1 min-24 h (preferably 10 min-2 h) at 40-44 ℃ under the action of an oxidation catalyst to realize online oxidation of the ketone-containing PPS tows to obtain polyphenylene sulfide sulfone ketone nascent fibers; the aryl alcohol compound is ethyl anthracenol, phenol, naphthol, bi-phenol, anthracenol or phenanthrenol. The mass of the aryl alcohol compound accounts for 1 to 40 weight percent (preferably 5 to 20 weight percent) of the mass of the oxygen saturated solution of water; the aryl alcohols are air oxidized to quinones which reoxidize the sulfides to sulfones and sulfoxides which are themselves reduced to aryl alcohols, thus the amount of oxygen or air added is not required.
When the ozone water solution is adopted, the ozone generated by the ozone oxidation device (namely, the ozone generator) is continuously introduced into the deionized water, and the TiO is added2、SnO2、ZrO2、MoO3Or WO3Adding the mixed solution serving as an auxiliary oxidant into deionized water to obtain an ozone water solution; soaking the ketone-containing PPS tows prepared in the step (1) in an ozone water solution, and oxidizing for 0.1-24 hours at 40-95 ℃ under the action of an oxidation catalyst to realize online oxidation of the ketone-containing PPS tows, so as to obtain polyphenylene sulfide sulfone ketone nascent fibers; the mass ratio of the ozone to the ketone-containing PPS tows is 48-96: 108. The mass of the auxiliary oxidant accounts for 0.1-5 wt% (preferably 0.5-2 wt%) of the mass of the ozone water solution.
(3) Washing the polyphenylene sulfide sulfone ketone nascent fiber prepared in the step (2) by deionized water to remove residual impurity agents (including an oxidation system and an oxidation catalyst), and drying to obtain the polyphenylene sulfide sulfone ketone fiber with oxidation resistance, high temperature resistance, no shrinkage and self-extinguishing property;
preferably, in the step (3), the drying temperature is 30 to 240 ℃ (preferably 60 to 200 ℃, more preferably 140 to 200 ℃) and the drying time is 0.1 to 24 hours (preferably 0.1 to 2 hours). The proper drying temperature can realize the self-repair of the defects of the polyphenylene sulfide sulfone ketone fiber, namely, the content or the proportion of sulfone and sulfoxide in fiber molecules is optimized at higher temperature, and finally the mechanical property of the polyphenylene sulfide sulfone ketone fiber is improved.
Preferably, the above steps (1) to (3) are carried out under normal pressure to 30 standard atmospheric pressures.
Example 1
(1) 5g of terephthalic acid and 1g of TiO2Blending, melting and granulating the ketone-containing PPS resin and 494g of PPS resin in a double-screw extruder at high temperature, wherein the temperature of a feed inlet of the screw extruder is 265 ℃, the temperature of a die head is 310 ℃, and the temperature of a middle zone of a spinning screw is controlled to be 300-325 ℃ to prepare the ketone-containing PPS resin slice;
then carrying out particle melt spinning on the ketone-containing PPS resin slice to obtain ketone-containing PPS tows; the temperature of a feeding port is 305 ℃, the temperature of a second zone is 320-330 ℃, the temperature of a third zone is 325-335 ℃, the temperature of a fourth zone is 325-335 ℃, and the temperature of a die head is 315 ℃; the hot stretching temperature is 95 ℃, and the stretching ratio is 3.5 times;
(2) a ketone-containing PPS tow (tensile strength 5.5CN/dt, elongation at break 28%) was immersed in 10 wt% H2O210 wt% acetic acid, 0.1 wt% HCl in water, ketone-containing PPS tow and oxidant solutionThe mass ratio of (1: 5) and the soaking at 60 ℃ for 30 min; filtering the solution by using a 200-400-mesh steel wire mesh to obtain polyphenylene sulfide sulfone ketone nascent fibers;
(3) and (3) washing the polyphenylene sulfide sulfone ketone nascent fiber prepared in the step (2) with deionized water for 3 times, and then drying in vacuum at 140 ℃ for 2h to obtain the polyphenylene sulfide sulfone ketone fiber.
The prepared polyphenylene sulfide sulfone ketone fiber has the advantages that the oxidation weight is increased by 18 wt%, the oxidation resistance, the high temperature resistance, the self-extinguishing property, the no-melt shrinkage, the no-melt-drip and the self-extinguishing property are realized, the glass transition temperature reaches 182-185 ℃, the tensile strength of the fiber is 4.5CN/dt, and the elongation at break is 18%. Compared with PPS protofilament, the polyphenylene sulfide sulfone ketone fiber has greatly improved temperature resistance, ultraviolet resistance and oxidation resistance.
As can be seen from figure 1, after the ketone-containing PPS is oxidized, S atoms are changed into sulfone groups, and the prepared modified fiber is proved to be the polyphenylene sulfide sulfone ketone fiber.
In fig. 2, the test conditions corresponding to abscissa 1 are: 98% H at 85 DEG C2SO4Treating for 24 h; the abscissa 2 corresponds to the test conditions: 60% H at 85 DEG C2SO4Treating for 24 h; the abscissa 3 corresponds to the test conditions: 60% HNO at 85 deg.C3Treating for 24 h; the test conditions for abscissa 4 are: treating with 40% NaOH at 85 deg.C for 24 hr; the test conditions for abscissa 5 are: 30% H at 50 ℃2O2Treating for 24 h; the abscissa 6 corresponds to the high temperature resistance test, the test conditions being: and treating at 230 ℃ for 24 h. As can be seen from figure 2, the PPS has poor high temperature resistance and oxidation resistance, and the polyphenylene sulfide sulfone ketone fiber of the invention has better temperature resistance, especially excellent oxidation resistance, so the polyphenylene sulfide sulfone ketone fiber of the invention has excellent high temperature resistance, oxidation resistance, acid and alkali resistance and other properties.
As can be seen from FIG. 3, through a combustion experiment, the PPS fiber has obvious fire-encountering fusibility and combustion fusibility, while the polyphenylene sulfide sulfone ketone fiber of the invention has no fusibility and no combustion fusibility. Currently, no method for simultaneously measuring the melt shrinkage and the burning droplet properties of the fibers and the fabric is found.
The burning test is to observe the carbonization process by using the fiber or the fabric under the condition of ignition or burning, if the fiber shrinks or forms molten drops by heating, the carbon residue after the fiber or the fabric burns is different from the original material shape or size before the burning. If heated to not shrink and burn to not melt, the carbon residue will be approximately the same shape or size as the original material prior to burning. The specific method is to burn the fiber fabric or fiber on the flame of the alcohol lamp without leaving the fire until the combustion and carbonization are completed. The polyphenylene sulfide sulfone ketone fiber has a very high limit oxygen index (32-34), and self-extinguishes when being away from fire.
As can be seen from FIG. 4, the melting point of PPS is 280-300 ℃, but the melting point of the polyphenylene sulfide sulfone ketone fiber is basically not observed, which shows that the polyphenylene sulfide sulfone ketone fiber has excellent temperature resistance.
As can be seen from fig. 5, the PPS fiber structure is severely damaged after uv irradiation. As can be seen from FIG. 6, the polyphenylene sulfide sulfone ketone fiber has ultraviolet resistance (contains nano ultraviolet resistance additives), and the polyphenylene sulfide sulfone ketone fiber is less affected by ultraviolet, which shows that the polyphenylene sulfide sulfone ketone fiber has good ultraviolet resistance, so that the polyphenylene sulfide sulfone ketone fiber has excellent ultraviolet resistance.
Example 2
(1) 3g malonic acid, 0.5g SnO2Blending, melting and granulating the obtained product and 496.5g of PPS resin in a double-screw extruder at a high temperature, wherein the temperature of a feed inlet of the screw extruder is 260 ℃, the temperature of a die head is 315 ℃, and the temperature of a middle area of a spinning screw is 295-320 ℃, so that a ketone-containing PPS resin slice is prepared;
then carrying out particle melt spinning on the ketone-containing PPS resin slice to obtain ketone-containing PPS tows; the temperature of a feeding port is 305 ℃, the temperature of a second zone is 325 ℃, the temperature of a third zone is 325 ℃, the temperature of a fourth zone is 330 ℃ and the temperature of a die head is 315 ℃; the hot stretching temperature is 100 ℃, and the stretching ratio is 4 times;
(2) soaking a ketone-containing PPS (tensile strength of 5.3CN/dt, elongation at break of 32%) in benzene containing 15 wt% of benzoyl peroxide, 5 wt% of butyric acid and 0.1 wt% of benzenesulfonic acid, wherein the mass ratio of the ketone-containing PPS tow to an oxidant solution is 1:11, and soaking for 10min at 60 ℃; filtering the solution by using a 200-400-mesh steel wire mesh to obtain polyphenylene sulfide sulfone ketone nascent fibers;
(3) and (3) washing the polyphenylene sulfide sulfone ketone nascent fiber prepared in the step (2) with deionized water for 2 times, and then drying the polyphenylene sulfide sulfone ketone nascent fiber in vacuum at the temperature of 140 ℃ for 2 hours to obtain the polyphenylene sulfide sulfone ketone fiber.
The prepared polyphenylene sulfide sulfone ketone fiber has the advantages that the oxidation weight is increased by 15 wt%, the oxidation resistance, the high temperature resistance, the self-extinguishing property, the melt shrinkage and the dripping and self-extinguishing phenomena are avoided, the glass transition temperature reaches 171-175 ℃, the tensile strength of the fiber is 4.6CN/dt, and the elongation at break is 20%.
Example 3
(1) 4g of adipic acid, 1g of ZrO2Mixing the PPS resin with 495g at high temperature in a double-screw extruder, melting and granulating, wherein the temperature of a feed inlet of the screw extruder is 265 ℃, the temperature of a die head is 310 ℃, and the temperature of a middle area of a spinning screw is 300-330 ℃, so as to prepare the ketone-containing PPS resin slice;
then carrying out particle melt spinning on the ketone-containing PPS resin slice to obtain ketone-containing PPS tows; the temperature of a feeding port is 300 ℃, the temperature of a second area is 330 ℃, the temperature of a third area is 330 ℃, the temperature of a fourth area is 330 ℃ and the temperature of a die head is 310 ℃; the hot stretching temperature is 95 ℃, and the stretching ratio is 3 times;
(2) soaking the PPS tows (tensile strength of 5.3CN/dt and elongation at break of 32%) containing ketone in an electrolytic oxidation device, wherein the electrolyte potassium hydrogen sulfate solution contains 2 wt% of acetic acid and 0.1 wt% of sulfuric acid, the anode and the cathode are inert electrodes, the voltage is 380V, and the current density is 500A/m2Electrolyzing and oxidizing for 1h to obtain polyphenylene sulfide sulfone ketone nascent fibers;
(3) and (3) washing the polyphenylene sulfide sulfone ketone nascent fiber prepared in the step (2) with deionized water for 3 times, and then drying the polyphenylene sulfide sulfone ketone nascent fiber in vacuum at 160 ℃ for 2 hours to obtain the polyphenylene sulfide sulfone ketone fiber.
The prepared polyphenylene sulfide sulfone ketone fiber has the advantages that the oxidation weight is increased by 12.5 wt%, the oxidation resistance, the high temperature resistance, the self-extinguishing property, the melt shrinkage and the dripping and self-extinguishing phenomena are avoided, the glass transition temperature reaches 165-170 ℃, the tensile strength of the fiber is 4.4CN/dt, and the elongation at break is 20%.
Example 4
(1) 4g of adipic acid, 1g of Al2O3Mixing the PPS resin with 495g at high temperature in a double-screw extruder, melting and granulating, wherein the temperature of a feed inlet of the screw extruder is 260 ℃, the temperature of a die head is 310 ℃, and the temperature of a middle area of a spinning screw is 295-320 ℃, so that the ketone-containing PPS resin slices are prepared;
then carrying out particle melt spinning on the ketone-containing PPS resin slice to obtain ketone-containing PPS tows; the temperature of a feeding port is 305 ℃, the temperature of a second zone is 325 ℃, the temperature of a third zone is 330 ℃, the temperature of a fourth zone is 330 ℃ and the temperature of a die head is 310 ℃; the hot stretching temperature is 100 ℃, and the stretching ratio is 3.8 times;
(2) introducing ozone generated by an ozone oxidation device into deionized water, and adding 5 wt% of acetic acid, 0.1 wt% of sulfuric acid and 0.5 wt% of auxiliary oxidant nano TiO2(ii) a Soaking the ketone-containing PPS filament bundle (tensile strength of 5.3CN/dt and elongation at break of 32%) into the PPS filament bundle, wherein the mass ratio of the ketone-containing PPS filament bundle to the ozone water solution is 1:5, and oxidizing the PPS filament bundle at 40 ℃ for 60min to obtain polyphenylene sulfide sulfone ketone nascent fibers; the mass ratio of the ozone to the ketone-containing PPS tows is 72: 108;
(3) and (3) washing the polyphenylene sulfide sulfone ketone nascent fiber prepared in the step (2) with deionized water for 3 times, and then drying the polyphenylene sulfide sulfone ketone nascent fiber in vacuum at 160 ℃ for 2 hours to obtain the polyphenylene sulfide sulfone ketone fiber.
The prepared polyphenylene sulfide sulfone ketone fiber has the advantages that the oxidation weight is increased by 14 wt%, the oxidation resistance, the high temperature resistance, the self-extinguishing property, the no-shrinkage, the no-dripping and the self-extinguishing phenomena are caused, the glass transition temperature reaches 165-170 ℃, the tensile strength of the fiber is 4.2CN/dt, and the elongation at break is 22%.
Example 5
(1) 4g of biphenyltricarboxylic acid and 1g of Ga2O3Mixing with 495g of PPS resin at high temperature in a double-screw extruder, melting and granulating, wherein the temperature of a feed inlet of the screw extruder is 275 ℃, the temperature of a die head is 315 ℃, and the temperature of a middle area of a spinning screw is 300-330 ℃, so as to prepare a ketone-containing PPS resin slice;
then carrying out particle melt spinning on the ketone-containing PPS resin slice to obtain ketone-containing PPS tows; the temperature of a feeding port is 300 ℃, the temperature of a second zone is 325 ℃, the temperature of a third zone is 330 ℃, the temperature of a fourth zone is 330 ℃ and the temperature of a die head is 320 ℃; the hot drawing temperature is 105 ℃, and the drawing ratio is 3 times;
(2) introducing ozone generated by an ozone oxidation device into deionized water, and adding 5 wt% of propionic acid, 0.2 wt% of hydrochloric acid and 1 wt% of auxiliary oxidant heteropoly acid; soaking the ketone-containing PPS filament bundle (tensile strength of 5.0CN/dt and elongation at break of 26%) into the PPS filament bundle, wherein the mass ratio of the ketone-containing PPS filament bundle to the ozone water solution is 1:5, and oxidizing the PPS filament bundle at the temperature of 45 ℃ for 30min to obtain polyphenylene sulfide sulfone ketone nascent fibers; the mass ratio of the ozone to the ketone-containing PPS tows is 72: 108;
(3) and (3) washing the polyphenylene sulfide sulfone ketone nascent fiber prepared in the step (2) with deionized water for 4 times, and then drying the polyphenylene sulfide sulfone ketone nascent fiber in vacuum at 150 ℃ for 1h to obtain the polyphenylene sulfide sulfone ketone fiber.
The prepared polyphenylene sulfide sulfone ketone fiber has the advantages of oxidation weight increment of 12 wt%, oxidation resistance, high temperature resistance, self-extinguishing property, no melt shrinkage, no melt drip and self-extinguishing property, glass transition temperature of 174-178 ℃, fiber tensile strength of 4.3CN/dt and elongation at break of 20%.
Example 6
(1) 3g of oxalic acid, 1g of ZnO and 496g of PPS resin are subjected to high-temperature blending, melting and granulation in a double-screw extruder, wherein the temperature of a feed inlet of the screw extruder is 255 ℃, the temperature of a die head is 305 ℃, the temperature of the middle zone of a spinning screw is 290-315 ℃, and ketone-containing PPS resin slices are prepared;
then carrying out particle melt spinning on the ketone-containing PPS resin slice to obtain ketone-containing PPS tows; the temperature of a feeding port is 295 ℃, the temperature of a second zone is 325 ℃, the temperature of a third zone is 325 ℃, the temperature of a fourth zone is 320 ℃, and the temperature of a die head is 315 ℃; the hot stretching temperature is 95 ℃, and the hot stretching is 3.5 times;
(2) soaking the PPS tows (tensile strength of 5.0CN/dt and elongation at break of 30%) containing ketone in an electrolytic oxidation device, wherein an electrolyte potassium hydrogen sulfate solution contains 5 wt% of acetic acid and 1 wt% of phosphoric acid, an anode and a cathode are inert electrodes, the voltage is 380V, and the current density is 600A/m2Electrolyzing and oxidizing for 20min to obtain polyphenylene sulfide sulfone ketone nascent fiber;
(3) and (3) washing the polyphenylene sulfide sulfone ketone nascent fiber prepared in the step (2) with deionized water for 3 times, and then drying the polyphenylene sulfide sulfone ketone nascent fiber in vacuum at 160 ℃ for 2 hours to obtain the polyphenylene sulfide sulfone ketone fiber.
The prepared polyphenylene sulfide sulfone ketone fiber has the advantages that the oxidation weight is increased by 17 wt%, the glass transition temperature reaches 201-205 ℃, the polyphenylene sulfide sulfone ketone fiber has the phenomena of oxidation resistance, high temperature resistance, self-extinguishing property, no fusion shrinkage, no molten drop and self-extinguishing property, the tensile strength of the fiber is 4.1CN/dt, and the elongation at break is 20%.
Example 7
(1) 5g of biphenyldicarboxylic acid and 1g of TiO2Blending and melting with 495g of PPS resin at high temperature in a double-screw extruderGranulating, wherein the temperature of a feed inlet of a screw extruder is 275 ℃, the temperature of a die head is 315 ℃, and the temperature of a middle area of a spinning screw is 300-330 ℃, so as to prepare the ketone-containing PPS resin slice;
then carrying out particle melt spinning on the ketone-containing PPS resin slice to obtain ketone-containing PPS tows; the temperature of a feeding port is 305 ℃, the temperature of a second zone is 325 ℃, the temperature of a third zone is 325 ℃, the temperature of a fourth zone is 325 ℃ and the temperature of a die head is 320 ℃; the hot drawing temperature is 110 ℃, and the hot drawing multiple is 3.5 times;
(2) soaking a ketone-containing PPS (tensile strength of 4.8CN/dt, elongation at break of 30%) in N, N-dimethylacetamide containing 10 wt% of cyclohexanone peroxide, 10 wt% of acetic acid and 2 wt% of naphthalene sulfonic acid, wherein the mass ratio of the ketone-containing PPS tow to an oxidant solution is 1:10, and soaking for 30min at 60 ℃; filtering the solution by using a 200-400-mesh steel wire mesh to obtain polyphenylene sulfide sulfone ketone nascent fibers;
(3) and (3) washing the polyphenylene sulfide sulfone ketone nascent fiber prepared in the step (2) with deionized water for 4 times, and then drying the polyphenylene sulfide sulfone ketone nascent fiber in vacuum at 150 ℃ for 5 hours to obtain the polyphenylene sulfide sulfone ketone fiber.
The prepared polyphenylene sulfide sulfone ketone fiber has the advantages that the oxidation weight is increased by 18 wt%, the glass transition temperature reaches 178-182 ℃, the polyphenylene sulfide sulfone ketone fiber has the phenomena of oxidation resistance, high temperature resistance, self-extinguishing property, no melt shrinkage, no melt dripping and self-extinguishing property, the tensile strength of the fiber is 4.0CN/dt, and the elongation at break is 19%.
As can be seen from FIG. 7, the polyphenylene sulfide sulfone ketone fiber has good temperature resistance, and the thermal decomposition temperature is more than 370 ℃. As can be seen from fig. 8, the polyphenylene sulfide sulfone ketone fiber contains a large amount of oxygen, and the oxygen is mainly in the form of sulfone.
Example 8
(1) 5g of naphthalenedicarboxylic acid and 1g of Al2O3Blending, melting and granulating the ketone-containing PPS resin and 494g of PPS resin in a double-screw extruder at a high temperature, wherein the temperature of a feed inlet of the screw extruder is 270 ℃, the temperature of a die head of the screw extruder is 315 ℃, and the temperature of a middle zone of a spinning screw is 300-330 ℃, so as to prepare the ketone-containing PPS resin slice;
then carrying out particle melt spinning on the ketone-containing PPS resin slice to obtain ketone-containing PPS tows; the temperature of a feeding port is 295 ℃, the temperature of a second zone is 325 ℃, the temperature of a third zone is 325 ℃, the temperature of a fourth zone is 325 ℃ and the temperature of a die head is 315 ℃; the hot stretching temperature is 100 ℃, and the hot stretching multiple is 3.5 times;
(2) soaking a ketone-containing PPS (tensile strength of 4.9CN/dt and elongation at break of 29%) in water containing 13 wt% of NaClO, 3 wt% of acetic acid and 1 wt% of boric acid, wherein the mass ratio of the ketone-containing PPS tow to an oxidant solution is 1:6, and soaking for 30min at 60 ℃; filtering the solution by using a 200-400-mesh steel wire mesh to obtain polyphenylene sulfide sulfone ketone nascent fibers;
(3) and (3) washing the polyphenylene sulfide sulfone ketone nascent fiber prepared in the step (2) with deionized water for 3 times, and then drying the fiber at 140 ℃ for 1 hour in vacuum to obtain the polyphenylene sulfide sulfone ketone fiber.
The prepared polyphenylene sulfide sulfone ketone fiber has the advantages that the oxidation weight is increased by 12 wt%, the glass transition temperature reaches 200-205 ℃, the polyphenylene sulfide sulfone ketone fiber has the phenomena of oxidation resistance, high temperature resistance, self-extinguishing property, no fusion shrinkage, no molten drop and self-extinguishing property, the tensile strength of the fiber is 3.8CN/dt, and the elongation at break is 17%.
Example 9
(1) 5g of naphthalenedicarboxylic acid and 1g of Al2O3Blending and melting the PPS resin with 494g in a double-screw extruder to carry out in-situ spinning by a one-step method to prepare ketone-containing PPS tows; the temperature of a feeding port is 285 ℃, the temperature of a second area is 320 ℃, the temperature of a third area is 325 ℃, the temperature of a fourth area is 330 ℃ and the temperature of a die head is 315 ℃; the hot stretching temperature is 100 ℃, and the hot stretching multiple is 3.5 times;
(2) soaking a ketone-containing PPS (tensile strength of 5.2CN/dt and elongation at break of 27%) in water containing 13 wt% of NaClO, 3 wt% of acetic acid and 1 wt% of boric acid, wherein the mass ratio of the ketone-containing PPS tow to an oxidant solution is 1:6, and soaking for 30min at 60 ℃; filtering the solution by using a 200-400-mesh steel wire mesh to obtain polyphenylene sulfide sulfone ketone nascent fibers;
(3) and (3) washing the polyphenylene sulfide sulfone ketone nascent fiber prepared in the step (2) with deionized water for 3 times, and then drying the fiber at 140 ℃ for 1 hour in vacuum to obtain the polyphenylene sulfide sulfone ketone fiber.
The prepared polyphenylene sulfide sulfone ketone fiber has the advantages that the oxidation weight is increased by 13 wt%, the glass transition temperature reaches 200-205 ℃, the polyphenylene sulfide sulfone ketone fiber has the phenomena of oxidation resistance, high temperature resistance, self-extinguishing property, no fusion shrinkage, no molten drop and self-extinguishing property, the tensile strength of the fiber is 4.0CN/dt, and the elongation at break is 17%.
It can be seen from fig. 9 and 10 that the fiber morphology is well maintained. As can be seen from fig. 9, the surface of the polyphenylene sulfide sulfone ketone fiber contains inorganic nanoparticles. As can be seen from fig. 10, the uniform dispersion of the nanoparticles can be achieved by the one-step spinning method, and it is also laterally demonstrated that the friedel-crafts acylation can effectively react in the one-step spinning method.
Nothing in this specification is said to apply to the prior art.
Claims (10)
1. The preparation method of the polyphenylene sulfide sulfone ketone fiber is characterized by comprising the following steps:
(1) taking metal oxide as a catalyst, and carrying out in-situ spinning on PPS resin, the metal oxide and carboxylic acid by a screw extrusion reaction blending melting one-step method to prepare ketone-containing PPS tows; or extruding PPS resin, metal oxide and carboxylic acid by using a screw to react, blending, melting and granulating to prepare ketone-containing PPS particles, and then carrying out particle melt spinning by using the ketone-containing PPS particles as a raw material to prepare ketone-containing PPS tows; the carboxylic acid is dicarboxylic acid or polycarboxylic acid;
(2) placing the ketone-containing PPS tows prepared in the step (1) in an oxidation system, and carrying out oxidation reaction under the action of an oxidation catalyst to obtain polyphenylene sulfide sulfone ketone nascent fibers;
(3) and (3) removing impurities from the polyphenylene sulfide sulfone ketone nascent fiber prepared in the step (2), and drying to obtain the polyphenylene sulfide sulfone ketone fiber.
2. The method for preparing polyphenylene sulfide sulfone ketone fiber as recited in claim 1, wherein in step (1), the dicarboxylic acid is terephthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid or biphenyldicarboxylic acid; the polybasic carboxylic acid is trimethyl acid containing benzene ring; the metal oxide is TiO2、SiO2、ZrO2、ZnO、SnO2、Al2O3、MoO3、WO3、CdO、GeO2Or Ga2O3At least one of (1).
3. The preparation method of the polyphenylene sulfide sulfone ketone fiber as recited in claim 1, wherein in the step (1), the mass of the carboxylic acid is 0.01 to 10 wt% of the total mass of the PPS resin, the metal oxide and the carboxylic acid; the mass of the metal oxide is 0.01 to 5 wt% of the total mass of the PPS resin, the metal oxide and the carboxylic acid.
4. The preparation method of the polyphenylene sulfide sulfone ketone fiber as claimed in claim 1, wherein in the step (1), the blending melting one-step in-situ spinning process comprises the following steps: mixing or not-mixing-melting by a screw extruder-metering pump-forced filtration-spinning pack-spun yarn-hot stretching-ketone-containing PPS tows;
the blending, melting and granulating process comprises the following steps: mixing or not-mixing, melting by a screw extruder, metering by a melt metering pump, forcibly filtering, wire drawing and granulating, and preparing ketone-containing PPS particles;
the process of particle melt spinning is as follows: drying the ketone-containing PPS particles, melting by a screw extruder, metering a melt pump, forcibly filtering, spinning a spinning pack, primary spinning, hot stretching, and spinning the ketone-containing PPS tows;
the hot stretching process is carried out at a hot stretching temperature of 90-200 ℃ and a stretching ratio of 2-10 times.
5. The preparation method of the polyphenylene sulfide sulfone ketone fiber as claimed in claim 1, wherein in the step (2), the mass of the ketone-containing PPS tows accounts for 0.1-40 wt% of the total mass of the ketone-containing PPS tows and the oxidation system; the mass concentration of the oxidation catalyst in the oxidation system is 0.1-40 wt%.
6. The preparation method of the polyphenylene sulfide sulfone ketone fiber as claimed in claim 1, wherein in the step (2), the oxidation catalyst is an inorganic acid and/or an organic acid; the inorganic acid is sulfuric acid, hydrochloric acid, carbonic acid, heteropolyacid, boric acid, phosphoric acid, nitric acid, molybdic acid, tungstic acid or acidic molecular sieve; the organic acid is formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, capric acid, benzoic acid, naphthoic acid, benzenesulfonic acid, naphthalenesulfonic acid, oxalic acid, malonic acid, succinic acid, adipic acid, or pimelic acid.
7. The method for preparing polyphenylene sulfide sulfone ketone fiber as recited in claim 1, wherein in the step (2), the oxidation system is an oxidant solution, an electrolyte, an oxygen saturated solution of water or an aqueous ozone solution;
when an oxidant solution is adopted, soaking the ketone-containing PPS tows prepared in the step (1) in the oxidant solution, and oxidizing the ketone-containing PPS tows at the temperature of 0-140 ℃ for 0.1 min-24 h under the action of an oxidation catalyst to obtain polyphenylene sulfide sulfone ketone nascent fibers;
when an electrolyte is adopted, the ketone-containing PPS tows prepared in the step (1) are soaked in the electrolyte of an electrolytic oxidation device, the initial pH of the electrolytic oxidation reaction is 4-7, an anode and a cathode are inert electrodes, the voltage is 2-380V, and the current density is 10-1000A/m2The electrolytic oxidation time is 0.1 min-10 h, and the polyphenylene sulfide sulfone ketone nascent fiber is obtained by oxidation under the action of an oxidation catalyst;
when the oxygen saturated solution of water is adopted, oxygen or air is continuously introduced into deionized water, and meanwhile, aryl alcohol compounds are used as oxidation auxiliary agents and added into the deionized water to obtain the oxygen saturated solution of water; soaking the ketone-containing PPS tows prepared in the step (1) in an oxygen saturated solution of water, and carrying out oxidation reaction for 1 min-24 h at 40-44 ℃ under the action of an oxidation catalyst to obtain polyphenylene sulfide sulfone ketone nascent fibers;
when the ozone aqueous solution is adopted, continuously introducing ozone generated by the ozone oxidation device into deionized water, and adding an auxiliary oxidant into the deionized water to obtain the ozone aqueous solution; and (2) soaking the ketone-containing PPS tows prepared in the step (1) in an ozone water solution, and oxidizing for 0.1-24 hours at 40-95 ℃ under the action of an oxidation catalyst to obtain the polyphenylene sulfide sulfone ketone nascent fiber.
8. The preparation method of the polyphenylene sulfide sulfone ketone fiber as recited in claim 7, wherein in the step (2), the oxidant solution is a solution with a mass concentration of 0.1-40 wt% formed by dissolving or dispersing an oxidant in a solvent; the oxidant is H2O2、Na2O2、NaClO、KClO、HClO、KMnO4、K2Cr2O7、MnO2、FeCl3、NO2、HNO3At least one of peracetic acid, performic acid, dicumyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, t-butyl peroxide, or perbenzoic acid; the solvent is at least one of water, benzene, toluene, ketone compounds, organic alcohol, amide compounds, dimethyl sulfoxide, tetrahydrofuran, diethyl ether, dimethyl ether, cyclohexane, n-hexane, organic acid or halogenated hydrocarbon.
9. The method for preparing polyphenylene sulfide sulfone ketone fiber as recited in claim 7, wherein in the step (2), the electrolyte is potassium hydrogen sulfate solution;
the aryl alcohol compound is ethyl anthracenol, phenol, naphthol, bi-phenol, anthracenol or phenanthrenol; the mass of the aryl alcohol compound accounts for 1-40 wt% of the mass of the oxygen saturated solution of water;
the auxiliary oxidant is TiO2、SnO2、ZrO2、MoO3Or WO3(ii) a The mass ratio of the ozone to the ketone-containing PPS tows is 48-96: 108; the mass of the auxiliary oxidant accounts for 0.1-5 wt% of the mass of the ozone water solution.
10. The preparation method of the polyphenylene sulfide sulfone ketone fiber as claimed in claim 1, wherein in the step (3), the drying temperature is 30-240 ℃ and the drying time is 0.1-24 h.
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| CN115513473A (en) * | 2022-09-29 | 2022-12-23 | 天津工业大学 | Polyphenylene sulfide-based hollow fiber with controllable wall thickness and preparation method and application thereof |
| CN115637582A (en) * | 2022-10-26 | 2023-01-24 | 清源创新实验室 | Method for preparing polyphenylene sulfone sulfoxide fiber by ozone-hydrogen peroxide synergistic heterogeneous oxidation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115513473A (en) * | 2022-09-29 | 2022-12-23 | 天津工业大学 | Polyphenylene sulfide-based hollow fiber with controllable wall thickness and preparation method and application thereof |
| CN115513473B (en) * | 2022-09-29 | 2024-04-26 | 天津工业大学 | Wall thickness controllable polyphenylene sulfide-based hollow fiber and preparation method and application thereof |
| CN115637582A (en) * | 2022-10-26 | 2023-01-24 | 清源创新实验室 | Method for preparing polyphenylene sulfone sulfoxide fiber by ozone-hydrogen peroxide synergistic heterogeneous oxidation |
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