CN110184811A - A kind of polyphenylene sulfide fibre and preparation method thereof of the anti-shrink under ignition - Google Patents
A kind of polyphenylene sulfide fibre and preparation method thereof of the anti-shrink under ignition Download PDFInfo
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- CN110184811A CN110184811A CN201910340267.8A CN201910340267A CN110184811A CN 110184811 A CN110184811 A CN 110184811A CN 201910340267 A CN201910340267 A CN 201910340267A CN 110184811 A CN110184811 A CN 110184811A
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Abstract
The present invention provides a kind of polyphenylene sulfide fibre and preparation method thereof of anti-shrink under ignition, belongs to fibrous material technical field.A kind of preparation method of the polyphenylene sulfide fibre of the anti-shrink under ignition, the following steps are included: (1) polyphenylene sulfide fibre is added in oxidizing agent solution impregnates 1-4h under conditions of 180-200 DEG C, 0.5h-1h then is impregnated under conditions of 160-180 DEG C；(2) polyphenylene sulfide fibre is added in antioxidant solution and impregnates 1-2h；(3) polyphenylene sulfide fibre washed, be dried in vacuo；(4) polyphenylene sulfide fibre after drying is added in polyacrylamide solution, impregnates 3-5h under conditions of 150-180 DEG C；(5) polyphenylene sulfide fibre is added in 1,4- dichloromethyl benzole soln and is crosslinked 3-5h；(6) polyphenylene sulfide fibre after crosslinking washed, be dried in vacuo obtained anti-shrink polyphenylene sulfide fibre.Molten drop, shrinkage phenomenon will not occurs in burning with preferable anti-contracility energy, mechanical performance, thermal stability in it.
Description
Technical field
The invention belongs to fibrous material technical fields, specifically, being related to a kind of polyphenyl of anti-shrink under ignition
Sulfide fibers and preparation method thereof.
Background technique
Polyphenylene sulfide fibre (polyphenylene sulfide fibre) is prepared by raw material of polyphenylene sulfide
Fiber, be the linear semi-crystalline polymer for being alternately arranged and being formed with the sulphur atom that connects on phenyl ring and its contraposition, pass through list
Polyphenylene sulfide is made in body polymerization reaction, and the polyphenylene sulfide of spinning-grade is being carried out melt spinning, hot-stretch and sizing
Etc. polyphenylene sulfide fibre is made after techniques.
Polyphenylene sulfide fibre has good heat resistance, is mainly used as high temperature filtration fabric, tolerable temperature is up to 190 DEG C.
But the exhaust temperature of plant emissions often reaches 190-220 DEG C, fibres show creep leads to web contraction under this hot environment,
And it causes polyphenylene sulfide fibre mechanical property to reduce and is reduced with the service life.Meanwhile polyphenylene sulfide fibre has the characteristics that thermoplastic, point
When combustion or burning, it may occur that melting is shunk, it may occur that the phenomenon that melt flow gel.It is poly- that CN108330680A discloses a kind of modification
The preparation method of diphenyl sulfide yarn, CN105113209B disclose a kind of preparation of PPS fiber with self-extinguishment and without molten drop
Method, all poly-p-phenylene sulfide ether fiber are aoxidized to change its collapsing performance, but modified polyphenylene sulfide fibre is intermolecular
Molecular force be affected, mechanical performance is affected.
Therefore, a kind of polyphenylene sulfide fibre and its system of anti-shrink under ignition for being able to solve the above problem is invented
Preparation Method becomes current urgent problem to be solved.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of the polyphenylene sulfide fibre of anti-shrink under ignition, sides
Method is simple, and polyphenylene sulfide fibre obtained has preferable anti-contracility energy, mechanical performance, thermal stability and high temperature resistant, i.e.,
Make will not to occur in ignition melting, shrink, phenomena such as melt flow gel.
Another object of the present invention is to provide a kind of polyphenylene sulfide fibres of anti-shrink under ignition, have preferable
Anti- contracility energy, mechanical performance, thermal stability and high temperature resistant, even if burning when molten drop, shrinkage phenomenon will not occur.
In order to achieve the above object, the solution that the present invention uses is:
The present invention provides a kind of preparation method of the polyphenylene sulfide fibre of anti-shrink under ignition, including following step
It is rapid:
(1) polyphenylene sulfide fibre is added in oxidizing agent solution and impregnates 1-4h under conditions of 180-200 DEG C, then existed
0.5h-1h is impregnated under conditions of 160-180 DEG C；
(2) polyphenylene sulfide fibre after step 1 dipping is added in antioxidant solution and is soaked under conditions of 120-140 DEG C
Stain 1-2h；
(3) polyphenylene sulfide fibre after step 2 dipping is washed with acetone, is then washed again with distilled water,
Polyphenylene sulfide fibre after cleaning is dried in vacuo；
(4) polyphenylene sulfide fibre after drying is added in polyacrylamide solution, is impregnated under conditions of 150-180 DEG C
3-5h；
(5) polyphenylene sulfide fibre after step 4 dipping is added in 1,4- dichloromethyl benzole soln and is crosslinked 3-5h；
(6) polyphenylene sulfide fibre after crosslinking is washed with dehydrated alcohol, is then washed again with distilled water, it will
Polyphenylene sulfide fibre after cleaning carries out the polyphenylene sulfide fibre for being dried in vacuo obtained anti-shrink.
The present invention provides a kind of polyphenylene sulfide fibre of anti-shrink under ignition, is made by above-mentioned preparation method.
A kind of beneficial effect of the polyphenylene sulfide fibre of anti-shrink under ignition provided by the invention and preparation method thereof
Fruit is that the surface S atom partial oxidation of oxidant poly-p-phenylene sulfide ether fiber is first added, to change the characteristic of polyphenylene sulfide fibre,
Improve its resist melt, anti-contracility energy, wherein be divided into two stages impregnates polyphenylene sulfide fibre respectively, to time and temperature into
Row control, so that the degree of oxidation of sulphur atom is controlled, to change the heatproof of polyphenylene sulfide fibre, resist melt, anti-shrink and machine
Tool performance；Antioxidant is added after oxidation to prevent the sulphur atom on polyphenylene sulfide fibre surface from continuing to aoxidize, it is former to retain part S
Son makes it keep certain flexibility and anti-flammability；By polyacrylamide in polyphenylene sulfide fibre introducing-CO- polar group,
The heat resistance and mechanical performance that fiber can be improved increase the intermolecular force between polyphenylene sulfide main chain, to improve
Its thermal stability, mechanical performance and thermal contraction performance；Isosorbide-5-Nitrae-xylylene dichlorides is added to be crosslinked it, forms fibrous inside
Three-dimensional net structure greatly improves the thermal contraction performance and mechanical performance of polyphenylene sulfide fibre；Pass through oxidation, modification and friendship
Connection etc. cooperates, and polyphenylene sulfide fibre obtained is enable to have preferable anti-contracility, mechanical performance, thermal stability and resistance to
Phenomena such as melting will not occur in ignition, shrink for high temperature, melt flow gel.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the schematic diagram after the commercially available polyphenylene sulfide fibre burning that experimental example of the present invention provides；
Fig. 2 is the schematic diagram after polyphenylene sulfide fibre burning prepared by the embodiment of the present invention 1；
Fig. 3 is the contrast schematic diagram for the commercially available polyphenylene sulfide fibre burning front and back that experimental example of the present invention provides；
Fig. 4 is the contrast schematic diagram of polyphenylene sulfide fibre burning front and back prepared by the embodiment of the present invention 1.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Below to a kind of polyphenylene sulfide fibre and preparation method thereof of anti-shrink under ignition of the embodiment of the present invention
It is specifically described.
A kind of preparation method of the polyphenylene sulfide fibre of anti-shrink under ignition provided in an embodiment of the present invention, including
Following steps:
(1) polyphenylene sulfide fibre is added in oxidizing agent solution and impregnates 1-4h under conditions of 160-180 DEG C, then existed
0.5h-1h is impregnated under conditions of 180-200 DEG C.
Linear polyphenylthioether (Polyp Henylene Sulfide, PPS) is the phenylene and bivalent sulfur atom by aligning
It is folded the high polymer being formed by connecting, is the simplest a kind of polymer of molecular structure in sulfur-containing aromatic.Polyphenylene sulfide has benzene
The upper macromolecular line style rigid structure for being connected with S atom and constituting of ring contraposition.Because the rigid annular structure and S of phenyl ring pi bond are former
Son bonds together to form chain structure, makes it have excellent properties, and therefore, polyphenylene sulfide fibre has preferable performance, such as resistance to height
Temperature etc., but the resist melt of polyphenylene sulfide fibre, anti-contracility can be poor.Wherein, the S atom in polyphenylene sulfide molecular structure with
σ key-shaped formula is in conjunction with the C atom in phenyl ring contraposition, and the bond order of C-S key is minimum in polyphenylene sulfide molecule, i.e., between C-S atom
It is most weak at bond strength.In the embodiment of the present invention, the surface S atom partial oxidation of oxidant poly-p-phenylene sulfide ether fiber is first added,
To change the characteristic of polyphenylene sulfide fibre, its resist melt, anti-shrink, mechanical performance and thermal stability are improved.
In the embodiment of the present invention, oxidizing agent solution is to be dissolved in oxidant in the first solvent being made, and oxidant is selected from K2O2
(potassium peroxide), H2SO4(sulfuric acid), HNO3(nitric acid), CCl4(carbon tetrachloride), KMnO4(potassium permanganate), KClO4(perchloric acid
At least one of potassium), the first solvent is acetone.Wherein, the quality of oxidizing agent solution cannot be too high, and too high be easy to cause aoxidized
Fastly, it is difficult to control the degree of oxidation of polyphenylene sulfide fibre, the quality of oxidizing agent solution cannot be too low, be easy to cause oxygen if too low
Change insufficient, influence the oxidation quality of polyphenylene sulfide fibre, therefore, the mass ratio of polyphenylene sulfide fibre and oxidizing agent solution is 1:
4-6.In the embodiment of the present invention, the mass concentration of the oxidant of oxidizing agent solution is 50-60%.
C-S's can significantly weaken at bond strength with the intensification of degree of oxidation on macromolecular chain.(it is oxidized to certain journey
Make backbone breaking occur to degrade after degree and releases SO2), in the embodiment of the present invention, it is divided into two temperature and impregnates polyphenylene sulfide respectively
Ether fiber controls the temperature and dip time of oxidation, to control the degree of oxidation of S atom by selecting suitable oxidant.
To change the heatproof, resist melt performance, anti-contracility energy of polyphenylene sulfide fibre.The embodiment of the present invention is first at 160-180 DEG C
Under the conditions of impregnate 1-4h, the surface S atom partial oxidation of poly-p-phenylene sulfide ether fiber, with the increase of oxidization time, C-S at
Stroke degree reduces, and then, poly-p-phenylene sulfide ether fiber carries out the dipping of second stage, dip time under conditions of 160-180 DEG C
For 0.5h-1h.By the oxidation in two stages, the effective property for changing polyphenylene sulfide fibre improves its heatproof, resist melt
Performance, anti-contracility energy.
(2) polyphenylene sulfide fibre after step 1 dipping is added in antioxidant solution and is soaked under conditions of 120-140 DEG C
Stain 1-2h.
Wherein, because polyphenylene sulfide molecular backbone is alternately arranged by phenyl ring and S atom, benzene ring structure presence makes polyphenylene sulfide
With rigidity characteris, and thioether bond (- S-) provides flexibility for polyphenylene sulfide, and molecular structure is symmetrical.Polyphenylene sulfide fibre simultaneously
With anti-flammability, since polyphenylene sulfide fibre sulfur content is high, itself has fire-retardant ability, and fire retardant is added just without additional
Reach very high anti-flammability.In the embodiment of the present invention, antioxidant is added after oxidation to prevent polyphenylene sulfide fibre surface
Sulphur atom continues to aoxidize, and retaining part S atom makes it keep certain flexibility and anti-flammability.
Antioxidant is a kind of substance for being able to suppress or delaying high molecular polymer oxidative degradation.In the embodiment of the present invention,
Antioxidant solution is to be dissolved in antioxidant in the second solvent being made, and antioxidant is selected from flavonoids, dibutyl hydroxy toluene
And at least one of tert-butyl hydroquinone, the second solvent are acetone.Wherein, the quality of antioxidant solution cannot be too high, too
Height is easily destroyed degree of oxidation, and the quality of antioxidant solution cannot be too low, too down to less than prevent completely reaction effect, because
This, the mass ratio of polyphenylene sulfide fibre and antioxidant solution is 1:2-3.In the embodiment of the present invention, antioxidant solution resists
The mass concentration of oxidant is 40-50%.
In the embodiment of the present invention, the initial freedom generated can be eliminated by chain tra nsfer by the way that antioxidant is added
Base makes itself to be changed into inactive free radical A, terminates oxidation reaction, can effectively retain part sulphur atom, thus
Make polyphenylene sulfide fibre that there is certain flexibility and anti-flammability.
(3) polyphenylene sulfide fibre after step 2 dipping is washed with acetone, is then washed again with distilled water,
Polyphenylene sulfide fibre after cleaning is dried in vacuo.
The solvent on polyphenylene sulfide fibre is washed off by cleaning, avoids influencing subsequent reaction.First with acetone by polyphenyl
Oxidant, antioxidant on sulfide fibers are washed, and are then washed again with distilled water, can be right by washing twice
Polyphenylene sulfide fibre is effectively cleaned.
Polyphenylene sulfide fibre after cleaning is dried in vacuo, vacuum drying is a kind of material to be placed in condition of negative pressure
Under, and suitably reach boiling point under negative pressure state or by cooling so that by molten point come drying after material solidification by heating
The drying mode of material, since isolation air can effectively retain the characteristic of polyphenylene sulfide fibre under negative pressure state.This
In inventive embodiments, vacuum drying temperature cannot be too high, the too high a part of characteristic for being easily destroyed polyphenylene sulfide fibre, vacuum
Dry temperature cannot be too low, too low to extend the dry time, while be easy to causeing dry insufficient, vacuum drying condition
Are as follows: 140-160 DEG C of temperature, time 2-3h.
(4) polyphenylene sulfide fibre after drying is added in polyacrylamide solution, is impregnated under conditions of 150-180 DEG C
3-5h。
During above-mentioned oxidation reaction, strand and the oxidant of polyphenylene sulfide fibre react, and can make polyphenyl
A part of strand of sulfide fibers disconnects to a certain extent, will affect the mechanical performance of polyphenylene sulfide fibre, resist melt,
Thermal stability and thermal contraction performance etc..
Since polyphenylene sulfide fibre is rich in phenyl ring, the chemical activity of phenyl ring can use, it, will by the method for chemical modification
Functional group is introduced into polyphenylene oxide macromolecular chain, improves the mechanical performance etc. of polyphenylene sulfide fibre, to deposit after making up oxidation reaction
Some shortcomings.Wherein, polar group, such as introducing-CO- are introduced in polyphenylene sulfide fibre, and the resistance to of fiber can be improved
Hot property and mechanical performance increase the intermolecular force between polyphenylene sulfide main chain, to improve its thermal stability, resist melt
Property, mechanical performance and thermal contraction performance.
In the embodiment of the present invention, by the way that polyacrylamide solution is added in polyphenylene sulfide fibre, by polyacrylamide to
Amido bond-CO-NH- is introduced in polyphenylene sulfide fibre macromolecular chain, can effectively be increased intermolecular between polyphenylene sulfide main chain
Active force improves its thermal stability, resist melt, mechanical performance and thermal contraction performance.The quality of polyacrylamide solution cannot
Too high, too high to be easy to cause polyphenylene sulfide fibre overreact, the quality of polyacrylamide solution cannot be too low, too low to be easy to make
It is insufficient at the introducing of polyphenylene sulfide fibre strand amido bond, influence the property of modified polyphenylene sulfide fibre, therefore, polyphenylene sulfide
The mass ratio of ether fiber and polyacrylamide solution is 1:2-4.In the embodiment of the present invention, polyacrylamide solution is by polypropylene
Amide is soluble in water, wherein the mass concentration of polyacrylamide is 45-55% in polyacrylamide solution.
(5) polyphenylene sulfide fibre after step 4 dipping is added in 1,4- dichloromethyl benzole soln and is crosslinked 3-5h.
In order to further increase mechanical performance, resist melt, thermal stability and the thermal contraction of modified polyphenylene sulfide fibre
Performance, improves intermolecular active force, intermolecular active force, in the embodiment of the present invention, crosslinking agent is added and is crosslinked to it,
By the way that polyphenylene sulfide fibre to be added in Isosorbide-5-Nitrae-dichloromethyl benzole soln, fibrous inside is set to form three-dimensional net structure, greatly
Improve the thermal contraction performance and mechanical performance of polyphenylene sulfide fibre.
In the embodiment of the present invention, the too high waste for causing crosslinking agent of Isosorbide-5-Nitrae-dichloromethyl benzole soln, too low cross-linking is insufficient,
Therefore, polyphenylene sulfide fibre and Isosorbide-5-Nitrae-dichloromethyl benzole soln mass ratio are 1:5-8, in the embodiment of the present invention, Isosorbide-5-Nitrae-dichloro
Methyl benzole soln is to be dissolved in Isosorbide-5-Nitrae-xylylene dichlorides in 1,2- dichloroethanes being made, Isosorbide-5-Nitrae-two in Isosorbide-5-Nitrae-dichloromethyl benzole soln
The concentration of chloromethylbenzene is 45-55%.
(6) polyphenylene sulfide fibre after crosslinking is washed with dehydrated alcohol, is then washed again with distilled water, it will
Polyphenylene sulfide fibre after cleaning carries out vacuum drying and the anti-shrink polyphenylene sulfide fibre is made.
Modifying agent remaining on polyphenylene sulfide fibre and crosslinking agent are washed off by cleaning, avoid influencing final obtained poly-
The property of sulfide fibers, in the embodiment of the present invention, first with dehydrated alcohol by the modifying agent and crosslinking agent on polyphenylene sulfide fibre
Washed, then washed again with distilled water, by wash twice can poly-p-phenylene sulfide ether fiber effectively cleaned.
Excellent in order to stablize the polyphenylene sulfide fibre performance after vacuum drying more, vacuum drying is divided into two stages:
First stage is dry 1-2h under conditions of temperature is 140-160 DEG C, carries out the drying of first stage at a lower temperature, makes
The performance of polyphenylene sulfide fibre is further stablized, and avoids just starting that drying temperature is too high, and the performance of poly-p-phenylene sulfide ether fiber carries out
It destroys；Second stage is dry 5-8h, polyphenylene sulfide fibre after drying in the first stage under conditions of temperature is 160-180 DEG C
Performance further stablized, then increase temperature carry out second stage drying, in order to promote rate of drying, together
When further promoted reinforce polyphenylene sulfide fibre mechanical performance, resist melt, thermal stability and thermal contraction performance.
The polyphenylene sulfide fibre as made from the above method has preferable anti-contracility energy, mechanical performance, thermal stability
In burning molten drop, shrinkage phenomenon will not occur for energy and high temperature resistant.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of preparation method of the polyphenylene sulfide fibre of the anti-shrink under ignition, comprising the following steps:
(1) K is added in polyphenylene sulfide fibre2O21h is impregnated under conditions of 180 DEG C in solution, then in 160 DEG C of condition
Lower dipping 0.5h, wherein K2O2K in solution2O2Mass concentration be 50%, polyphenylene sulfide fibre and K2O2The mass ratio of solution is
1:4；
(2) polyphenylene sulfide fibre after step 1 dipping is added in flavonoids solution and impregnates 1h under conditions of 120 DEG C,
Wherein, the mass concentration of flavonoids is 40% in flavonoids solution, and the mass ratio of polyphenylene sulfide fibre and flavonoids solution is 1:
2；
(3) polyphenylene sulfide fibre after step 2 dipping is washed with acetone, is then washed again with distilled water,
Polyphenylene sulfide fibre after cleaning is dried in vacuo, vacuum drying temperature is 140 DEG C, time 2h；
(4) polyphenylene sulfide fibre after drying is added in polyacrylamide solution, impregnates 3h under conditions of 150 DEG C,
Wherein, the mass concentration of polyacrylamide is 45% in polyacrylamide solution, polyphenylene sulfide fibre and polyacrylamide solution
Mass ratio be 1:2；
(5) polyphenylene sulfide fibre after step 4 dipping is added in Isosorbide-5-Nitrae-dichloromethyl benzole soln and is crosslinked 3h, wherein 1,
Isosorbide-5-Nitrae-xylylene dichlorides concentration is 45% in 4- dichloromethyl benzole soln, polyphenylene sulfide fibre and Isosorbide-5-Nitrae-dichloromethyl benzole soln
Mass ratio be 1:5；
(6) polyphenylene sulfide fibre after crosslinking is washed with dehydrated alcohol, is then washed again with distilled water, it will
Polyphenylene sulfide fibre after cleaning carries out the polyphenylene sulfide fibre that the anti-shrink under ignition is made in vacuum drying, vacuum drying
Be divided into two stages: the first stage is dry 1h under conditions of temperature is 140 DEG C；It is 160 DEG C that second stage, which is in temperature,
Under the conditions of dry 5h.
Embodiment 2
A kind of preparation method of the polyphenylene sulfide fibre of the anti-shrink under ignition, comprising the following steps:
(1) H is added in polyphenylene sulfide fibre2SO41.5h is impregnated under conditions of 185 DEG C in solution, then at 165 DEG C
Under the conditions of impregnate 0.6h, wherein H2SO4H in solution2SO4Mass concentration be 52%, polyphenylene sulfide fibre and H2SO4Solution
Mass ratio is 1:4.5；
(2) polyphenylene sulfide fibre after step 1 dipping is added in flavonoids solution and is impregnated under conditions of 125 DEG C
1.2h, wherein the mass concentration of flavonoids is 42% in flavonoids solution, the mass ratio of polyphenylene sulfide fibre and flavonoids solution
For 1:2.2；
(3) polyphenylene sulfide fibre after step 2 dipping is washed with acetone, is then washed again with distilled water,
Polyphenylene sulfide fibre after cleaning is dried in vacuo, vacuum drying temperature is 145 DEG C, time 2.2h；
(4) polyphenylene sulfide fibre after drying is added in polyacrylamide solution, is impregnated under conditions of 155 DEG C
3.2h, wherein the mass concentration of polyacrylamide is 48% in polyacrylamide solution, polyphenylene sulfide fibre and polyacrylamide
The mass ratio of solution is 1:2.5；
(5) polyphenylene sulfide fibre after step 4 dipping is added in Isosorbide-5-Nitrae-dichloromethyl benzole soln and is crosslinked 3.5h, wherein
Isosorbide-5-Nitrae-xylylene dichlorides concentration is 48% in Isosorbide-5-Nitrae-dichloromethyl benzole soln, and polyphenylene sulfide fibre and Isosorbide-5-Nitrae-xylylene dichlorides are molten
The mass ratio of liquid is 1:5.5；
(6) polyphenylene sulfide fibre after crosslinking is washed with dehydrated alcohol, is then washed again with distilled water, it will
Polyphenylene sulfide fibre after cleaning carries out the polyphenylene sulfide fibre that the anti-shrink under ignition is made in vacuum drying, vacuum drying
Be divided into two stages: the first stage is dry 1.2h under conditions of temperature is 145 DEG C；It is 165 DEG C that second stage, which is in temperature,
Under conditions of dry 5.2h.
Embodiment 3
A kind of preparation method of the polyphenylene sulfide fibre of the anti-shrink under ignition, comprising the following steps:
(1) HNO is added in polyphenylene sulfide fibre32h is impregnated under conditions of 190 DEG C in solution, then in 170 DEG C of item
0.7h is impregnated under part, wherein HNO3HNO in solution3Mass concentration be 52%, polyphenylene sulfide fibre and HNO3The quality of solution
Than for 1:5；
(2) polyphenylene sulfide fibre after step 1 dipping is added in dibutyl hydroxy toluene solution under conditions of 130 DEG C
Impregnate 1.4h, wherein the mass concentration of dibutyl hydroxy toluene is 45% in dibutyl hydroxy toluene solution, polyphenylene sulfide fibre
Mass ratio with dibutyl hydroxy toluene solution is 1:2.5；
(3) polyphenylene sulfide fibre after step 2 dipping is washed with acetone, is then washed again with distilled water,
Polyphenylene sulfide fibre after cleaning is dried in vacuo, vacuum drying temperature is 150 DEG C, time 2.5h；
(4) polyphenylene sulfide fibre after drying is added in polyacrylamide solution, is impregnated under conditions of 160 DEG C
3.5h, wherein the mass concentration of polyacrylamide is 50% in polyacrylamide solution, polyphenylene sulfide fibre and polyacrylamide
The mass ratio of solution is 1:3；
(5) polyphenylene sulfide fibre after step 4 dipping is added in Isosorbide-5-Nitrae-dichloromethyl benzole soln and is crosslinked 4h, wherein 1,
Isosorbide-5-Nitrae-xylylene dichlorides concentration is 50% in 4- dichloromethyl benzole soln, polyphenylene sulfide fibre and Isosorbide-5-Nitrae-dichloromethyl benzole soln
Mass ratio be 1:6；
(6) polyphenylene sulfide fibre after crosslinking is washed with dehydrated alcohol, is then washed again with distilled water, it will
Polyphenylene sulfide fibre after cleaning carries out the polyphenylene sulfide fibre that the anti-shrink under ignition is made in vacuum drying, vacuum drying
Be divided into two stages: the first stage is dry 1.5h under conditions of temperature is 150 DEG C；It is 170 DEG C that second stage, which is in temperature,
Under conditions of dry 5.8h.
Embodiment 4
A kind of preparation method of the polyphenylene sulfide fibre of the anti-shrink under ignition, comprising the following steps:
(1) CCl is added in polyphenylene sulfide fibre42.5h is impregnated under conditions of 195 DEG C in solution, then at 175 DEG C
Under the conditions of impregnate 0.8h, wherein CCl4CCl in solution4Mass concentration be 55%, polyphenylene sulfide fibre and CCl4The matter of solution
Amount is than being 1:5.5；
(2) polyphenylene sulfide fibre after step 1 dipping is added in dibutyl hydroxy toluene solution under conditions of 135 DEG C
Impregnate 1.6h, wherein the mass concentration of tert-butyl hydroquinone is 48% in tert-butyl hydroquinone solution, polyphenylene sulfide fibre
Mass ratio with tert-butyl hydroquinone solution is 1:2.8；
(3) polyphenylene sulfide fibre after step 2 dipping is washed with acetone, is then washed again with distilled water,
Polyphenylene sulfide fibre after cleaning is dried in vacuo, vacuum drying temperature is 155 DEG C, time 2.8h；
(4) polyphenylene sulfide fibre after drying is added in polyacrylamide solution, is impregnated under conditions of 165 DEG C
3.8h, wherein the mass concentration of polyacrylamide is 52% in polyacrylamide solution, polyphenylene sulfide fibre and polyacrylamide
The mass ratio of solution is 1:3.5；
(5) polyphenylene sulfide fibre after step 4 dipping is added in Isosorbide-5-Nitrae-dichloromethyl benzole soln and is crosslinked 4.5h, wherein
Isosorbide-5-Nitrae-xylylene dichlorides concentration is 55% in Isosorbide-5-Nitrae-dichloromethyl benzole soln, and polyphenylene sulfide fibre and Isosorbide-5-Nitrae-xylylene dichlorides are molten
The mass ratio of liquid is 1:7；
(6) polyphenylene sulfide fibre after crosslinking is washed with dehydrated alcohol, is then washed again with distilled water, it will
Polyphenylene sulfide fibre after cleaning carries out the polyphenylene sulfide fibre that the anti-shrink under ignition is made in vacuum drying, vacuum drying
Be divided into two stages: the first stage is dry 1.8h under conditions of temperature is 155 DEG C；It is 175 DEG C that second stage, which is in temperature,
Under conditions of dry 6.2h.
Embodiment 5
A kind of preparation method of the polyphenylene sulfide fibre of the anti-shrink under ignition, comprising the following steps:
(1) KMnO is added in polyphenylene sulfide fibre43h is impregnated under conditions of 200 DEG C in solution, then in 180 DEG C of item
1h is impregnated under part, wherein KMnO4KMnO in solution4Mass concentration be 60%, polyphenylene sulfide fibre and KMnO4The quality of solution
Than for 1:6；
(2) polyphenylene sulfide fibre after step 1 dipping is added in dibutyl hydroxy toluene solution under conditions of 140 DEG C
Impregnate 2h, wherein in tert-butyl hydroquinone solution the mass concentration of tert-butyl hydroquinone be 50%, polyphenylene sulfide fibre with
The mass ratio of tert-butyl hydroquinone solution is 1:3；
(3) polyphenylene sulfide fibre after step 2 dipping is washed with acetone, is then washed again with distilled water,
Polyphenylene sulfide fibre after cleaning is dried in vacuo, vacuum drying temperature is 160 DEG C, time 3h；
(4) polyphenylene sulfide fibre after drying is added in polyacrylamide solution, impregnates 4h under conditions of 170 DEG C,
Wherein, the mass concentration of polyacrylamide is 55% in polyacrylamide solution, polyphenylene sulfide fibre and polyacrylamide solution
Mass ratio be 1:4；
(5) polyphenylene sulfide fibre after step 4 dipping is added in Isosorbide-5-Nitrae-dichloromethyl benzole soln and is crosslinked 5h, wherein 1,
Isosorbide-5-Nitrae-xylylene dichlorides concentration is 55% in 4- dichloromethyl benzole soln, polyphenylene sulfide fibre and Isosorbide-5-Nitrae-dichloromethyl benzole soln
Mass ratio be 1:8；
(6) polyphenylene sulfide fibre after crosslinking is washed with dehydrated alcohol, is then washed again with distilled water, it will
Polyphenylene sulfide fibre after cleaning carries out the polyphenylene sulfide fibre that the anti-shrink under ignition is made in vacuum drying, vacuum drying
Be divided into two stages: the first stage is dry 2h under conditions of temperature is 160 DEG C；It is 180 DEG C that second stage, which is in temperature,
Under the conditions of dry 7h.
Embodiment 6
A kind of preparation method of the polyphenylene sulfide fibre of the anti-shrink under ignition, comprising the following steps:
(1) KClO is added in polyphenylene sulfide fibre44h is impregnated under conditions of 200 DEG C in solution, then in 180 DEG C of item
1h is impregnated under part, wherein KClO4KClO in solution4Mass concentration be 60%, polyphenylene sulfide fibre and KMnO4The quality of solution
Than for 1:6；
(2) polyphenylene sulfide fibre after step 1 dipping is added in dibutyl hydroxy toluene solution under conditions of 140 DEG C
Impregnate 2h, wherein in tert-butyl hydroquinone solution the mass concentration of tert-butyl hydroquinone be 50%, polyphenylene sulfide fibre with
The mass ratio of tert-butyl hydroquinone solution is 1:3；
(3) polyphenylene sulfide fibre after step 2 dipping is washed with acetone, is then washed again with distilled water,
Polyphenylene sulfide fibre after cleaning is dried in vacuo, vacuum drying temperature is 160 DEG C, time 3h；
(4) polyphenylene sulfide fibre after drying is added in polyacrylamide solution, impregnates 5h under conditions of 180 DEG C,
Wherein, the mass concentration of polyacrylamide is 55% in polyacrylamide solution, polyphenylene sulfide fibre and polyacrylamide solution
Mass ratio be 1:4；
(5) polyphenylene sulfide fibre after step 4 dipping is added in Isosorbide-5-Nitrae-dichloromethyl benzole soln and is crosslinked 5h, wherein 1,
Isosorbide-5-Nitrae-xylylene dichlorides concentration is 55% in 4- dichloromethyl benzole soln, polyphenylene sulfide fibre and Isosorbide-5-Nitrae-dichloromethyl benzole soln
Mass ratio be 1:8；
(6) polyphenylene sulfide fibre after crosslinking is washed with dehydrated alcohol, is then washed again with distilled water, it will
Polyphenylene sulfide fibre after cleaning carries out the polyphenylene sulfide fibre that the anti-shrink under ignition is made in vacuum drying, vacuum drying
Be divided into two stages: the first stage is dry 2h under conditions of temperature is 160 DEG C；It is 180 DEG C that second stage, which is in temperature,
Under the conditions of dry 8h.
Comparative example 1
A kind of preparation method of the polyphenylene sulfide fibre of the anti-shrink under ignition, comprising the following steps:
(1) K is added in polyphenylene sulfide fibre2O21h is impregnated under conditions of 180 DEG C in solution, wherein K2O2In solution
K2O2Mass concentration be 50%, polyphenylene sulfide fibre and K2O2The mass ratio of solution is 1:4；
(2) polyphenylene sulfide fibre after step 1 dipping is added in flavonoids solution and impregnates 1h under conditions of 120 DEG C,
Wherein, the mass concentration of flavonoids is 40% in flavonoids solution, and the mass ratio of polyphenylene sulfide fibre and flavonoids solution is 1:
2；
(3) polyphenylene sulfide fibre after step 2 dipping is washed with acetone, is then washed again with distilled water,
Polyphenylene sulfide fibre after cleaning is dried in vacuo, vacuum drying temperature is 140 DEG C, time 2h；
(4) polyphenylene sulfide fibre after drying is added in polyacrylamide solution, impregnates 3h under conditions of 150 DEG C,
Wherein, the mass concentration of polyacrylamide is 45% in polyacrylamide solution, polyphenylene sulfide fibre and polyacrylamide solution
Mass ratio be 1:2；
(5) polyphenylene sulfide fibre after step 4 dipping is added in Isosorbide-5-Nitrae-dichloromethyl benzole soln and is crosslinked 3h, wherein 1,
Isosorbide-5-Nitrae-xylylene dichlorides concentration is 45% in 4- dichloromethyl benzole soln, polyphenylene sulfide fibre and Isosorbide-5-Nitrae-dichloromethyl benzole soln
Mass ratio be 1:5；
(6) polyphenylene sulfide fibre after crosslinking is washed with dehydrated alcohol, is then washed again with distilled water, it will
Polyphenylene sulfide fibre after cleaning carries out the polyphenylene sulfide fibre that the anti-shrink under ignition is made in vacuum drying, vacuum drying
Be divided into two stages: the first stage is dry 1h under conditions of temperature is 140 DEG C；It is 160 DEG C that second stage, which is in temperature,
Under the conditions of dry 5h.
Comparative example 2
A kind of preparation method of the polyphenylene sulfide fibre of the anti-shrink under ignition, comprising the following steps:
(1) K is added in polyphenylene sulfide fibre2O21h is impregnated under conditions of 180 DEG C in solution, then in 160 DEG C of condition
Lower dipping 0.5h, wherein K2O2K in solution2O2Mass concentration be 50%, polyphenylene sulfide fibre and K2O2The mass ratio of solution is
1:4；
(2) polyphenylene sulfide fibre after step 1 dipping is added in flavonoids solution and impregnates 1h under conditions of 120 DEG C,
Wherein, the mass concentration of flavonoids is 40% in flavonoids solution, and the mass ratio of polyphenylene sulfide fibre and flavonoids solution is 1:
2；
(3) polyphenylene sulfide fibre after step 2 dipping is washed with acetone, is then washed again with distilled water,
Polyphenylene sulfide fibre after cleaning is dried in vacuo, vacuum drying temperature is 140 DEG C, time 2h；
(4) polyphenylene sulfide fibre after step 3 dipping is added in Isosorbide-5-Nitrae-dichloromethyl benzole soln and is crosslinked 3h, wherein 1,
Isosorbide-5-Nitrae-xylylene dichlorides concentration is 45% in 4- dichloromethyl benzole soln, polyphenylene sulfide fibre and Isosorbide-5-Nitrae-dichloromethyl benzole soln
Mass ratio be 1:5；
(5) polyphenylene sulfide fibre after crosslinking is washed with dehydrated alcohol, is then washed again with distilled water, it will
Polyphenylene sulfide fibre after cleaning carries out the polyphenylene sulfide fibre that the anti-shrink under ignition is made in vacuum drying, vacuum drying
Be divided into two stages: the first stage is dry 1h under conditions of temperature is 140 DEG C；It is 160 DEG C that second stage, which is in temperature,
Under the conditions of dry 5h.
Comparative example 3
A kind of preparation method of the polyphenylene sulfide fibre of the anti-shrink under ignition, comprising the following steps:
(1) K is added in polyphenylene sulfide fibre2O21h is impregnated under conditions of 180 DEG C in solution, then in 160 DEG C of condition
Lower dipping 0.5h, wherein K2O2K in solution2O2Mass concentration be 50%, polyphenylene sulfide fibre and K2O2The mass ratio of solution is
1:4；
(2) polyphenylene sulfide fibre after step 1 dipping is added in flavonoids solution and impregnates 1h under conditions of 120 DEG C,
Wherein, the mass concentration of flavonoids is 40% in flavonoids solution, and the mass ratio of polyphenylene sulfide fibre and flavonoids solution is 1:
2；
(3) polyphenylene sulfide fibre after step 2 dipping is washed with acetone, is then washed again with distilled water,
Polyphenylene sulfide fibre after cleaning is dried in vacuo, vacuum drying temperature is 140 DEG C, time 2h；
(4) polyphenylene sulfide fibre after drying is added in polyacrylamide solution, impregnates 3h under conditions of 150 DEG C,
Wherein, the mass concentration of polyacrylamide is 45% in polyacrylamide solution, polyphenylene sulfide fibre and polyacrylamide solution
Mass ratio be 1:2；
(5) above-mentioned polyphenylene sulfide fibre is washed with dehydrated alcohol, is then washed again with distilled water, will cleaned
Polyphenylene sulfide fibre afterwards carries out the polyphenylene sulfide fibre that the anti-shrink under ignition is made in vacuum drying, and vacuum drying is divided into
Two stages: the first stage is dry 1h under conditions of temperature is 140 DEG C；Second stage is the condition for being 160 DEG C in temperature
Lower dry 5h.
Experimental example 1
Polyphenylene sulfide prepared by commercially available polyphenylene sulfide fibre (that is to say unmodified polyphenylene sulfide fibre) and embodiment 1
Ether fiber burns respectively, and the figure after burning is as shown in 1-4.
Fig. 1 is the figure after the burning of commercially available polyphenylene sulfide fibre, and Fig. 3 is pair of commercially available polyphenylene sulfide fibre burning front and back
Than schematic diagram, as can be seen from Figure 1 occur the phenomenon that melting, not burning directly after commercially available polyphenylene sulfide fibre burning
It at carbon (powder), is easy to cause harm to the human body when in use, for example, melting in the case where burning when being made into clothes
The case where, it is easy burned skin；From being evident that in Fig. 3 after commercially available polyphenylene sulfide fibre burning than commercially available polyphenylene sulfide
It is apparent short before fiber burning, namely there is the phenomenon that contraction after being commercially available polyphenylene sulfide fibre burning, it can in conjunction with Fig. 1
To there is the phenomenon that collapsing after finding out the burning of commercially available polyphenylene sulfide fibre, as high temperature filtration fabric in use, not only
Reduce its service life, after combustion, the phenomenon that collapsing occur, will increase the cleaning difficulty of staff；
Fig. 2 is the figure after polyphenylene sulfide fibre burning prepared by embodiment 1, and as can be seen from Figure 2 prepared by embodiment 1
The phenomenon that melting after polyphenylene sulfide fibre burning, directly at carbon (powder) after burning, as clothing in use, greatly
The phenomenon that big increases its safety, such as when clothes burns, and is not in melting, will not stick to the skin, to skin
Skin causes to damage.Fig. 4 is the contrast schematic diagram of the polyphenylene sulfide fibre burning front and back of polyphenylene sulfide fibre prepared by embodiment 1,
As can be seen from Figure 4 the polyphenylene sulfide fibre burning anterior-posterior length variation that prepared by embodiment 1 is unobvious, that is to say embodiment 1
Without the phenomenon that shrinking after the polyphenylene sulfide fibre burning of preparation, in conjunction with Fig. 1 it can be seen that polyphenylene sulfide prepared by embodiment 1
There is not the phenomenon that collapsing after the burning of ether fiber, its safety is greatly increased when using as clothing, as high temperature mistake
Its service life can not only be improved when filtering fabric use, even if after burning, the difficulty of staff's cleaning is smaller.
Experimental example 2
The polyphenylene sulfide fibre of polyphenylene sulfide fibre, comparative example 1-3 preparation prepared by embodiment 1-6 and commercially available system
Standby polyphenylene sulfide fibre is tested for the property, and collapsing phenomenon is as shown in table 1, and mechanical performance is as shown in table 2.
Table 1
From table 1 it follows that the polyphenylene sulfide fibre of embodiment 1-6 preparation is at 380 DEG C of higher temperature without melting, nothing
Shrinkage phenomenon generates, even if will not occur melting contracting phenomenon, comparative example 1 is in the oxidation degree or not in when there is combustion case
The step of section does not impregnate in two stages, and polyacrylamide solution dipping is not added in comparative example 2, comparative example 3 is not added
The step of 1,4- xylylene dichlorides solution crosslinking.
Table 2
From table 2 it can be seen that the polyphenylene sulfide fibre of embodiment 1-6 preparation has preferable elongation at break and stretches strong
Degree, at 200 degrees Celsius, the conservation rate of intensity is 85% or more.
In conclusion the embodiment of the present invention provides polyphenylene sulfide fibre and its preparation of a kind of anti-shrink under ignition
Method, wherein the surface S atom partial oxidation of oxidant poly-p-phenylene sulfide ether fiber is added, first to change polyphenylene sulfide fibre
Characteristic improves its resist melt, anti-contracility energy, wherein be divided into two stages impregnates polyphenylene sulfide fibre respectively, to time and temperature
Degree is controlled, so that the degree of oxidation of sulphur atom is controlled, to change the heatproof of polyphenylene sulfide fibre, resist melt, anti-shrink
Performance；Antioxidant is added after oxidation to prevent the sulphur atom on polyphenylene sulfide fibre surface from continuing to aoxidize, retains part S atom
It is set to keep certain flexibility and anti-flammability；By polyacrylamide in polyphenylene sulfide fibre introducing-CO- polar group, can
To improve the heat resistance and mechanical performance of fiber, increase the intermolecular force between polyphenylene sulfide main chain, to improve it
Thermal stability, mechanical performance and thermal contraction performance；Isosorbide-5-Nitrae-xylylene dichlorides is added to be crosslinked it, fibrous inside is made to form three
Network structure is tieed up, the thermal contraction performance of polyphenylene sulfide fibre is greatly improved；By oxidation, modification and the phases interworking such as it is crosslinked
It closes, enables polyphenylene sulfide fibre obtained that there is preferable anti-contracility, mechanical performance, thermal stability and high temperature resistant, even if
Molten drop, shrinkage phenomenon will not occur in burning.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the polyphenylene sulfide fibre of the anti-shrink under ignition, it is characterised in that: the following steps are included:
(1) polyphenylene sulfide fibre is added in oxidizing agent solution and impregnates 1-4h under conditions of 180-200 DEG C, then in 160-
0.5h-1h is impregnated under conditions of 180 DEG C；
(2) polyphenylene sulfide fibre after step 1 dipping is added in antioxidant solution and impregnates 1- under conditions of 120-140 DEG C
2h；
(3) polyphenylene sulfide fibre after step 2 dipping is washed with acetone, is then washed again with distilled water, it will be clear
Polyphenylene sulfide fibre after washing is dried in vacuo；
(4) polyphenylene sulfide fibre after drying is added in polyacrylamide solution, impregnates 3- under conditions of 150-180 DEG C
5h；
(5) polyphenylene sulfide fibre after step 4 dipping is added in 1,4- dichloromethyl benzole soln and is crosslinked 3-5h；
(6) polyphenylene sulfide fibre after crosslinking is washed with dehydrated alcohol, is then washed again with distilled water, will cleaned
Polyphenylene sulfide fibre afterwards carries out vacuum drying and the poly- sulfide fibers of the anti-shrink is made.
2. the preparation method of the polyphenylene sulfide fibre of the anti-shrink according to claim 1 under ignition, feature exist
In: the oxidizing agent solution is to be dissolved in oxidant in the first solvent being made, and the oxidant is selected from K2O2、H2SO4、HNO3
CCl4、KMnO4And KClO4At least one of, first solvent is acetone.
3. the preparation method of the polyphenylene sulfide fibre of the anti-shrink according to claim 2 under ignition, feature exist
In: the mass ratio of polyphenylene sulfide fibre described in step 1 and the oxidizing agent solution is 1:4-6.
4. the preparation method of the polyphenylene sulfide fibre of the anti-shrink according to claim 1 under ignition, feature exist
In: the antioxidant solution is to be dissolved in antioxidant in the second solvent being made, and the antioxidant is selected from flavonoids, two fourths
At least one of base hydroxy-methylbenzene and tert-butyl hydroquinone, second solvent are acetone.
5. the preparation method of the polyphenylene sulfide fibre of the anti-shrink according to claim 4 under ignition, feature exist
In: the mass ratio of polyphenylene sulfide fibre described in step 2 and the antioxidant solution is 1:2-3.
6. the preparation method of the polyphenylene sulfide fibre of the anti-shrink according to claim 1 under ignition, feature exist
In: vacuum drying condition in step 3 are as follows: 140-160 DEG C of temperature, time 2-3h.
7. the preparation method of the polyphenylene sulfide fibre of the anti-shrink according to claim 1 under ignition, feature exist
In: the vacuum drying in step 6 is divided into two stages: the first stage is dry 1-2h under conditions of temperature is 140-160 DEG C；
Second stage is dry 5-8h under conditions of temperature is 160-180 DEG C.
8. the preparation method of the polyphenylene sulfide fibre of the anti-shrink according to claim 1 under ignition, feature exist
In: the mass ratio of polyphenylene sulfide fibre described in step 4 and the polyacrylamide solution is 1:2-4.
9. the preparation method of the polyphenylene sulfide fibre of the anti-shrink according to claim 1 under ignition, feature exist
In: the mass ratio of polyphenylene sulfide fibre described in step 5 and the 1,4- dichloromethyl benzole soln is 1:5-8.
10. a kind of polyphenylene sulfide fibre of the anti-shrink under ignition, it is characterised in that: by any one of claim 1-9 institute
The preparation method stated is made.
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| 刘程等主编: "《表面活性剂》", 31 August 1995, 化学工业出版社 * |
| 范如霖等编译: "《有机合成中的相转移催化作用》", 28 February 1982, 上海科学技术出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113481626A (en) * | 2021-07-14 | 2021-10-08 | 天津工业大学 | Preparation method of polyphenylene sulfide sulfone ketone fiber |
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