CN106279692B - A kind of method that polyphenylene sulfide oligomer recycles - Google Patents
A kind of method that polyphenylene sulfide oligomer recycles Download PDFInfo
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Abstract
The present invention relates to a kind of methods that polyphenylene sulfide oligomer recycles, more particularly to a kind of method with polyphenylene sulfide oligomer synthetic fibers grade polyphenylene sulfide.Mainly polymerization is carried out as raw material with polyphenylene sulfide oligomer and prepares fiber-grade polyphenyl thioether using deficiency, the present invention existing for landfill and burning disposal mode based on existing polyphenylene sulfide oligomer.
Description
Technical field
The present invention relates to a kind of methods that polyphenylene sulfide oligomer recycles, and polyphenylene sulfide is used more particularly to a kind of
The method of ether oligomer synthetic fibers grade polyphenylene sulfide.
Background technology
The english abbreviation of polyphenylene sulfide be PPS, have heat resistance outstanding, excellent chemical resistance, inherently
Anti-flammability, excellent mechanical property and electrical property, outstanding dimensional stability and good moulding processability and opposite
Low cost price becomes the outstanding person in special engineering plastics (also known as high performance engineering plastics).PPS can also be processed
At fiber, with the rapid development of industry, discharge of industrial wastes getting worse has jeopardized natural environment and the health of people.
Flue gas ash removal is the important component of pollution administration, and bag-type dusting is exactly the important method for administering flue gas.Flue gas is administered to need
High temperature resistant, corrosion resistant tencel, PPS fibers can meet completely more than requirement.
Fibre-grade PPS industrial productions make catalyst, N- methyl usually using vulcanized sodium and paracide as raw material, with alkali metal
Pyrrolidone as solvent prepares PPS under certain temperature and pressure, and the difference of PPS chaining length can form of different-grain diameter
Grain object.The difference of particle size can cause physics, the performance of chemistry different, in order to enable the fibre-grade PPS products arrived
Performance is as convergent as possible, needs to wash product with deionized water, and PPS need to be the particulate matter of different-grain diameter point after washing
It opens, the big PPS of grain size obtains fibre-grade PPS products after drying, and the small PPS of grain size is then when oligomer processing.
1 ton of fibre-grade PPS, which is produced, according to prior art about generates 0.1 ton of PPS oligomer, the processing of PPS oligomer at present
Mode is predominantly filled and is burned.It is difficult to degrade that PPS, which is handled as the special engineering plastics that performance is stablized by land-fill method,；This
Outside, contain element sulphur in PPS molecules, burning process will produce sulfur dioxide.Therefore, the existing processing mode of PPS oligomer is deposited
Environmental pollution, it is of high cost the deficiencies of.
Based on deficiency existing for existing PPS oligomer processing mode, inventors discovered through research that the presence of PPS oligomer can
With the active end group-Cl and-SNa that the reaction was continued.Therefore, the present invention carries out polymerization as raw material with PPS oligomer and prepares fibre-grade
PPS。
Invention content
Purpose of the present invention is to be to provide a kind of method with PPS oligomer synthetic fibers grades PPS.
To achieve the object of the present invention, the present invention uses following experimental method：It is low that PPS is put into autoclave according to a certain ratio
Polymers, catalysts and solvents need to control coefficient, and feed intake the oxygen finished in logical nitrogen displacement system；Envelope kettle liter is finished in displacement
Temperature to predetermined temperature, insulation reaction to predetermined time obtains polymer material；It is filtered after polymer material cooling, it is thick to obtain polymer
Product；Polymer crude product is repeatedly washed with quantitative deionized water, obtains washing post-consumer polymer；Washing post-consumer polymer is with quantitatively going
Ionized water repeatedly rinses separation of oligomeric, obtains fibre-grade PPS wet basis and PPS oligomer；Fibre-grade PPS wet basis is in certain temperature
Be dried to the predetermined time under vacuum degree, obtain fibre-grade PPS butts, yield is more than 90%；Isolated PPS oligomer,
Synthesis of the set for next batch fibre-grade PPS after drying.
Autoclave material of the present invention be 300 series-chromiumnickel austenite stainless steel, titanium series TA1-TA8, preferably
316L stainless steels and titanium TA3, more preferable titanium TA3.
Catalyst of the present invention be sodium phosphate, sodium carbonate, sodium tungstate, sodium sulphate, lithium chloride, lithium sulfate, sodium acetate,
Potassium phosphate, potassium phosphate,monobasic, potassium dihydrogen phosphate, lithium chloride and sodium acetate mixed catalyst, preferably lithium chloride, lithium sulfate, acetic acid
Sodium, lithium chloride and sodium acetate mixed catalyst, more preferable lithium chloride and sodium acetate mixed catalyst.
Lithium chloride of the present invention is lithium chloride with sodium acetate mixed catalyst mol ratio：Sodium acetate=1~99：99
~1, preferably lithium chloride：Sodium acetate=30~70：70~30, more preferable lithium chloride：Sodium acetate=50：50.
Solvent of the present invention is N-Methyl pyrrolidone, hexamethylphosphoramide, N,N-dimethylformamide, N, N-
Dimethylacetylamide, caprolactam, nitrobenzene, dimethyl sulfoxide (DMSO), preferably N-Methyl pyrrolidone and hexamethylphosphoramide, more
It is preferred that N-Methyl pyrrolidone.
The mol ratio of PPS oligomer and catalyst of the present invention is oligomer：Catalyst=1:2~0.1, preferably
Oligomer：Catalyst=1:1.5~0.8, more preferable oligomer：Catalyst=1:1.
The mol ratio of PPS oligomer and solvent of the present invention is oligomer：Solvent=1:8~2, it is preferably oligomeric
Object：Solvent=1:6~4, more preferable oligomer：Solvent=1:5.
Autoclave charge coefficient of the present invention control is 0.8~0.2, preferably coefficient control 0.7~0.4,
More preferable coefficient control is 0.6.
Reaction temperature of the present invention is 220~280 DEG C, and preferable reaction temperature is 250~270 DEG C, is more preferably reacted
Temperature is 260 DEG C.
Reaction time of the present invention is 1~10 hour, and preferred reaction time is 3~8 hours, the more preferable reaction time
It is 5 hours.
Single wash water of the present invention is 2~10 times of polymer crude product quality, preferably 4~8 times, more preferable 6
Times.
Polymer crude product washing times of the present invention are 3~15 times, preferably 4~10 times, more preferable 7 times.
Single oligomer of the present invention rinsing water is 2~10 times of polymer crude product quality, preferably 4~8 times, more
It is preferred that 6 times.
Single oligomer rinsing times of the present invention are 1~5 time, preferably 2~4 times, more preferable 3 times.
The temperature of fibre-grade PPS wet basis drying of the present invention is 50~200 DEG C, and preferably drying temperature is 80~150
DEG C, more preferable drying temperature is 120 DEG C.
The vacuum degree of fibre-grade PPS wet basis drying of the present invention is -0.01~-0.1MPa, preferably dries vacuum degree
For -0.08~-0.095MPa, it is -0.095MPa more preferably to dry vacuum degree.
The time of fibre-grade PPS wet basis drying of the present invention is 1~10 hour, and preferably drying time is 4~6 small
When, more preferable drying time is 5 hours.
Main advantages of the present invention are：1. realizing the recycling of PPS oligomer, save fibre-grade PPS's
Production cost；2. reaction condition is mildly easily controllable；3. the reaction time is short, production efficiency is high；4. the PPS qualities prepared reach
The requirement of fibre-grade.
Specific implementation mode
Illustrate technical scheme of the present invention with specific example below, but the scope of the present invention is not limited thereto.
Embodiment 1
By 1 mole of PPS oligomer 109g, 0.5 mole of lithium chloride and 0.5 molar sodium acetate mixed catalyst 62g, 5 moles
N-Methyl pyrrolidone 495g, input, in 1 liter of titanium TA3 autoclave of temperature measurer, are led in nitrogen displacement system equipped with stirring
Oxygen 3 times, envelope kettle are warming up to 260 DEG C of heat preservation polymerisations 5 hours, and polymerisation, which finishes, to be cooled to 80 DEG C and filter while hot, must be polymerize
Object crude product；Polymer crude product single is filtered with 600g deionized water agitator treatings, is repeated agitator treating and is filtered 7 times；Gather after washing
It closes object single and rinses oligomer with 600g deionized waters, repeat rinsing 3 times, obtain PPS wet basis；PPS wet basis is placed in vacuum drying chamber
It is interior in -0.095MPa, be warming up to 120 DEG C of dryings 5 hours；Dry complete PPS is down to room temperature, obtains butt 99.0g, yield 90.8%；
PPS after tested, melt index 95g/10min, 285 DEG C of fusing point, performance indicator meet fibre-grade PPS melt index be less than 170g/
10min requirements.
Embodiment 2
By 1 mole of PPS oligomer 109g, 0.2 mole of lithium chloride and 0.8 molar sodium acetate mixed catalyst 74.1g, 5 rub
You are N-Methyl pyrrolidone 495g, in 1 liter of titanium TA3 autoclave of the input equipped with stirring and temperature measurer, leads to nitrogen and replaces system
Middle oxygen 3 times, envelope kettle are warming up to 260 DEG C of heat preservation polymerisations 5 hours, and polymerisation, which finishes, to be cooled to 80 DEG C and filter while hot, is obtained poly-
Close object crude product；Polymer crude product single is filtered with 600g deionized water agitator treatings, is repeated agitator treating and is filtered 7 times；After washing
Polymer single rinses oligomer with 600g deionized waters, repeats rinsing 3 times, obtains PPS wet basis；PPS wet basis is placed in vacuum drying
In -0.095MPa in case, it is warming up to 120 DEG C of dryings 5 hours；Dry complete PPS is down to room temperature, obtains butt 93.5g, yield
85.8%；After tested, melt index 181g/10min, 282 DEG C of fusing point, performance indicator cannot meet fibre-grade PPS melting and refer to PPS
Number is less than 170g/10min requirements.
Embodiment 3
By 1 mole of PPS oligomer 109g, 1.0 mole of phosphoric acid sodium mixed catalyst 164g, 5 moles of N-methyl pyrrolidones
495g, input, in 1 liter of titanium TA3 autoclave of temperature measurer, lead to oxygen 3 times in nitrogen displacement system, seal kettle liter equipped with stirring
To 260 DEG C of heat preservation polymerisations 5 hours, polymerisation finishes to be cooled to 80 DEG C and filters while hot temperature, obtains polymer crude product；Polymer is thick
Product single is filtered with 600g deionized water agitator treatings, is repeated agitator treating and is filtered 7 times；Washing post-consumer polymer single is gone with 600g
Ionized water rinses oligomer, repeats rinsing 3 times, obtains PPS wet basis；PPS wet basis is placed in vacuum drying chamber in -0.095MPa, is risen
Temperature to 120 DEG C it is 5 hours dry；Dry complete PPS is down to room temperature, obtains butt 101.3g, yield 92.9%；After tested, melting refers to PPS
Number 874g/10min, 285 DEG C of fusing point, performance indicator cannot meet fibre-grade PPS melt index less than 170g/10min requirements.
Embodiment 4
By 1 mole of PPS oligomer 109g, 1.0 mol sulfuric acid lithium 110g, 5 moles of N-methyl pyrrolidones 495g, input dress
In 1 liter of titanium TA3 autoclave for having stirring and temperature measurer, lead to oxygen 3 times in nitrogen displacement system, envelope kettle is warming up to 260 DEG C of guarantors
Warm polymerisation 5 hours, polymerisation, which finishes, to be cooled to 80 DEG C and filters while hot, and polymer crude product is obtained；Polymer crude product single is used
600g deionized water agitator treatings filter, and repeat agitator treating and filter 7 times；Post-consumer polymer single is washed to be floated with 600g deionized waters
Oligomer is washed, rinsing 3 times is repeated, obtains PPS wet basis；PPS wet basis is placed in vacuum drying chamber in -0.095MPa, is warming up to 120 DEG C
It is 5 hours dry；Dry complete PPS is down to room temperature, obtains butt 97.3g, yield 89.3%；PPS after tested, melt index 386g/
10min, 285 DEG C of fusing point, performance indicator cannot meet fibre-grade PPS melt index less than 170g/10min requirements.
Embodiment 5
By 1 mole of PPS oligomer 109g, 1.0 mole of either sodium carbonate catalyst 106g, 5 moles of N-methyl pyrrolidones 495g,
In 1 liter of titanium TA3 autoclave of the input equipped with stirring and temperature measurer, lead to oxygen 3 times in nitrogen displacement system, envelope kettle is warming up to
260 DEG C of heat preservation polymerisations 5 hours, polymerisation, which finishes, to be cooled to 80 DEG C and filters while hot, and polymer crude product is obtained；Polymer crude product list
It is secondary to be filtered with 600g deionized water agitator treatings, it repeats agitator treating and filters 7 times；Wash post-consumer polymer single 600g deionizations
Water rinses oligomer, repeats rinsing 3 times, obtains PPS wet basis；PPS wet basis is placed in vacuum drying chamber in -0.095MPa, is warming up to
120 DEG C of dryings 5 hours；Dry complete PPS is down to room temperature, obtains butt 94.3g, yield 86.5%；PPS after tested, melt index
568g/10min, 279 DEG C of fusing point, performance indicator cannot meet fibre-grade PPS melt index less than 170g/10min requirements.
Embodiment 6
By 1 mole of PPS oligomer 109g, 0.5 mole of lithium chloride and 0.5 molar sodium acetate mixed catalyst 62g, 5 moles
Hexamethylphosphoramide 495g, input, in 1 liter of titanium TA3 autoclave of temperature measurer, are led in nitrogen displacement system equipped with stirring
Oxygen 3 times, envelope kettle are warming up to 260 DEG C of heat preservation polymerisations 5 hours, and polymerisation, which finishes, to be cooled to 80 DEG C and filter while hot, must be polymerize
Object crude product；Polymer crude product single is filtered with 600g deionized water agitator treatings, is repeated agitator treating and is filtered 7 times；Gather after washing
It closes object single and rinses oligomer with 600g deionized waters, repeat rinsing 3 times, obtain PPS wet basis；PPS wet basis is placed in vacuum drying chamber
It is interior in -0.095MPa, be warming up to 120 DEG C of dryings 5 hours；Dry complete PPS is down to room temperature, obtains butt 92.8g, yield 85.1%；
After tested, melt index 432g/10min, 280 DEG C of fusing point, performance indicator cannot meet fibre-grade PPS melt index and be less than PPS
170g/10min requirements.
Embodiment 7
By 1 mole of PPS oligomer 109g, 0.5 mole of lithium chloride and 0.5 molar sodium acetate mixed catalyst 62g, 5 moles
N,N-Dimethylformamide 495g, input, in 1 liter of titanium TA3 autoclave of temperature measurer, lead to nitrogen and replace system equipped with stirring
Middle oxygen 3 times, envelope kettle are warming up to 260 DEG C of heat preservation polymerisations 5 hours, and polymerisation, which finishes, to be cooled to 80 DEG C and filter while hot, is obtained poly-
Close object crude product；Polymer crude product single is filtered with 600g deionized water agitator treatings, is repeated agitator treating and is filtered 7 times；After washing
Polymer single rinses oligomer with 600g deionized waters, repeats rinsing 3 times, obtains PPS wet basis；PPS wet basis is placed in vacuum drying
In -0.095MPa in case, it is warming up to 120 DEG C of dryings 5 hours；Dry complete PPS is down to room temperature, obtains butt 99.5g, yield
91.3%；After tested, melt index 1210g/10min, 278 DEG C of fusing point, performance indicator cannot meet fibre-grade PPS melting to PPS
Index is less than 170g/10min requirements.
Embodiment 8
By 1 mole of PPS oligomer 109g, 0.5 mole of lithium chloride and 0.5 molar sodium acetate mixed catalyst 62g, 7 moles
N-Methyl pyrrolidone 693g, input, in 1 liter of titanium TA3 autoclave of temperature measurer, are led in nitrogen displacement system equipped with stirring
Oxygen 3 times, envelope kettle are warming up to 260 DEG C of heat preservation polymerisations 5 hours, and polymerisation, which finishes, to be cooled to 80 DEG C and filter while hot, must be polymerize
Object crude product；Polymer crude product single is filtered with 600g deionized water agitator treatings, is repeated agitator treating and is filtered 7 times；Gather after washing
It closes object single and rinses oligomer with 600g deionized waters, repeat rinsing 3 times, obtain PPS wet basis；PPS wet basis is placed in vacuum drying chamber
It is interior in -0.095MPa, be warming up to 120 DEG C of dryings 5 hours；Dry complete PPS is down to room temperature, obtains butt 99.2g, yield 91.0%；
PPS after tested, melt index 118g/10min, 284 DEG C of fusing point, performance indicator meet fibre-grade PPS melt index be less than 170g/
10min requirements.
Embodiment 9
By 1 mole of PPS oligomer 109g, 0.5 mole of lithium chloride and 0.5 molar sodium acetate mixed catalyst 62g, 3 moles
N-Methyl pyrrolidone 297g, input, in 1 liter of titanium TA3 autoclave of temperature measurer, are led in nitrogen displacement system equipped with stirring
Oxygen 3 times, envelope kettle are warming up to 260 DEG C of heat preservation polymerisations 5 hours, and polymerisation, which finishes, to be cooled to 80 DEG C and filter while hot, must be polymerize
Object crude product；Polymer crude product single is filtered with 600g deionized water agitator treatings, is repeated agitator treating and is filtered 7 times；Gather after washing
It closes object single and rinses oligomer with 600g deionized waters, repeat rinsing 3 times, obtain PPS wet basis；PPS wet basis is placed in vacuum drying chamber
It is interior in -0.095MPa, be warming up to 120 DEG C of dryings 5 hours；Dry complete PPS is down to room temperature, obtains butt 90.5g, yield 83.0%；
After tested, melt index 424g/10min, 280 DEG C of fusing point, performance indicator cannot meet fibre-grade PPS melt index and be less than PPS
170g/10min requirements.
Embodiment 10
By 1 mole of PPS oligomer 109g, 0.5 mole of lithium chloride and 0.5 molar sodium acetate mixed catalyst 62g, 5 moles
N-Methyl pyrrolidone 495g, input, in 1 liter of 304 stainless steel autoclave of temperature measurer, lead to nitrogen and replace system equipped with stirring
Middle oxygen 3 times, envelope kettle are warming up to 260 DEG C of heat preservation polymerisations 5 hours, and polymerisation, which finishes, to be cooled to 80 DEG C and filter while hot, is obtained poly-
Close object crude product；Polymer crude product single is filtered with 600g deionized water agitator treatings, is repeated agitator treating and is filtered 7 times；After washing
Polymer single rinses oligomer with 600g deionized waters, repeats rinsing 3 times, obtains PPS wet basis；PPS wet basis is placed in vacuum drying
In -0.095MPa in case, it is warming up to 120 DEG C of dryings 5 hours；Dry complete PPS is down to room temperature, obtains butt 94.6g, yield
86.8%；After tested, melt index 203g/10min, 280 DEG C of fusing point, performance indicator cannot meet fibre-grade PPS melting and refer to PPS
Number is less than 170g/10min requirements.
Embodiment 11
By 1 mole of PPS oligomer 109g, 0.5 mole of lithium chloride and 0.5 molar sodium acetate mixed catalyst 62g, 5 moles
N-Methyl pyrrolidone 495g, input, in 1 liter of 316L stainless steel autoclave of temperature measurer, lead to nitrogen and replace system equipped with stirring
Middle oxygen 3 times, envelope kettle are warming up to 260 DEG C of heat preservation polymerisations 5 hours, and polymerisation, which finishes, to be cooled to 80 DEG C and filter while hot, is obtained poly-
Close object crude product；Polymer crude product single is filtered with 600g deionized water agitator treatings, is repeated agitator treating and is filtered 7 times；After washing
Polymer single rinses oligomer with 600g deionized waters, repeats rinsing 3 times, obtains PPS wet basis；PPS wet basis is placed in vacuum drying
In -0.095MPa in case, it is warming up to 120 DEG C of dryings 5 hours；Dry complete PPS is down to room temperature, obtains butt 98.6g, yield
90.5%；After tested, melt index 108g/10min, 284 DEG C of fusing point, it is small that performance indicator meets fibre-grade PPS melt index to PPS
In 170g/10min requirements.
Embodiment 12
By 1 mole of PPS oligomer 109g, 0.5 mole of lithium chloride and 0.5 molar sodium acetate mixed catalyst 62g, 5 moles
N-Methyl pyrrolidone 495g, input, in the 1L titanium TA3 autoclaves of temperature measurer, lead to oxygen in nitrogen displacement system equipped with stirring
Gas 3 times, envelope kettle are warming up to 240 DEG C of heat preservation polymerisations 5 hours, and polymerisation, which finishes, to be cooled to 80 DEG C and filter while hot, and polymer is obtained
Crude product；Polymer crude product single is filtered with 600g deionized water agitator treatings, is repeated agitator treating and is filtered 7 times；It polymerize after washing
Object single rinses oligomer with 600g deionized waters, repeats rinsing 3 times, obtains PPS wet basis；PPS wet basis is placed in vacuum drying chamber
In -0.095MPa, it is warming up to 120 DEG C of dryings 5 hours；Dry complete PPS is down to room temperature, obtains butt 78.4g, yield 71.9%；PPS
After tested, melt index 831g/10min, 278 DEG C of fusing point, performance indicator cannot meet fibre-grade PPS melt index and be less than
170g/10min requirements.
Embodiment 13
By 1 mole of PPS oligomer 109g, 0.5 mole of lithium chloride and 0.5 molar sodium acetate mixed catalyst 62g, 5 moles
N-Methyl pyrrolidone 495g, input, in the 1L titanium TA3 autoclaves of temperature measurer, lead to oxygen in nitrogen displacement system equipped with stirring
Gas 3 times, envelope kettle are warming up to 280 DEG C of heat preservation polymerisations 5 hours, and polymerisation, which finishes, to be cooled to 80 DEG C and filter while hot, and polymer is obtained
Crude product；Polymer crude product single is filtered with 600g deionized water agitator treatings, is repeated agitator treating and is filtered 7 times；It polymerize after washing
Object single rinses oligomer with 600g deionized waters, repeats rinsing 3 times, obtains PPS wet basis；PPS wet basis is placed in vacuum drying chamber
In -0.095MPa, it is warming up to 120 DEG C of dryings 5 hours；Dry complete PPS is down to room temperature, obtains butt 88.6g, yield 81.3%；PPS
After tested, melt index 311g/10min, 281 DEG C of fusing point, performance indicator cannot meet fibre-grade PPS melt index and be less than
170g/10min requirements.
Embodiment 14
By 1 mole of PPS oligomer 109g, 0.5 mole of lithium chloride and 0.5 molar sodium acetate mixed catalyst 62g, 5 moles
N-Methyl pyrrolidone 495g, input, in the 1L titanium TA3 autoclaves of temperature measurer, lead to oxygen in nitrogen displacement system equipped with stirring
Gas 3 times, envelope kettle are warming up to 260 DEG C of heat preservation polymerisations 3 hours, and polymerisation, which finishes, to be cooled to 80 DEG C and filter while hot, and polymer is obtained
Crude product；Polymer crude product single is filtered with 600g deionized water agitator treatings, is repeated agitator treating and is filtered 7 times；It polymerize after washing
Object single rinses oligomer with 600g deionized waters, repeats rinsing 3 times, obtains PPS wet basis；PPS wet basis is placed in vacuum drying chamber
In -0.095MPa, it is warming up to 120 DEG C of dryings 5 hours；Dry complete PPS is down to room temperature, obtains butt 91.2g, yield 83.7%；PPS
After tested, melt index 213g/10min, 281 DEG C of fusing point, performance indicator cannot meet fibre-grade PPS melt index and be less than
170g/10min requirements.
Embodiment 15
By 1 mole of PPS oligomer 109g, 0.5 mole of lithium chloride and 0.5 molar sodium acetate mixed catalyst 62g, 5 moles
N-Methyl pyrrolidone 495g, input, in the 1L titanium TA3 autoclaves of temperature measurer, lead to oxygen in nitrogen displacement system equipped with stirring
Gas 3 times, envelope kettle are warming up to 260 DEG C of heat preservation polymerisations 8 hours, and polymerisation, which finishes, to be cooled to 80 DEG C and filter while hot, and polymer is obtained
Crude product；Polymer crude product single is filtered with 600g deionized water agitator treatings, is repeated agitator treating and is filtered 7 times；It polymerize after washing
Object single rinses oligomer with 600g deionized waters, repeats rinsing 3 times, obtains PPS wet basis；PPS wet basis is placed in vacuum drying chamber
In -0.095MPa, it is warming up to 120 DEG C of dryings 5 hours；Dry complete PPS is down to room temperature, obtains butt 96.5g, yield 88.5%；PPS
After tested, melt index 122g/10min, 283 DEG C of fusing point, performance indicator meet fibre-grade PPS melt index and are less than 170g/
10min requirements.
Claims (10)
1. a kind of method of PPS oligomer synthetic fibers grade PPS, it is characterised in that：It is low that PPS is put into autoclave according to a certain ratio
Polymers, catalysts and solvents control coefficient, and feed intake the oxygen finished in logical nitrogen displacement system；Displacement is finished envelope kettle and is warming up to
Reaction temperature, reaction certain time obtain polymer material；It is filtered after polymer material cooling, obtains polymer crude product；Polymer is thick
Product are repeatedly washed with quantitative deionized water, obtain washing post-consumer polymer；It is multiple with quantitative deionized water to wash post-consumer polymer
Separation of oligomeric is rinsed, fibre-grade PPS wet basis and PPS oligomer are obtained；Fibre-grade PPS wet basis is under certain temperature and vacuum degree
It is dried to the predetermined time, obtains fibre-grade PPS butts；Isolated PPS oligomer, set is fine for next batch after drying
Tie up the synthesis of grade PPS.
2. the method for PPS oligomer synthetic fibers grade PPS according to claim 1, it is characterised in that：The catalyst
For sodium phosphate, sodium carbonate, sodium tungstate, sodium sulphate, lithium chloride, lithium sulfate, sodium acetate, potassium phosphate, potassium phosphate,monobasic, biphosphate
Potassium, lithium chloride and sodium acetate mixed catalyst.
3. the method for PPS oligomer synthetic fibers grade PPS according to claim 2, it is characterised in that：The lithium chloride
It is lithium chloride with sodium acetate mixed catalyst mol ratio：Sodium acetate=1~99：99~1.
4. the method for PPS oligomer synthetic fibers grade PPS according to claim 1, it is characterised in that：The solvent is
N-Methyl pyrrolidone, hexamethylphosphoramide, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, caprolactam, nitro
Benzene, dimethyl sulfoxide (DMSO).
5. the method for PPS oligomer synthetic fibers grade PPS according to claim 1, it is characterised in that：The PPS is low
The mol ratio of polymers and catalyst is 1:2~0.1；The mol ratio of the PPS oligomer and solvent is 1:8~2.
6. the method for PPS oligomer synthetic fibers grade PPS according to claim 1, it is characterised in that：The autoclave
Coefficient control is 0.8~0.2；The reaction temperature is 220~280 DEG C；The reaction time is 1~10 hour.
7. the method for PPS oligomer synthetic fibers grade PPS according to claim 1, it is characterised in that：The single is washed
Wash 2~10 times that water is polymer crude product quality；The polymer crude product washing times are 3~15 times.
8. the method for PPS oligomer synthetic fibers grade PPS according to claim 1, it is characterised in that：The single is low
Polymers rinses 2~10 times that water is polymer crude product quality, and the single oligomer rinsing times are 1~5 time.
9. the method for PPS oligomer synthetic fibers grade PPS according to claim 1, it is characterised in that：The fibre-grade
The temperature of PPS wet basis drying is 50~200 DEG C；Vacuum degree is -0.01~-0.1Mpa；The time of drying is 1~10 hour.
10. the method for PPS oligomer synthetic fibers grade PPS according to claim 1, it is characterised in that：Autoclave material
For 300 series-chromiumnickel austenite stainless steel, titanium series TA1-TA8.
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| CN107383272B (en) * | 2017-07-21 | 2019-08-23 | 江苏扬农化工集团有限公司 | A method of the oligomer for being catalyzed aldol condensation polymer catalyst recycles |
| CN107936250B (en) * | 2017-11-29 | 2020-06-16 | 中国石油化工股份有限公司 | Method for recycling polyphenylene sulfide oligomer |
| CN111825862A (en) * | 2020-08-18 | 2020-10-27 | 南京工业职业技术学院 | Polyphenylene sulfide oligomer corrosion removing method and recycled material and application thereof |
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| CN102276838A (en) * | 2011-06-15 | 2011-12-14 | 南京大学 | Separation and recovery method for n-methylpyrrolidone (NMP) and lithium chloride catalyst during polyphenylene sulfide producing |
| CN102634210A (en) * | 2012-04-20 | 2012-08-15 | 陈逊 | Process for manufacturing fiber-grade polyphenylene sulfide resin slices |
| CN103242529A (en) * | 2013-05-31 | 2013-08-14 | 常熟市金泉化纤织造有限责任公司 | Purifying refining method for high-molecular-weight polyphenylene sulfide |
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