CN102560734A - Antioxidant toughening modified polyphenylene sulfide monofilament and preparation method thereof - Google Patents
Antioxidant toughening modified polyphenylene sulfide monofilament and preparation method thereof Download PDFInfo
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- CN102560734A CN102560734A CN2011104505302A CN201110450530A CN102560734A CN 102560734 A CN102560734 A CN 102560734A CN 2011104505302 A CN2011104505302 A CN 2011104505302A CN 201110450530 A CN201110450530 A CN 201110450530A CN 102560734 A CN102560734 A CN 102560734A
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- polyphenylene sulfide
- oxidant
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- modifying polyphenylene
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- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 190
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 190
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 142
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 142
- 238000002360 preparation method Methods 0.000 title claims abstract description 60
- 239000000843 powder Substances 0.000 claims abstract description 47
- 238000009987 spinning Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 15
- 235000006708 antioxidants Nutrition 0.000 claims description 133
- 239000007822 coupling agent Substances 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 25
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 16
- 238000002074 melt spinning Methods 0.000 claims description 16
- 238000010276 construction Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 9
- 238000005453 pelletization Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000004804 winding Methods 0.000 claims description 9
- 230000004927 fusion Effects 0.000 claims description 8
- -1 alcohol ester Chemical class 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 238000000048 melt cooling Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000012745 toughening agent Substances 0.000 abstract 2
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 230000003026 anti-oxygenic effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 125000003143 4-hydroxybenzyl group Chemical group [H]C([*])([H])C1=C([H])C([H])=C(O[H])C([H])=C1[H] 0.000 description 1
- 229920000784 Nomex Polymers 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004763 nomex Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
Abstract
The invention discloses an antioxidant toughening modified polyphenylene sulfide (PPS) monofilament and a preparation method of the PPS monofilament. The method of the invention comprises the steps of adding an antioxidant, a toughener, and a dispersing coupler into the polyphenylene sulfide powder to prepare antioxidant toughening modified polyphenylene sulfide chip, and melting and spinning; wherein the antioxidant toughening modified polyphenylene sulfide chip consists of the following components by weight: 95-97% of polyphenylene sulfide powder, 0.2-0.6% of antioxidant, 1-4% of inorganic toughener and 1-2% of dispersing coupler. According to the formula of the antioxidant toughening modified polyphenylene sulfide chip and the preparation method of the antioxidant toughening modified polyphenylene sulfide monofilament of the invention, modified polyphenylene sulfide monofilaments with superior breaking strength, breaking elongation, dry-heat shrinkage, antioxidant performance and toughness can be produced, and the method is stable in production process, low in cost, and good in product quality.
Description
Technical field
The present invention relates to the special chemical fiber field, relate in particular to a kind of anti-oxidant toughening modifying polyphenylene sulfide filaments and preparation method thereof.
Background technology
Polyphenylene sulfide (English name Polyphenylene Sulfide, abbreviation PPS) fiber is at first succeeded in developing by U.S.'s Philips (Philip) oil company.The said firm developed the PPS resin of fibre-grade in 1979 in PPS resin suitability for industrialized production in 1973, the industrialization of nineteen eighty-three PPS staple fibre.Because polyphenylene sulfide fibre has good serviceability, Japanese Japan is spun, east is beautiful, Supreme Being people and Bayer A.G also develop and produce polyphenylene sulfide fibre in succession.
Polyphenylene sulfide can be made into long filament and staple fibre, can also process monofilament.Because textile processibility ability and good chemical resistance, heat endurance, heat-resisting quantity and anti-flammability are preferably arranged; In environmental protection, flue and fields such as chemical industry high temperature filtration and Aero-Space, have widely and use, like steam power plant, coal-burning boiler, waste incineration, cement plant high-temperature flue filter bag; Corrosion-resistant filter cloth in the chemical industry; Dry zone in paper industry and the electrical industry, Nomex; The special cable cladding; Flame-retardant textile in the aerospace industry etc.Polyphenylene sulfide filaments also can be applicable to fields such as filtering material, hairbrush, net blanket and stamp net.
Although polyphenylene sulfide filaments has each item excellent properties in above Application Areas at present, still there is the shortcoming of non-oxidizability difference and fragility in existing polyphenylene sulfide filaments filter cloth on the filtering material field.
Therefore, prior art awaits to improve and development.
Summary of the invention
Deficiency in view of above-mentioned prior art the object of the present invention is to provide a kind of anti-oxidant toughening modifying polyphenylene sulfide filaments and preparation method thereof, is intended to solve the problem that existing polyphenylene sulfide filaments exists antioxygenic property difference and fragility.
Technical scheme of the present invention is following:
A kind of preparation method of anti-oxidant toughening modifying polyphenylene sulfide filaments; Wherein, Said anti-oxidant toughening modifying polyphenylene sulfide filaments preparation method; Be in the former powder of polyphenylene sulfide, to add antioxidant, flexibilizer and dispersion coupling agent, process anti-oxidant toughening modifying polyphenylene sulfide slice, carry out melt spinning again;
Wherein, said anti-oxidant toughening modifying polyphenylene sulfide slice is by weight percentage, and is composed of the following components:
The former powder of polyphenylene sulfide: 95 ~ 97%;
Antioxidant: 0.2 ~ 0.6%;
Inorganic flexibilizer: 1 ~ 4%;
Disperse coupling agent: 1 ~ 2%.
The preparation method of described anti-oxidant toughening modifying polyphenylene sulfide filaments, wherein, said anti-oxidant toughening modifying polyphenylene sulfide filaments preparation method specifically may further comprise the steps:
The preparation of S100, anti-oxidant toughening modifying polyphenylene sulfide slice:
S101, in the former powder of polyphenylene sulfide, add antioxidant, flexibilizer and dispersion coupling agent, mix;
S102, anti-oxidant toughening modifying polyphenylene sulfide slice is processed in the pelletizing of the former powder tie rod of the polyphenylene sulfide that mixes;
The preparation of S200, anti-oxidant toughening modifying polyphenylene sulfide filaments:
S202, melt spinning: anti-oxidant toughening modifying polyphenylene sulfide slice is carried out high-temperature fusion, and melt gets into filament spinning component, in filament spinning component, is sprayed by the spinneret orifice on the spinnerets;
S203, melt cooling: the melt thread cooling curing of ejection is configured as monfil;
S204, multiple tracks drawing-off reel: the monfil of solidified forming is laggardly gone into the water-bath drawing-off and is carried out the first road drawing-off through oiling; Carry out the second road hot-air drawing-off; Carry out the hot-air typing; Be wound into anti-oxidant toughening modifying polyphenylene sulfide filaments finished product.
The preparation method of described anti-oxidant toughening modifying polyphenylene sulfide filaments, wherein, before said step S202, further comprising the steps of:
Dry before S201, the fusion: as in vacuum drum or preparatory crystallizing and drying equipment, anti-oxidant toughening modifying polyphenylene sulfide slice to be carried out drying, be dried to moisture content≤80PPM.
The preparation method of described anti-oxidant toughening modifying polyphenylene sulfide filaments, wherein, the melt temperature of melt spinning described in the step S202 is 290 ~ 350 ℃; 0.5 ~ 2.5mm is selected in the aperture of said spinneret orifice for use, and draw ratio L/D is 3.0 ~ 10.0.
The preparation method of described anti-oxidant toughening modifying polyphenylene sulfide filaments, wherein, the cooling of melt described in the step S203 is that 6 ~ 15cm place is provided with a bosh below being positioned at said spinnerets, to melt thread water inlet cooling, bath temperature is controlled at 30 ~ 80 ℃.
The preparation method of described anti-oxidant toughening modifying polyphenylene sulfide filaments, wherein, among the step S204, said monfil total draft multiple is 2.5 ~ 10.0 times.
The preparation method of described anti-oxidant toughening modifying polyphenylene sulfide filaments, wherein, among the step S204, the drawing temperature of the said first road drawing-off is 80 ~ 98 ℃, drafting multiple accounts for 70 ~ 97% of general times; The drawing temperature of the said second road hot-air drawing-off is 150 ~ 220 ℃, and drafting multiple accounts for 3 ~ 30% of general times; The temperature of said hot-air typing is 180 ~ 280 ℃, and winding speed is 100 ~ 200m/min.
The preparation method of described anti-oxidant toughening modifying polyphenylene sulfide filaments; Wherein, The former powder of said polyphenylene sulfide is the polymer of linear structure;
construction unit content>=70% mol/mol wherein, melt index is 20 ~ 300g/10min.
The preparation method of described anti-oxidant toughening modifying polyphenylene sulfide filaments, wherein, said anti-oxidant is made up of among antioxidant AO1179 or the anti-oxidant AO110 one or both.
The preparation method of described anti-oxidant toughening modifying polyphenylene sulfide filaments, wherein, said inorganic flexibilizer is nanometer grade calcium carbonate.
The preparation method of described anti-oxidant toughening modifying polyphenylene sulfide filaments, wherein, said dispersion coupling agent is end amino polybasic alcohol ester.
A kind of anti-oxidant toughening modifying polyphenylene sulfide filaments that adopts above-mentioned preparation method to obtain, wherein, the diameter of said anti-oxidant toughening modifying polyphenylene sulfide filaments is at 0.2 ~ 0.7mm.
Beneficial effect: the preparation method of anti-oxidant toughening modifying polyphenylene sulfide slice prescription provided by the present invention and the anti-oxidant toughening modifying polyphenylene sulfide filaments of said preparation; Can produce all more excellent modified polyphenyl thioether monofilament of fracture strength, extension at break, dry-hot shrinkage, antioxygen property and toughness, its stable production process, low, the good product quality of cost.
The specific embodiment
The present invention provides a kind of anti-oxidant toughening modifying polyphenylene sulfide filaments and preparation method thereof, and is clearer, clear and definite for making the object of the invention, technical scheme and effect, below to further explain of the present invention.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
Said anti-oxidant toughening modifying polyphenylene sulfide filaments preparation method is provided among the present invention; Be in the former powder of polyphenylene sulfide (the former powder of PPS), to add antioxidant, flexibilizer and dispersion coupling agent; Process anti-oxidant toughening modifying polyphenylene sulfide slice, carry out melt spinning again.
Said anti-oxidant toughening modifying polyphenylene sulfide slice by weight percentage, mainly is grouped into by following one-tenth:
The former powder of PPS: 95 ~ 97%;
Antioxidant: 0.2 ~ 0.6%;
Inorganic flexibilizer: 1 ~ 4%;
Disperse coupling agent: 1 ~ 2%.
The former powder of said polyphenylene sulfide (the former powder of PPS) is a kind of polymer of linear structure; Wherein,
construction unit content>=70% mol/mol; Best>=90% mol/mol; Construction unit content is big more, explains that PPS purity is high more, just is beneficial to the performance of products of stabilizing and increasing of spinning production more.The former powder melt index of said PPS (MFR) should be 20 ~ 300g/10min, is preferably 30 ~ 300g/10min.Because MFR is excessive, the fiberizing difficulty, and MFR is low excessively, melt extrudes difficulty, is difficult to processing.Adopting MFR in the present invention is the former powder of PPS of 30 ~ 300g/10min, when producing, melt extrude handling ease, and fiberizing is good.
Said anti-oxidant can antioxidant AO1179 or anti-oxidant AO110 in one or both compositions.When containing antioxidant AO1179 and anti-oxidant AO110 in the said anti-oxidant, said anti-oxidant toughening modifying polyphenylene sulfide slice is preferably by following one-tenth and is grouped into by weight percentage:
The former powder of PPS: 95 ~ 97%;
Anti-oxidant 1179:0.1---0.3%;
Anti-oxidant AO110:0.1---0.3%;
Inorganic flexibilizer: 1 ~ 4%;
Disperse coupling agent: 1 ~ 2%.
Wherein, the main component of said antioxidant AO1179 is 3,5, three (3,5-di-t-butyl, 4-hydroxybenzyl) s-triazine and 2,4,6-(1H, 3H, 5H) triketone.The main component of said anti-oxidant AO110 is 4,4'-[1, the 1'-xenyl] subunit di 2 ethylhexyl phosphonic acid-four [2,4-two 2-methyl-2-phenylpropane bases] ester.In production polyphenylene sulfide slice process; Added said anti-oxidant; Can use the produced polyphenylene sulfide filaments of said polyphenylene sulfide slice to strengthen its antioxygenic property, have the effect that suppresses and delay outer its oxidation of bound pair, prolong the service life of polyphenylene sulfide filaments.Said anti-oxidant also can adopt the anti-oxidant of other kinds to replace, and can allocate according to technical staff's needs.
Said inorganic flexibilizer is nanometer grade calcium carbonate, is used to improve the toughness of polyphenylene sulfide filaments, improves the shortcoming that there is fragility in existing polyphenylene sulfide filaments.
Said dispersion coupling agent can be selected for use and disperse coupling agent EK602 for end amino polybasic alcohol ester.Said dispersion coupling agent can improve the compatibility of each component of system well as coupling agent and dispersant between the anti-oxidant toughening modifying polyphenylene sulfide slice raw material, promotes plasticizing;, section reduces melt viscosity in carrying out the process of fusion; Improve processing fluidity, reduce the thickener phenomenon, enhance productivity; And can improve the shock strength and the elongation at break of polyphenylene sulfide filaments, improve product surface gloss simultaneously.
Said anti-oxidant toughening modifying polyphenylene sulfide filaments preparation method specifically may further comprise the steps:
The preparation of S100, anti-oxidant toughening modifying polyphenylene sulfide slice:
S101, in the former powder of PPS, add antioxidant, flexibilizer and dispersion coupling agent, in high-speed mixer, mix; Wherein, because the high-speed mixing heat release can make the material temperature rise play certain desiccation;
S102, the former powder of the PPS that mixes is extruded the tie rod pelletizing by double screw extruder process anti-oxidant toughening modifying polyphenylene sulfide slice, supply spinning to produce the PPS monofilament and use.
The preparation of S200, anti-oxidant toughening modifying polyphenylene sulfide filaments:
Dry before S201, the fusion: as in vacuum drum or preparatory crystallizing and drying equipment, anti-oxidant toughening modifying polyphenylene sulfide slice to be carried out drying;
S202, melt spinning: anti-oxidant toughening modifying polyphenylene sulfide slice is carried out high-temperature fusion extrude in screw extruder; Melt gets into filament spinning component after the measuring pump metering, in filament spinning component, form certain pressure and evenly sprayed by the porous spinneret orifice on the spinnerets;
S203, melt cooling: melt thread cooling curing in bosh of ejection is configured as monfil;
S204, multiple tracks drawing-off reel: the monfil of solidified forming oils laggardly to go into the water-bath drawing-off and carry out the first road drawing-off through oiling roller, carries out the second road hot-air drawing-off again, carries out the hot-air typing, is wound into anti-oxidant toughening modifying polyphenylene sulfide filaments finished product then.
Said anti-oxidant toughening modifying polyphenylene sulfide filaments preparation method before melt spinning, can carry out drying, i.e. step S201 are carried out in modification linear polyphenylene sulfide section.Like this, can avoid polyphenylene sulfide slice to melt extrude and produce putty in the process, cause pressure oscillation, hydrolysis and situation such as crosslinked at screw rod.Dry run before the said fusion is preferably polyphenylene sulfide slice is dried to moisture content≤80PPM.
In said melt spinning process, melt temperature is 290 ~ 350 ℃.0.5 ~ 2.5mm is selected in the aperture of said spinneret orifice for use, because polyphenylene sulfide belongs to the high-elasticity thermoplastic material, spinneret orifice draw ratio L/D is 3.0 ~ 10.0 comparatively suitable, and the monofilament of production different thicknesses can be selected different spinneret orifice diameters for use.
Said melt cooling is that 6 ~ 15cm place is provided with a bosh below being positioned at spinnerets, and to melt thread water inlet cooling, bath temperature is controlled at 30 ~ 80 ℃.The low inhomogeneous cooling that causes easily of the mistake of said bath temperature is even, forms skin-core structure, and the too high then cooling effect of temperature is bad.
The drafting forming process of said monfil is to be higher than the process of carrying out drawing-off and typing in the polyphenylene sulfide glass temperature environment at one, and in this process, control monfil total draft multiple is 2.5 ~ 10.0 times.In order to improve the intensity of fiber, adopted twice continuous drafting operation among the preparation method of the present invention, the drawing-off in water-bath of first road, drawing temperature is 80 ~ 98 ℃, drafting multiple accounts for 70 ~ 97% of general times; The second road drawing-off is carried out in hot-air, and drawing temperature is 150 ~ 220 ℃, and drafting multiple accounts for 3 ~ 30% of general times.Said type-approval process carries out loose typing in hot-air, be beneficial to reduce dry-hot shrinkage, and temperature is 180 ~ 280 ℃, and loose rate is 0 ~ 10%, and winding speed is 100 ~ 200m/min.
The diameter of resulting anti-oxidant toughening modifying PPS monofilament is at 0.2 ~ 0.7mm, and relative intensity is 2.5 ~ 4.0cN/dtex, and extension at break is that 20 ~ 40%, 180 ℃ of dry-hot shrinkages are less than 3%.Said anti-oxidant toughening modifying polyphenylene sulfide filaments is compared with conventional polyphenylene sulfide filaments, and identical heat resistance and chemical-resistant stability are arranged, and is applicable to filtering material, and better antioxygenic property and toughness are arranged again simultaneously.
Embodiment 1
Adopting MFR is the former powder of 168g/10min linear polyphenylene sulfide, and its construction unit content >=90% mol/mol produces anti-oxidant toughening modifying polyphenylene sulfide slice through following prescription:
The former powder of PPS: 96%
Anti-oxidant AO1179:0.2%
Anti-oxidant AO110:0.2%
Nanometer grade calcium carbonate: 2.6%
Disperse coupling agent EK602:1%
The preparation of anti-oxidant toughening modifying polyphenylene sulfide slice: in the former powder of PPS, add antioxidant, flexibilizer and dispersion coupling agent, in high-speed mixer, mix and drying; The former powder of the PPS that combination drying is good is extruded the tie rod pelletizing by double screw extruder and is processed anti-oxidant toughening modifying polyphenylene sulfide slice, supplies spinning to produce the PPS monofilament and uses.
The preparation of anti-oxidant toughening modifying polyphenylene sulfide filaments: before melt spinning, drying is carried out in the section of p-poly-phenyl thioether in vacuum drum, and moisture content is 49PPM.Extruder temperature is 310 ℃ during spinning, 310 ℃ of measuring pump temperature, and 310 ℃ of assembly temperatures, The hole diameter of spinneret 0.9mm, draw ratio (L/D) is 6, the spinnerets hole count is 45 holes, 55 ℃ of bosh water temperatures; Adopt the twice drawing-off to carry out drawing-off, the total draft multiple is 4.03 times, each road drawing roller temperature and multiple, and setting temperature, winding speed and polyphenylene sulfide filaments physical index are referring to shown in the table 1.
Embodiment 2
Adopting MFR is the former powder of 200g/10min linear polyphenylene sulfide, and its construction unit content >=70% mol/mol produces anti-oxidant toughening modifying polyphenylene sulfide slice through following prescription:
The former powder of PPS: 95.8%
Anti-oxidant AO1179:0.3%
Nanometer grade calcium carbonate: 2.9%
Disperse coupling agent EK602:1%
The preparation of anti-oxidant toughening modifying polyphenylene sulfide slice: in the former powder of PPS, add antioxidant, flexibilizer and dispersion coupling agent, in high-speed mixer, mix and drying; The former powder of the PPS that combination drying is good is extruded the tie rod pelletizing by double screw extruder and is processed anti-oxidant toughening modifying polyphenylene sulfide slice, supplies spinning to produce the PPS monofilament and uses.
The preparation of anti-oxidant toughening modifying polyphenylene sulfide filaments: before melt spinning, drying is carried out in the section of p-poly-phenyl thioether in vacuum drum, and moisture content is 50PPM.Extruder temperature is 310 ℃ during spinning, 310 ℃ of measuring pump temperature, and 310 ℃ of assembly temperatures, The hole diameter of spinneret 0.9mm, draw ratio (L/D) is 6, the spinnerets hole count is 45 holes, 55 ℃ of bosh water temperatures; Adopt the twice drawing-off to carry out drawing-off, the total draft multiple is 4.03 times, each road drawing roller temperature and multiple, and setting temperature, winding speed and polyphenylene sulfide filaments physical index are referring to shown in the table 1.
Embodiment 3
Adopting MFR is the former powder of 168g/10min linear polyphenylene sulfide, and its construction unit content >=90% mol/mol produces anti-oxidant toughening modifying polyphenylene sulfide slice through following prescription:
The former powder of PPS: 97%
Anti-oxidant AO110:0.3%
Nanometer grade calcium carbonate: 1%
Disperse coupling agent EK602:1.7%
The preparation of anti-oxidant toughening modifying polyphenylene sulfide slice: in the former powder of PPS, add antioxidant, flexibilizer and dispersion coupling agent, in high-speed mixer, mix and drying; The former powder of the PPS that combination drying is good is extruded the tie rod pelletizing by double screw extruder and is processed anti-oxidant toughening modifying polyphenylene sulfide slice, supplies spinning to produce the PPS monofilament and uses.
The preparation of anti-oxidant toughening modifying polyphenylene sulfide filaments: before melt spinning, drying is carried out in the section of p-poly-phenyl thioether in vacuum drum, and moisture content is 45PPM.Extruder temperature is 310 ℃ during spinning, 310 ℃ of measuring pump temperature, and 310 ℃ of assembly temperatures, The hole diameter of spinneret 0.9mm, draw ratio (L/D) is 6, the spinnerets hole count is 45 holes, 55 ℃ of bosh water temperatures; Adopt the twice drawing-off to carry out drawing-off, the total draft multiple is 4.03 times, each road drawing roller temperature and multiple, and setting temperature, winding speed and polyphenylene sulfide filaments physical index are referring to shown in the table 1.
Embodiment 4
Having adopted MFR is the linear polyphenylene sulfide section of 210g/10min, its construction unit content >=90%.The aperture is the spinnerets of 1.6 mm, and other condition is with embodiment 1, and drawing-off coiling condition and physical index are seen shown in the table 1.
Embodiment 5
Adopting MFR is the former powder of 300g/10min linear polyphenylene sulfide, and its construction unit content >=80% mol/mol produces anti-oxidant toughening modifying polyphenylene sulfide slice through following prescription:
The former powder of PPS: 95%
Anti-oxidant AO1179:0.3%
Anti-oxidant AO110:0.3%
Nanometer grade calcium carbonate: 2%
Disperse coupling agent EK602:1.4%
The preparation of anti-oxidant toughening modifying polyphenylene sulfide slice: in the former powder of PPS, add antioxidant, flexibilizer and dispersion coupling agent, in high-speed mixer, mix and drying; The former powder of the PPS that combination drying is good is extruded the tie rod pelletizing by double screw extruder and is processed anti-oxidant toughening modifying polyphenylene sulfide slice, supplies spinning to produce the PPS monofilament and uses.
The preparation of anti-oxidant toughening modifying polyphenylene sulfide filaments: before melt spinning, drying is carried out in the section of p-poly-phenyl thioether in vacuum drum, and moisture content is 45PPM.Extruder temperature is 300 ℃ during spinning, 300 ℃ of measuring pump temperature, and 300 ℃ of assembly temperatures, The hole diameter of spinneret 0.5mm, draw ratio (L/D) is 8, the spinnerets hole count is 150 holes, 30 ℃ of bosh water temperatures; Adopt the twice drawing-off to carry out drawing-off, the total draft multiple is 3.92 times, each road drawing roller temperature and multiple, and setting temperature, winding speed and polyphenylene sulfide filaments physical index are referring to shown in the table 1.
Embodiment 6
Adopting MFR is the former powder of 100g/10min linear polyphenylene sulfide, and its construction unit content >=80% mol/mol produces anti-oxidant toughening modifying polyphenylene sulfide slice through following prescription:
The former powder of PPS: 96.1%
Anti-oxidant AO110:0.3%
Nanometer grade calcium carbonate: 2.6%
Disperse coupling agent EK602:1%
The preparation of anti-oxidant toughening modifying polyphenylene sulfide slice: in the former powder of PPS, add antioxidant, flexibilizer and dispersion coupling agent, in high-speed mixer, mix and drying; The former powder of the PPS that combination drying is good is extruded the tie rod pelletizing by double screw extruder and is processed anti-oxidant toughening modifying polyphenylene sulfide slice, supplies spinning to produce the PPS monofilament and uses.
The preparation of anti-oxidant toughening modifying polyphenylene sulfide filaments: before melt spinning, drying is carried out in the section of p-poly-phenyl thioether in vacuum drum, and moisture content is 60PPM.Extruder temperature is 330 ℃ during spinning, 330 ℃ of measuring pump temperature, and 330 ℃ of assembly temperatures, The hole diameter of spinneret 2.5mm, draw ratio (L/D) is 8, the spinnerets hole count is 16 holes, 80 ℃ of bosh water temperatures; Adopt the twice drawing-off to carry out drawing-off, the total draft multiple is 4.48 times, each road drawing roller temperature and multiple, and setting temperature, winding speed and polyphenylene sulfide filaments physical index are referring to shown in the table 1.
Embodiment 7
Adopting MFR is the former powder of 30g/10min linear polyphenylene sulfide, and its construction unit content >=80% mol/mol produces anti-oxidant toughening modifying polyphenylene sulfide slice through following prescription:
The former powder of PPS: 96.1%
Anti-oxidant AO1179:0.3%
Nanometer grade calcium carbonate: 2.6%
Disperse coupling agent EK602:1%
The preparation of anti-oxidant toughening modifying polyphenylene sulfide slice: in the former powder of PPS, add antioxidant, flexibilizer and dispersion coupling agent, in high-speed mixer, mix and drying; The former powder of the PPS that combination drying is good is extruded the tie rod pelletizing by double screw extruder and is processed anti-oxidant toughening modifying polyphenylene sulfide slice, supplies spinning to produce the PPS monofilament and uses.
The preparation of anti-oxidant toughening modifying polyphenylene sulfide filaments: before melt spinning, drying is carried out in the section of p-poly-phenyl thioether in vacuum drum, and moisture content is 80PPM.Extruder temperature is 340 ℃ during spinning, 340 ℃ of measuring pump temperature, and 340 ℃ of assembly temperatures, The hole diameter of spinneret 2mm, draw ratio (L/D) is 8, the spinnerets hole count is 25 holes, 60 ℃ of bosh water temperatures; Adopt the twice drawing-off to carry out drawing-off, the total draft multiple is 4.48 times, each road drawing roller temperature and multiple, and setting temperature, winding speed and polyphenylene sulfide filaments physical index are referring to shown in the table 1.
Wherein, what unmodified polyphenylene sulfide filaments adopted in table 1 is that MFR is the former powder of 168g/10min linear polyphenylene sulfide, its construction unit content >=90% mol/mol, and its processing parameter and physical property are as shown in table 1.
Table 1 embodiment technological parameter and rerum natura table
﹡ fracture strength unit is converted into line density dtex with filament diameter mm to calculate and get.
The ﹡ non-oxidizability is that monofilament is placed in 180 ℃ of baking ovens, has to dry by the fire after 48 hours under the air conditions to test its intensity again, comes to weigh qualitatively with the size of loss of strength.
The inflexible target of ﹡ initial modulus reflection monofilament also reflects its toughness index conversely, and promptly initial modulus is big, and the monofilament rigidity is big, poor toughness, and initial modulus is little, and the monofilament rigidity is little, good toughness.
Result according to embodiment 1 ~ 7; Can find out; Under identical and preparation condition inequality; Compare with unmodified monofilament according to the prepared modified polyphenyl thioether monofilament that obtains of prescription provided by the present invention and method, the polyphenylene sulfide filaments of modification all has identical heat resistance and chemical-resistant stability, has better antioxygenic property and toughness simultaneously again.
Should be understood that application of the present invention is not limited to above-mentioned giving an example, concerning those of ordinary skills, can improve or conversion that all these improvement and conversion all should belong to the protection domain of accompanying claims of the present invention according to above-mentioned explanation.
Claims (12)
1. the preparation method of an anti-oxidant toughening modifying polyphenylene sulfide filaments; It is characterized in that; Said anti-oxidant toughening modifying polyphenylene sulfide filaments preparation method; Be in the former powder of polyphenylene sulfide, to add antioxidant, flexibilizer and dispersion coupling agent, process anti-oxidant toughening modifying polyphenylene sulfide slice, carry out melt spinning again;
Wherein, said anti-oxidant toughening modifying polyphenylene sulfide slice is by weight percentage, and is composed of the following components:
The former powder of polyphenylene sulfide: 95 ~ 97%;
Antioxidant: 0.2 ~ 0.6%;
Inorganic flexibilizer: 1 ~ 4%;
Disperse coupling agent: 1 ~ 2%.
2. the preparation method of anti-oxidant toughening modifying polyphenylene sulfide filaments according to claim 1 is characterized in that, said anti-oxidant toughening modifying polyphenylene sulfide filaments preparation method specifically may further comprise the steps:
The preparation of S100, anti-oxidant toughening modifying polyphenylene sulfide slice:
S101, in the former powder of polyphenylene sulfide, add antioxidant, flexibilizer and dispersion coupling agent, mix;
S102, anti-oxidant toughening modifying polyphenylene sulfide slice is processed in the pelletizing of the former powder tie rod of the polyphenylene sulfide that mixes;
The preparation of S200, anti-oxidant toughening modifying polyphenylene sulfide filaments:
S202, melt spinning: anti-oxidant toughening modifying polyphenylene sulfide slice is carried out high-temperature fusion, and melt gets into filament spinning component, in filament spinning component, is sprayed by the spinneret orifice on the spinnerets;
S203, melt cooling: the melt thread cooling curing of ejection is configured as monfil;
S204, multiple tracks drawing-off reel: the monfil of solidified forming is laggardly gone into the water-bath drawing-off and is carried out the first road drawing-off through oiling; Carry out the second road hot-air drawing-off; Carry out the hot-air typing; Be wound into anti-oxidant toughening modifying polyphenylene sulfide filaments finished product.
3. the preparation method of anti-oxidant toughening modifying polyphenylene sulfide filaments according to claim 2 is characterized in that, and is before said step S202, further comprising the steps of:
Dry before S201, the fusion: as in vacuum drum or preparatory crystallizing and drying equipment, anti-oxidant toughening modifying polyphenylene sulfide slice to be carried out drying, be dried to moisture content≤80PPM.
4. the preparation method of anti-oxidant toughening modifying polyphenylene sulfide filaments according to claim 2 is characterized in that, the melt temperature of melt spinning described in the step S202 is 290 ~ 350 ℃; 0.5 ~ 2.5mm is selected in the aperture of said spinneret orifice for use, and draw ratio L/D is 3.0 ~ 10.0.
5. the preparation method of anti-oxidant toughening modifying polyphenylene sulfide filaments according to claim 2; It is characterized in that; The cooling of melt described in the step S203 is that 6 ~ 15cm place is provided with a bosh below being positioned at said spinnerets, and to melt thread water inlet cooling, bath temperature is controlled at 30 ~ 80 ℃.
6. the preparation method of anti-oxidant toughening modifying polyphenylene sulfide filaments according to claim 2 is characterized in that, among the step S204, said monfil total draft multiple is 2.5 ~ 10.0 times.
7. the preparation method of anti-oxidant toughening modifying polyphenylene sulfide filaments according to claim 2 is characterized in that, among the step S204, the drawing temperature of the said first road drawing-off is 80 ~ 98 ℃, and drafting multiple accounts for 70 ~ 97% of general times; The drawing temperature of the said second road hot-air drawing-off is 150 ~ 220 ℃, and drafting multiple accounts for 3 ~ 30% of general times; The temperature of said hot-air typing is 180 ~ 280 ℃, and winding speed is 100 ~ 200m/min.
8. the preparation method of anti-oxidant toughening modifying polyphenylene sulfide filaments according to claim 1; It is characterized in that; The former powder of said polyphenylene sulfide is the polymer of linear structure;
construction unit content>=70% mol/mol wherein, melt index is 20 ~ 300g/10min.
9. the preparation method of anti-oxidant toughening modifying polyphenylene sulfide filaments according to claim 1 is characterized in that, said anti-oxidant is made up of among antioxidant AO1179 or the anti-oxidant AO110 one or both.
10. the preparation method of anti-oxidant toughening modifying polyphenylene sulfide filaments according to claim 1 is characterized in that, said inorganic flexibilizer is nanometer grade calcium carbonate.
11. the preparation method of anti-oxidant toughening modifying polyphenylene sulfide filaments according to claim 1 is characterized in that, said dispersion coupling agent is end amino polybasic alcohol ester.
12. an anti-oxidant toughening modifying polyphenylene sulfide filaments that adopts the arbitrary described preparation method of claim 1 ~ 11 to obtain is characterized in that the diameter of said anti-oxidant toughening modifying polyphenylene sulfide filaments is at 0.2 ~ 0.7mm.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102776601A (en) * | 2012-08-16 | 2012-11-14 | 敦煌西域特种新材股份有限公司 | Polyphenylene sulfide fiber spinning technology |
| CN103556297A (en) * | 2013-10-17 | 2014-02-05 | 绍兴文理学院 | Preparation method of highly antioxidative colored PPS filaments |
| CN104195669A (en) * | 2014-09-15 | 2014-12-10 | 马海燕 | Large-diameter polyphenylene sulfide monofilament and production method thereof |
| CN108360085A (en) * | 2018-01-12 | 2018-08-03 | 安徽工程大学 | Anti-oxidant fiber of a kind of polyphenylene sulfide based on laminar nano particle and preparation method thereof |
| CN110205704A (en) * | 2019-06-03 | 2019-09-06 | 太原理工大学 | A kind of antioxidant polyphenylene sulfide/Quercetin composite fibre and preparation method thereof |
| CN110295402A (en) * | 2019-06-11 | 2019-10-01 | 宜宾天原集团股份有限公司 | A kind of preparation method of polyphenylene sulfide fibre |
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| CN113426670A (en) * | 2020-09-18 | 2021-09-24 | 台州市文龙网业科技有限公司 | PPS (polyphenylene sulfite) screen for filtering fish meal and preparation method thereof |
| CN113561474A (en) * | 2021-08-03 | 2021-10-29 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | Preparation system and method of continuous carbon fiber reinforced PPS printing wire and application of preparation system |
| CN114134583A (en) * | 2021-12-28 | 2022-03-04 | 南通新帝克单丝科技股份有限公司 | High-dpf polyphenylene sulfide long fiber and production method thereof |
| CN114395823A (en) * | 2021-12-09 | 2022-04-26 | 安徽元琛环保科技股份有限公司 | Preparation method of oxidation-resistant PPS filtering material and prepared modified PPS fiber |
| CN114540976A (en) * | 2021-12-28 | 2022-05-27 | 南通新帝克单丝科技股份有限公司 | Production method of high-toughness high-strength polyphenylene sulfide monofilament |
| TWI780360B (en) * | 2018-09-27 | 2022-10-11 | 日商東麗股份有限公司 | Copolymerized polyphenylene sulfide fiber |
| CN117107378A (en) * | 2023-10-12 | 2023-11-24 | 山东明化新材料有限公司 | Equipment and spinning method for spinning modified polyphenylene sulfide composite fiber |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5818409A (en) * | 1981-07-24 | 1983-02-03 | Toray Ind Inc | Production of polyphenylene sulfide fiber |
| CN1856545A (en) * | 2003-08-18 | 2006-11-01 | 切夫里昂菲利普化学有限责任公司 | Polyphenylene sulfide composition and application |
| CN1962973A (en) * | 2006-12-04 | 2007-05-16 | 祝万山 | Method for preparing anti-oxygen polyphenyl thioether fiber |
| CN100999833A (en) * | 2007-01-09 | 2007-07-18 | 江苏省纺织研究所有限公司 | Production process of poly-phenyl thio-ether fibre |
| CN101126182A (en) * | 2007-10-09 | 2008-02-20 | 东华大学 | Ultraviolet radiation resisting polyphenylene sulfide and preparation method thereof |
| CN101363144A (en) * | 2008-09-25 | 2009-02-11 | 东华大学 | Polyphenyl thioether/superfine calcium carbonate microparticle complex fiber and preparation method thereof |
| CN101368300A (en) * | 2008-08-04 | 2009-02-18 | 东华大学 | Polyphenyl thioether/ultra-fine calcium carbonate particulate composite fiber and preparation method thereof |
-
2011
- 2011-12-29 CN CN 201110450530 patent/CN102560734B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5818409A (en) * | 1981-07-24 | 1983-02-03 | Toray Ind Inc | Production of polyphenylene sulfide fiber |
| CN1856545A (en) * | 2003-08-18 | 2006-11-01 | 切夫里昂菲利普化学有限责任公司 | Polyphenylene sulfide composition and application |
| CN1962973A (en) * | 2006-12-04 | 2007-05-16 | 祝万山 | Method for preparing anti-oxygen polyphenyl thioether fiber |
| CN100999833A (en) * | 2007-01-09 | 2007-07-18 | 江苏省纺织研究所有限公司 | Production process of poly-phenyl thio-ether fibre |
| CN101126182A (en) * | 2007-10-09 | 2008-02-20 | 东华大学 | Ultraviolet radiation resisting polyphenylene sulfide and preparation method thereof |
| CN101368300A (en) * | 2008-08-04 | 2009-02-18 | 东华大学 | Polyphenyl thioether/ultra-fine calcium carbonate particulate composite fiber and preparation method thereof |
| CN101363144A (en) * | 2008-09-25 | 2009-02-11 | 东华大学 | Polyphenyl thioether/superfine calcium carbonate microparticle complex fiber and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 祝万山等: "抗氧聚苯硫醚(PPS)纤维的研究与开发", 《非织造布》 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102776601A (en) * | 2012-08-16 | 2012-11-14 | 敦煌西域特种新材股份有限公司 | Polyphenylene sulfide fiber spinning technology |
| CN103556297A (en) * | 2013-10-17 | 2014-02-05 | 绍兴文理学院 | Preparation method of highly antioxidative colored PPS filaments |
| CN104195669A (en) * | 2014-09-15 | 2014-12-10 | 马海燕 | Large-diameter polyphenylene sulfide monofilament and production method thereof |
| CN108360085A (en) * | 2018-01-12 | 2018-08-03 | 安徽工程大学 | Anti-oxidant fiber of a kind of polyphenylene sulfide based on laminar nano particle and preparation method thereof |
| TWI780360B (en) * | 2018-09-27 | 2022-10-11 | 日商東麗股份有限公司 | Copolymerized polyphenylene sulfide fiber |
| CN110205704B (en) * | 2019-06-03 | 2021-12-28 | 太原理工大学 | Antioxidant polyphenylene sulfide/quercetin composite fiber and preparation method thereof |
| CN110205704A (en) * | 2019-06-03 | 2019-09-06 | 太原理工大学 | A kind of antioxidant polyphenylene sulfide/Quercetin composite fibre and preparation method thereof |
| CN110295402A (en) * | 2019-06-11 | 2019-10-01 | 宜宾天原集团股份有限公司 | A kind of preparation method of polyphenylene sulfide fibre |
| CN110295402B (en) * | 2019-06-11 | 2021-02-09 | 宜宾天原集团股份有限公司 | Preparation method of polyphenylene sulfide fiber |
| CN111394808A (en) * | 2020-03-20 | 2020-07-10 | 湖南翰坤实业有限公司 | Material capable of being used for manufacturing high-altitude construction safety rope |
| CN113426670A (en) * | 2020-09-18 | 2021-09-24 | 台州市文龙网业科技有限公司 | PPS (polyphenylene sulfite) screen for filtering fish meal and preparation method thereof |
| CN113561474A (en) * | 2021-08-03 | 2021-10-29 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | Preparation system and method of continuous carbon fiber reinforced PPS printing wire and application of preparation system |
| CN114395823A (en) * | 2021-12-09 | 2022-04-26 | 安徽元琛环保科技股份有限公司 | Preparation method of oxidation-resistant PPS filtering material and prepared modified PPS fiber |
| CN114395823B (en) * | 2021-12-09 | 2023-10-31 | 安徽元琛环保科技股份有限公司 | Method for manufacturing oxidation-resistant PPS (polyphenylene sulfide) filter material and prepared modified PPS fiber |
| CN114134583A (en) * | 2021-12-28 | 2022-03-04 | 南通新帝克单丝科技股份有限公司 | High-dpf polyphenylene sulfide long fiber and production method thereof |
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| CN117107378A (en) * | 2023-10-12 | 2023-11-24 | 山东明化新材料有限公司 | Equipment and spinning method for spinning modified polyphenylene sulfide composite fiber |
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