CN102560734B - 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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- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 138
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 138
- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 101
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- 239000000843 powder Substances 0.000 claims abstract description 47
- 238000009987 spinning Methods 0.000 claims abstract description 21
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 6
- 235000006708 antioxidants Nutrition 0.000 claims description 129
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 85
- 150000003568 thioethers Chemical class 0.000 claims description 85
- 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
- 238000002074 melt spinning Methods 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 238000010276 construction Methods 0.000 claims description 12
- 238000004804 winding Methods 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
- 238000001816 cooling Methods 0.000 claims description 8
- 238000000048 melt cooling Methods 0.000 claims description 6
- -1 alcohol ester Chemical class 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 230000004927 fusion Effects 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000012745 toughening agent Substances 0.000 abstract 2
- 239000000835 fiber Substances 0.000 description 7
- 241000208340 Araliaceae Species 0.000 description 6
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 6
- 235000003140 Panax quinquefolius Nutrition 0.000 description 6
- 235000008434 ginseng Nutrition 0.000 description 6
- 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
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- 239000003921 oil Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004753 textile Substances 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
- 241000196324 Embryophyta Species 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
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
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- 229920005989 resin Polymers 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
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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 antioxidant toughening modified polyphenyl thioether monofilament 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 Industry in 1973 production, 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 in succession development and production go out polyphenylene sulfide fibre.
Polyphenylene sulfide can be made into long filament and staple fibre, can also make monofilament.Because preferably textile process performance and good chemical resistance, heat endurance, heat-resisting quantity and anti-flammability being arranged, in environmental protection, flue and the fields such as chemical industry high temperature filtration and Aero-Space, have widely and use, such as 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 the fields such as filtering material, hairbrush, net blanket and stamp net.
Although at present polyphenylene sulfide filaments has every excellent properties in above Application Areas, still there is the shortcoming of the poor and fragility of non-oxidizability in existing polyphenylene sulfide filaments filter cloth on the filtering material field.
Therefore, prior art has yet to be improved and developed.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of antioxidant toughening modified polyphenyl thioether monofilament and preparation method thereof, be intended to solve the problem that there is the poor and fragility of antioxygenic property in existing polyphenylene sulfide filaments.
Technical scheme of the present invention is as follows:
A kind of preparation method of antioxidant toughening modified polyphenyl thioether monofilament, wherein, described antioxidant toughening modified polyphenyl thioether monofilament preparation method, in the former powder of polyphenylene sulfide, to add antioxidant, flexibilizer and dispersion coupling agent, make the section of antioxidant toughening modified polyphenyl thioether, carry out again melt spinning;
Wherein, described antioxidant toughening modified polyphenyl thioether section 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 antioxidant toughening modified polyphenyl thioether monofilament, wherein, described antioxidant toughening modified polyphenyl thioether monofilament preparation method specifically may further comprise the steps:
The preparation of S100, the section of antioxidant toughening modified polyphenyl thioether:
S101, in the former powder of polyphenylene sulfide, add antioxidant, flexibilizer and dispersion coupling agent, mix;
S102, antioxidant toughening modified polyphenyl thioether section is made in the pelletizing of the former powder tie rod of the polyphenylene sulfide that mixes;
The preparation of S200, antioxidant toughening modified polyphenyl thioether monofilament:
S202, melt spinning: high-temperature fusion is carried out in the section of antioxidant toughening modified polyphenyl thioether, and melt enters filament spinning component, is sprayed by the spinneret orifice on the spinnerets in filament spinning component;
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 laggardly enters the water-bath drawing-off and carries out the first drawing-off through oiling; Carry out the drawing-off of second hot-air; Carry out the hot-air typing; Be wound into antioxidant toughening modified polyphenyl thioether monofilament finished product.
The preparation method of described antioxidant toughening modified polyphenyl thioether monofilament, wherein, before described step S202, further comprising the steps of:
Dry before S201, the melting: as in vacuum drum or pre-crystallized 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 antioxidant toughening modified polyphenyl thioether monofilament, 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 described spinneret orifice, and draw ratio L/D is 3.0 ~ 10.0.
The preparation method of described antioxidant toughening modified polyphenyl thioether monofilament, wherein, melt cooling described in the step S203 is that 6 ~ 15cm place arranges a bosh below being positioned at described spinnerets, to melt thread water inlet cooling, bath temperature is controlled at 30 ~ 80 ℃.
The preparation method of described antioxidant toughening modified polyphenyl thioether monofilament, wherein, among the step S204, described monfil total draft multiple is 2.5 ~ 10.0 times.
The preparation method of described antioxidant toughening modified polyphenyl thioether monofilament, wherein, among the step S204, the drawing temperature of described first drawing-off is 80 ~ 98 ℃, drafting multiple accounts for 70 ~ 97% of general times; The drawing temperature of described second hot-air drawing-off is 150 ~ 220 ℃, and drafting multiple accounts for 3 ~ 30% of general times; The temperature of described hot-air typing is 180 ~ 280 ℃, and winding speed is 100 ~ 200m/min.
The preparation method of described antioxidant toughening modified polyphenyl thioether monofilament, wherein, the former powder of described polyphenylene sulfide is the polymer of linear structure, wherein
Construction unit content 〉=70% mol/mol, melt index are 20 ~ 300g/10min.
The preparation method of described antioxidant toughening modified polyphenyl thioether monofilament, wherein, described antioxidant is comprised of among antioxidant AO1179 or the antioxidant AO110 one or both.
The preparation method of described antioxidant toughening modified polyphenyl thioether monofilament, wherein, described inorganic flexibilizer is nanometer grade calcium carbonate.
The preparation method of described antioxidant toughening modified polyphenyl thioether monofilament, wherein, described dispersion coupling agent is end amino polybasic alcohol ester.
A kind of antioxidant toughening modified polyphenyl thioether monofilament that adopts above-mentioned preparation method to obtain, wherein, the diameter of described antioxidant toughening modified polyphenyl thioether monofilament is at 0.2 ~ 0.7mm.
Beneficial effect: the preparation method of antioxidant toughening modified polyphenyl thioether slice formulation provided by the present invention and described preparation antioxidant toughening modified polyphenyl thioether monofilament, 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, cost are low, good product quality.
The specific embodiment
The invention provides a kind of antioxidant toughening modified polyphenyl thioether monofilament and preparation method thereof, clearer, clear and definite for making purpose of the present invention, technical scheme and effect, below the present invention is described in more detail.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
Described antioxidant toughening modified polyphenyl thioether monofilament preparation method is provided among the present invention, in the former powder of polyphenylene sulfide (the former powder of PPS), to add antioxidant, flexibilizer and dispersion coupling agent, make the section of antioxidant toughening modified polyphenyl thioether, carry out again melt spinning.
Described antioxidant toughening modified polyphenyl thioether section by weight percentage, mainly consists of the following composition:
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 described 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 larger, illustrates that PPS purity is higher, just more is beneficial to the performance of stabilizing and increasing product that spinning is produced.The former powder melt index of described PPS (MFR) should be 20 ~ 300g/10min, is preferably 30 ~ 300g/10min.Because MFR is excessive, the fiberizing difficulty, and MFR is excessively low, melt extrudes difficulty, is difficult to processing.Adopting in the present invention MFR is the former powder of PPS of 30 ~ 300g/10min, when producing, melt extrude handling ease, and fiberizing is good.
Described antioxidant can antioxidant AO1179 or antioxidant AO110 in one or both compositions.When containing antioxidant AO1179 and antioxidant AO110 in the described antioxidant, described antioxidant toughening modified polyphenyl thioether is cut into slices by weight percentage, is preferably to consist of the following composition:
The former powder of PPS: 95 ~ 97%;
Antioxidant 1179:0.1---0.3%;
Antioxidant AO110:0.1---0.3%;
Inorganic flexibilizer: 1 ~ 4%;
Disperse coupling agent: 1 ~ 2%.
Wherein, the main component of described 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 described antioxidant 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 described antioxidant, can use the produced polyphenylene sulfide filaments of described 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.Described antioxidant also can adopt the antioxidant of other kinds to replace, and can allocate according to technical staff's needs.
Described inorganic flexibilizer is nanometer grade calcium carbonate, is used for improving the toughness of polyphenylene sulfide filaments, improves the shortcoming that there is fragility in existing polyphenylene sulfide filaments.
Described dispersion coupling agent can be selected and disperse coupling agent EK602 for end amino polybasic alcohol ester.Described dispersion coupling agent is as coupling agent and dispersant between the antioxidant toughening modified polyphenyl thioether section raw material, can improve well the compatibility of each component of system, promote plasticizing, in carrying out the process of melting, section reduces melt viscosity, improve processing fluidity, reduce the thickener phenomenon, enhance productivity, and can improve shock strength and the elongation at break of polyphenylene sulfide filaments, improve simultaneously product surface gloss.
Described antioxidant toughening modified polyphenyl thioether monofilament preparation method specifically may further comprise the steps:
The preparation of S100, the section of antioxidant toughening modified polyphenyl thioether:
S101, in the former powder of PPS, add antioxidant, flexibilizer and dispersion coupling agent, in high-speed mixer, mix; Wherein, because the mixed at high speed heat release can make material temperature raise and play certain desiccation;
S102, the former powder of the PPS that mixes is extruded the tie rod pelletizing by double screw extruder make antioxidant toughening modified polyphenyl thioether section, for spinning production PPS monofilament.
The preparation of S200, antioxidant toughening modified polyphenyl thioether monofilament:
Dry before S201, the melting: as in vacuum drum or pre-crystallized drying equipment, anti-oxidant toughening modifying polyphenylene sulfide slice to be carried out drying;
S202, melt spinning: high-temperature fusion is carried out in the section of antioxidant toughening modified polyphenyl thioether extrude in screw extruder, melt enters filament spinning component after the measuring pump metering, form certain pressure and evenly sprayed by the porous spinneret orifice on the spinnerets in filament spinning component;
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 enter the water-bath drawing-off and carry out the first drawing-off through oiling roller, carries out the drawing-off of second hot-air again, carries out the hot-air typing, then is wound into antioxidant toughening modified polyphenyl thioether monofilament finished product.
Described antioxidant toughening modified polyphenyl thioether monofilament 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 at screw rod and produce putty in the process, cause pressure oscillation, hydrolysis and the situation such as crosslinked.Dry run before the described melting is preferably polyphenylene sulfide slice is dried to moisture content≤80PPM.
In described melt spinning process, melt temperature is 290 ~ 350 ℃.0.5 ~ 2.5mm is selected in the aperture of described spinneret orifice, 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.
Described melt cooling is that 6 ~ 15cm place arranges 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 easily causes of the mistake of described bath temperature is even, forms skin-core structure, and excess Temperature then cooling effect is bad.
The drafting forming process of described 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, first is drawing-off in water-bath, and drawing temperature is 80 ~ 98 ℃, and drafting multiple accounts for 70 ~ 97% of general times; The second drawing-off is carried out in hot-air, and drawing temperature is 150 ~ 220 ℃, and drafting multiple accounts for 3 ~ 30% of general times.Described 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 antioxidant toughening MODIFIED PP S 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%.Described antioxidant toughening modified polyphenyl thioether monofilament 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 the section of antioxidant toughening modified polyphenyl thioether by following prescription:
The former powder of PPS: 96%
Antioxidant AO1179:0.2%
Antioxidant AO110:0.2%
Nanometer grade calcium carbonate: 2.6%
Disperse coupling agent EK602:1%
The preparation of antioxidant toughening modified polyphenyl thioether section: 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 made the section of antioxidant toughening modified polyphenyl thioether, produces the PPS monofilament for spinning.
The preparation of antioxidant toughening modified polyphenyl thioether monofilament: 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 ginseng are shown in 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 the section of antioxidant toughening modified polyphenyl thioether by following prescription:
The former powder of PPS: 95.8%
Antioxidant AO1179:0.3%
Nanometer grade calcium carbonate: 2.9%
Disperse coupling agent EK602:1%
The preparation of antioxidant toughening modified polyphenyl thioether section: 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 made the section of antioxidant toughening modified polyphenyl thioether, produces the PPS monofilament for spinning.
The preparation of antioxidant toughening modified polyphenyl thioether monofilament: 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 ginseng are shown in 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 the section of antioxidant toughening modified polyphenyl thioether by following prescription:
The former powder of PPS: 97%
Antioxidant AO110:0.3%
Nanometer grade calcium carbonate: 1%
Disperse coupling agent EK602:1.7%
The preparation of antioxidant toughening modified polyphenyl thioether section: 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 made the section of antioxidant toughening modified polyphenyl thioether, produces the PPS monofilament for spinning.
The preparation of antioxidant toughening modified polyphenyl thioether monofilament: 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 ginseng are shown in 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 winding condition and physical index are shown in 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 the section of antioxidant toughening modified polyphenyl thioether by following prescription:
The former powder of PPS: 95%
Antioxidant AO1179:0.3%
Antioxidant AO110:0.3%
Nanometer grade calcium carbonate: 2%
Disperse coupling agent EK602:1.4%
The preparation of antioxidant toughening modified polyphenyl thioether section: 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 made the section of antioxidant toughening modified polyphenyl thioether, produces the PPS monofilament for spinning.
The preparation of antioxidant toughening modified polyphenyl thioether monofilament: 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 ginseng are shown in 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 the section of antioxidant toughening modified polyphenyl thioether by following prescription:
The former powder of PPS: 96.1%
Antioxidant AO110:0.3%
Nanometer grade calcium carbonate: 2.6%
Disperse coupling agent EK602:1%
The preparation of antioxidant toughening modified polyphenyl thioether section: 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 made the section of antioxidant toughening modified polyphenyl thioether, produces the PPS monofilament for spinning.
The preparation of antioxidant toughening modified polyphenyl thioether monofilament: 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 ginseng are shown in 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 the section of antioxidant toughening modified polyphenyl thioether by following prescription:
The former powder of PPS: 96.1%
Antioxidant AO1179:0.3%
Nanometer grade calcium carbonate: 2.6%
Disperse coupling agent EK602:1%
The preparation of antioxidant toughening modified polyphenyl thioether section: 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 made the section of antioxidant toughening modified polyphenyl thioether, produces the PPS monofilament for spinning.
The preparation of antioxidant toughening modified polyphenyl thioether monofilament: 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 ginseng are shown in 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 physical property 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, weighs qualitatively with the size of loss of strength.
The inflexible target of ﹡ initial modulus reflection monofilament also reflects its toughness index conversely, and namely initial modulus is large, and the monofilament rigidity is large, 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 not identical preparation condition, compare with unmodified monofilament according to the preparation-obtained modified polyphenyl thioether monofilament 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 again better antioxygenic property and toughness simultaneously.
Should be understood that, application of the present invention is not limited to above-mentioned giving an example, and for those of ordinary skills, can be improved according to the above description or conversion, and all these improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (8)
1. the preparation method of an antioxidant toughening modified polyphenyl thioether monofilament, it is characterized in that, described antioxidant toughening modified polyphenyl thioether monofilament preparation method, in the former powder of polyphenylene sulfide, to add antioxidant, inorganic flexibilizer and disperse coupling agent, make the section of antioxidant toughening modified polyphenyl thioether, carry out again melt spinning;
Wherein, described antioxidant toughening modified polyphenyl thioether section 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 former powder of described polyphenylene sulfide is the polymer of linear structure, wherein
Construction unit content 〉=70% mol/mol, melt index are 20 ~ 300g/10min;
Described antioxidant is comprised of among antioxidant AO1179 or the antioxidant AO110 one or both;
Described inorganic flexibilizer is nanometer grade calcium carbonate;
Described dispersion coupling agent is end amino polybasic alcohol ester.
2. the preparation method of antioxidant toughening modified polyphenyl thioether monofilament according to claim 1 is characterized in that, described antioxidant toughening modified polyphenyl thioether monofilament preparation method specifically may further comprise the steps:
The preparation of S100, the section of antioxidant toughening modified polyphenyl thioether:
S101, in the former powder of polyphenylene sulfide, add antioxidant, inorganic flexibilizer and disperse coupling agent, mix;
S102, antioxidant toughening modified polyphenyl thioether section is made in the pelletizing of the former powder tie rod of the polyphenylene sulfide that mixes;
The preparation of S200, antioxidant toughening modified polyphenyl thioether monofilament:
S202, melt spinning: high-temperature fusion is carried out in the section of antioxidant toughening modified polyphenyl thioether, and melt enters filament spinning component, is sprayed by the spinneret orifice on the spinnerets in filament spinning component;
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 laggardly enters the water-bath drawing-off and carries out the first drawing-off through oiling; Carry out the drawing-off of second hot-air; Carry out the hot-air typing; Be wound into antioxidant toughening modified polyphenyl thioether monofilament finished product.
3. the preparation method of antioxidant toughening modified polyphenyl thioether monofilament according to claim 2 is characterized in that, and is before described step S202, further comprising the steps of:
Dry before S201, the melting: as in vacuum drum or pre-crystallized 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 antioxidant toughening modified polyphenyl thioether monofilament 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 described spinneret orifice, and draw ratio L/D is 3.0 ~ 10.0.
5. the preparation method of antioxidant toughening modified polyphenyl thioether monofilament according to claim 2, it is characterized in that, melt cooling described in the step S203 is that 6 ~ 15cm place arranges a bosh below being positioned at described spinnerets, and to melt thread water inlet cooling, bath temperature is controlled at 30 ~ 80 ℃.
6. the preparation method of antioxidant toughening modified polyphenyl thioether monofilament according to claim 2 is characterized in that, among the step S204, described monfil total draft multiple is 2.5 ~ 10.0 times.
7. the preparation method of antioxidant toughening modified polyphenyl thioether monofilament according to claim 2 is characterized in that, among the step S204, the drawing temperature of described first drawing-off is 80 ~ 98 ℃, and drafting multiple accounts for 70 ~ 97% of general times; The drawing temperature of described second hot-air drawing-off is 150 ~ 220 ℃, and drafting multiple accounts for 3 ~ 30% of general times; The temperature of described hot-air typing is 180 ~ 280 ℃, and winding speed is 100 ~ 200m/min.
8. an antioxidant toughening modified polyphenyl thioether monofilament that adopts the arbitrary described preparation method of claim 1 ~ 7 to obtain is characterized in that, the diameter of described antioxidant toughening modified polyphenyl thioether monofilament is at 0.2 ~ 0.7mm.
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| CN102776601B (en) * | 2012-08-16 | 2013-06-19 | 敦煌西域特种新材股份有限公司 | Polyphenylene sulfide fiber spinning technology |
| CN103556297B (en) * | 2013-10-17 | 2015-12-02 | 绍兴文理学院 | The preparation method of the coloured PPS long filament of high anti-oxidation |
| CN104195669B (en) * | 2014-09-15 | 2016-01-20 | 马海燕 | Large-diameter polyphenylene sulfide monofilament and production method thereof |
| CN108360085B (en) * | 2018-01-12 | 2021-02-26 | 安徽工程大学 | Polyphenylene sulfide antioxidant fiber based on layered nanoparticles and preparation method thereof |
| KR20210060458A (en) * | 2018-09-27 | 2021-05-26 | 도레이 카부시키가이샤 | 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 |
| 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 |
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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 |
| 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 |
| 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 |
| 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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