CN104451937A - Antifouling, flame retardant and anti-dripping multifunctional copolyester fibers and preparation method thereof - Google Patents
Antifouling, flame retardant and anti-dripping multifunctional copolyester fibers and preparation method thereof Download PDFInfo
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- CN104451937A CN104451937A CN201410767791.0A CN201410767791A CN104451937A CN 104451937 A CN104451937 A CN 104451937A CN 201410767791 A CN201410767791 A CN 201410767791A CN 104451937 A CN104451937 A CN 104451937A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 91
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 87
- 239000000835 fiber Substances 0.000 title claims abstract description 70
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 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 title abstract description 21
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 132
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 121
- 229920000728 polyester Polymers 0.000 claims abstract description 103
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000005886 esterification reaction Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 4
- 238000009987 spinning Methods 0.000 claims description 45
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 230000032050 esterification Effects 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 11
- 238000007664 blowing Methods 0.000 claims description 7
- 239000012530 fluid Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 22
- 239000011737 fluorine Substances 0.000 abstract description 21
- 238000002074 melt spinning Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 6
- 239000004753 textile Substances 0.000 abstract description 4
- 239000000155 melt Substances 0.000 abstract 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 238000010036 direct spinning Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 20
- 230000002209 hydrophobic effect Effects 0.000 description 9
- 238000007334 copolymerization reaction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000005020 polyethylene terephthalate Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000004744 fabric Substances 0.000 description 7
- 238000006068 polycondensation reaction Methods 0.000 description 7
- -1 polyethylene terephthalate Polymers 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
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- 238000006116 polymerization reaction Methods 0.000 description 6
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- 238000000576 coating method Methods 0.000 description 5
- 235000021050 feed intake Nutrition 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- 239000012209 synthetic fiber Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical class ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 description 1
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004044 disperse dyeing Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 230000001343 mnemonic effect Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000005365 phosphate glass Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Artificial Filaments (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses antifouling, flame retardant and anti-dripping multifunctional copolyester fibers and a preparation method thereof. Copolyester masterbatches with high content of fluorine and the antifouling, flame retardant and anti-dripping functions are prepared by using terephthalic acid, ethylene glycol and hexafluoropropylene oxide as raw materials, subjecting hexafluoropropylene oxide to ring-opening reaction and then subjecting hexafluoropropylene oxide subjected to ring-opening reaction and terephthalic acid to low temperature reaction, and then carrying out high temperature esterification reaction. The antifouling, flame retardant and anti-dripping multifunctional copolyester fibers are prepared by controlling the melt flow and the online addition flow by adopting a melt direct spinning addition method after drying the copolyester masterbatches, melt-spinning and forming a melt with a profiled spinneret and carrying out cooling, drafting and stretching processes. The prepared antifouling and flame retardant polyester fibers have hydrophobicity and lipophilicity, are unnecessary to be oiled in the preparation process, have excellent flame retardance and antifouling and anti-dripping properties and have extensive prospects in the field of home textiles.
Description
Technical field
The present invention relates to multi-functional copolyester fiber of a kind of antifouling fire-retardant anti-molten droplet and preparation method thereof, belong to multifunctional polyester modification field.
Background technology
Polyester fiber by the polyester of organic dibasic acid and dihydroxylic alcohols polycondensation, then through the synthetic fiber of melt spinning gained.Usual polyester fiber refers to the fiber of polyethylene terephthalate spinning, and Chinese commodity is called terylene, is the first kind of synthetic fiber at present.Polyester fiber has the excellent properties such as high-strength, Gao Mo, shape-retaining ability are good, DIMENSIONAL STABILITY is high, is widely used in each fields such as clothes, decoration, industrial or agricultural.The output of Chinese polyester fiber in 2012 is to reach 3,200 ten thousand tons, but because product homogeneity phenomenon is serious, added value of product is not high, many enterprises are all faced with the difficult predicament that goes into operation, therefore exploitation has the polyester fiber of high added value to the market competitiveness improving enterprise, and the predicament reversing polyester enterprise difficult at present has profound significance.Simultaneously along with growth in the living standard, people propose requirements at the higher level to taking fiber, with from traditional warming be pursuit for what wear that object develops into today with fashion, health, safety etc.Except in the field of taking, spin the comfortable security polyester product in field in automotive trim product, family and all have and apply very widely.Therefore the polyester fiber new product developed around comfortable and safe property is needing of further developing of polyester is also the demand that Market Consumer increases day by day.
In the preparation research of antifouling flame retardant polyester, Chinese scholars and structure have expanded relevant research.McCarthy etc. utilize the method for plasma polymerization, prepare seven perfluoroalkyl acrylate ester films (Chen W, Fadeev A Y, McCarthy T J, et al.Langmuir, 1999,15:3395-3399) on the surface in polyethylene terephthalate; Young-Yeon Ji etc. utilizes plasma polymerisation process, carry hexamethyldisiloxane siloxanes (HMDSO) with argon gas and apply polyester fiber, obtain hydrophobic surface (Young-Yeon Ji, Yong-CheolHong, Suck-Hyun Lee, Sung-Dae Kim, Sang-SikKim.Surface & Coatings Technology.202 (2008) 5663-5667).AshrafM etc. are by regulating and controlling hydrophily and the hydrophobicity of fabric at polyester textile surface coating zinc oxide nano rod.(AshrafM，Campagne C，Perwuelz A，et al.Developmentof superhydrophilic and superhydrophobic polyester fabric by growing Zinc Oxidenanorods[J].Journal ofcolloid and interface science，2013，394：545-553)。Chinese patent " a kind of preparation method of polyester fiber antibacterial hydrophobic complexing agent " (application number CN 201310027956) has first synthesized a kind of polyester fiber antibacterial hydrophobic complexing agent, again complexing agent is incorporated in polyester molecule chain by the means of copolymerization, thus gives copolyesters antibacterial hydrophobic performance.The preparation method that " a kind of preparation method of high-hydrophobic polyester " (application number CN 201010611582) relates to a kind of high-hydrophobic polyester and the high-hydrophobic polyester with the micro-nano stratum composite construction of similar lotus leaf prepared, adopt crystallization of the dissolution and precipitation legal system for the preparation method of high-hydrophobic polyester.Patent " method of endowing polyester fiber with hydrophobic function " (application number CN200810208040) adds man-hour in disperse dyeing, what polyester fiber thing was soaked in the dihalo compound in triazine class and polynary amino-compound with hydrophilic and dye liquor coexists in solution, through dipping repeatedly and high-temperature heat treatment, the hydrophobic polyester fiber of final preparation.In the research of fire-retardant anti-molten droplet polyester, same Chinese scholars has done a large amount of work:
In fire-retardant polyester fibre research, at present research the most extensively and industrialized be utilize phosphorus flame retardant.Aromatic binary carboxylic acid, dihydroxylic alcohols and phosphonium flame retardant mix by Chinese patent " a kind of preparation method of inflame-retardant anti-dripping polyester composite fibers " (application number CN102277653 B), add catalyst and heat stabilizer simultaneously, react and obtain flame-proof copolyester, copolyesters and phosphate glass blended and namely obtain inflame-retardant anti-dripping polyester composite fibers through melt spinning.2-carboxyethyl phenyl phosphinic acid (CEPPA) or hydroxymethyl phenyl hypophosphorous acid (HMPPA) directly add in polyester raw material terephthalic acid (TPA) and ethylene glycol mixed slurry by " a kind of preparation method of fire retardant co-polymerization modified polyester " (application number CN102020766 A), enter production of polyester system, generate modified flame-retardant polyester through esterification, polymerization.Phosphorus flame retardant has high effect nontoxic, be main mainly with CEPPA class from research report, but the dissymmetrical structure of CEPPA molecule two terminal hydroxy group and carboxyl, and end carboxyl free in polymerization process is difficult to occur further esterification, therefore the CEPPA added has a strong impact on polyester degree, is difficult to the production requirement meeting high content of phosphorus fused mass directly spinning polyester fiber.
According to the above report preparing pertinent literature and patent around antifouling fire-retardant anti-molten droplet function copolyesters, following method can be generalized into: (1) has finishing agent that is antifouling, flame-retarding characteristic to the fiber of polyester melt spinning moulding or fabric coating.This method to be coated on polyester textile thus to give the functional of fabric by finishing agent, from implementing process, in order to improve the load of finishing agent at fabric face, needs through techniques such as dipping heating repeatedly, complex operation, inefficiency.Simultaneously this method makes the style sclerosis of fiber strengthen, and then the physical friction caused due to the kneading action of washing etc. also easily makes resin involucra peel off, thus durability is still restricted; (2) conventionally by with there is antifouling, fire retardant carry out blended thus realize the antifouling anti-flaming function of polyester.Relate to functional agglomerate to relate to and preparation, had higher requirement in the modified high-efficient of master batch, heat endurance, the aspect such as comixing compatibility and fibre forming property.(3) antifouling fire-retardant anti-molten droplet copolyesters is prepared by introducing fire-retardant or antifouling modified component in polymerization with the form of combined polymerization, these class methods carry out design modification from polyester molecule chemistry level, can give permanent hydrophobic, the oleophobic of polyester fiber and flame-retarding characteristic.This method is especially applicable to the polyester process systems at present based on fused mass directly spinning simultaneously, has the feature that efficiency is high, cost is low.Process for copolymerization is prepared antifouling fire-retardant anti-molten droplet polyester key and is that the copolyesters sequential structure that the modified component introduced prepares is controlled, has good fibre forming property.
In addition in these reports to study antifouling or fire-retardant a certain item performance, have concurrently antifouling less with flame-retardant and anti-dripping characteristic to the polyester of preparation, this key factor is introduced in polyester in multicomponent, and the fibre forming property of polyester is subject to larger impact; Cooperative effect between the modified component introduced is indefinite, and modification lacks high efficiency, easily causes modification cost significantly to improve.
Summary of the invention
Problem to be solved by this invention is to provide the multi-functional copolyester fiber of a kind of antifouling fire-retardant anti-molten droplet makes polyester have hydrophobic, fuel shedding quality, improves polyester resistance to soiling, anti-flammability.
In order to solve the problem, the invention provides the preparation method of the multi-functional copolyesters of a kind of antifouling fire-retardant anti-molten droplet, it is characterized in that, raw material adopts terephthalic acid (TPA), ethylene glycol, hexafluoropropylene oxide, first being passed in ethylene glycol solution by hexafluoropropylene oxide gas makes hexafluoropropylene oxide first carry out ring-opening reaction, then mix with terephthalic acid (TPA) terephthalic acid (TPA), esterification is carried out by the hexafluoropropylene oxide of terephthalic acid (TPA) and ethylene glycol and open loop under first step pressurized conditions, second step is first being heated, precondensation is carried out under normal pressure, heating again, finishing reaction is carried out under vacuum condition, prepare and antifoulingly fire-retardantly put the multi-functional copolyesters of molten drop.
Preferably, described hexafluoropropylene oxide and glycol reaction temperature are 15 ~ 45 DEG C, and it is 0.5h ~ 3.0h that hexafluoropropylene oxide passes into time controling.
Preferably, the mol ratio of described terephthalic acid (TPA) and ethylene glycol is 1: 1.25 ~ 1.67, and the mol ratio of ethylene glycol and hexafluoropropylene oxide is 1: 0.05 ~ 1: 0.20.
Preferably, the reaction condition of the esterification of the described first step is: under nitrogen protection, and pressure is 0.5 ~ 0.8MPa, and reaction temperature is 160 ~ 185 DEG C, and the reaction time is 6 ~ 10h.
Preferably, the reaction condition of the prepolymerization reaction of described second step is: reaction temperature is 260 ~ 280 DEG C, and the reaction time is 4 ~ 6h.
Preferably, the reaction condition of the finishing reaction of described second step is: low vacuum is in 60Pa, and reaction temperature is 270 ~ 290 DEG C, and the reaction time is 3 ~ 5h.
Present invention also offers the preparation method of the multi-functional copolyester fiber of a kind of antifouling fire-retardant anti-molten droplet, it is characterized in that, adopt the above-mentioned antifouling fire-retardant multi-functional copolyesters of molten drop of putting as master batch, adopt the method that fused mass directly spinning adds online, take normal polyester as pipeline melt, added to by master batch in online adding set, control melt flow and add flow online, melt prepares antifouling fire-retardant polyester fibre again after profile spinneret spinning technique, cooling, drawing-off and 1 ~ 3 times of stretching.
Preferably, described antifouling fire-retardant put the multi-functional copolyesters of molten drop before use must at 120 DEG C dry 24h.
Preferably, the mass ratio of described master batch and normal polyester is 1: 0.5 ~ 20, and the inherent viscosity of the multi-functional copolyesters master batch of described antifouling fire-retardant anti-molten droplet is 0.56 ~ 0.65dL/g.
Preferably, the cross sectional shape of described abnormal-shape spinneret plate is for being hollow, U-shaped, cross, 8 fonts or yi word pattern.
Preferably, the technological parameter in described spinning process is: in fused mass directly spinning, pipeline fluid flow and online adding set flow ratio are 1: 0.5 ~ 20; Spinning temperature is 260 ~ 290 DEG C; POY spinning speed is 3000 ~ 4000m/min; Lateral blowing temperature is 26 ~ 28 DEG C; Air-supply relative humidity is 70 ~ 80%; Wind speed is 0.4 ~ 0.5m/s.
The multi-functional copolyester fiber of above-mentioned antifouling fire-retardant anti-molten droplet, is characterized in that, the multi-functional copolyester fiber surface energy of described antifouling fire-retardant anti-molten droplet is not more than 24mJ/cm
2, limited oxygen index is not less than 32, and fracture strength is not less than 2.8cN/dtex, and elongation at break is not less than 15%.
Preferably, the cross section of described antifouling fire-retardant polyester fibre is hollow, U-shaped, cross, 8 fonts or yi word pattern.
Compared with prior art, feature of the present invention is:
The present invention prepares antifouling fire-retardant anti-molten droplet function copolyester fiber with fluorine-containing polyester master particle through online mode of adding spinning, develop reaction by high activity hexafluoropropylene oxide and terephthalic acid (TPA) and prepare high reaction activity functional fluoropolymer monomer, for modification by copolymerization, polycondensation is carried out by functional fluoropolymer monomer and ethylene glycol, polyester backbone is introduced fluorine-containing hydrophobic comb oil and fire-retardant segment, improve polyester hydro-oleophobicity and fire resistance, give hydrophobic oleophobic and the fire resistance of polyester master particle excellence; Adopt online mode of adding the spinning after melt blending of fluorine-containing polyester master particle simultaneously, because the difficulty combustion characteristic of fluorocarbon material itself makes material have excellent fire resistance, simultaneously fluorine atom is uniformly distributed in polyester segment, the copolyester fiber of preparation is had be difficult to the antifouling property of molten drop and fluorine material low-surface-energy; The HFC-236fa base simultaneously introduced in fluorine-containing polyester master particle molecule has similar polytrimethylene terephthalate structure, and molecular structure has soft and mnemonic energy; And adopt the method for copolymerization to make fluoro-containing group grafting on polyester backbone, avoid fluorine resin and polyester blend is difficult to compatible problem, prepared fluorine-containing antifouling flame retardant polyester master batch good flame resistance, surface of polyester can be low, the distinguishing features such as excellent performance, the fields such as family is spun, industrial yarn that are applied to have broad application prospects.
Accompanying drawing explanation
Fig. 1 is the reaction equation of antifouling fire-retardant anti-molten droplet provided by the invention multi-functional copolyesters master batch when preparing;
Fig. 2 is the nuclear magnetic resonance of carbon collection of illustrative plates of the multi-functional copolyesters master batch of antifouling fire-retardant anti-molten droplet prepared by embodiment 3.
Detailed description of the invention
For making the present invention become apparent, hereby with preferred embodiment, and accompanying drawing is coordinated to be described in detail below.
The performance test of sample prepared by embodiment 1-5 is the test employing video contact angle instrument of wherein surface energy, and with water, ethylene glycol for surface energy test agent, probe temperature is 25 DEG C, and test sample is antifouling fire-retardant polyester fibre sample; Limited oxygen index test is simultaneously according to GB GB/T2406-1993, and the batten of preparation is made 42cm length can be tested by self-supporting yarn; Characteristic viscosity determining employing mass ratio is phenol and the tetrachloroethanes solution of 1: 1, and adopt full-automatic viscosity determinator, capillary diameter is 1.2mm, measures the inherent viscosity of polyester; Adopt strength of filament tester, according to GB (GB/T 14344-2003) synthetic fiber filament Erichsen test method, brute force and percentage elongation etc. are carried out to the monofilament of antifouling fire-retardant polyester fibre and test.
Embodiment 1
The preparation of the multi-functional copolyesters master batch of the antifouling fire-retardant anti-molten droplet of the first step: be raw material by terephthalic acid (TPA), ethylene glycol, hexafluoropropylene oxide, be 1: 1.67 by the mol ratio of terephthalic acid (TPA) and ethylene glycol, and the mol ratio of ethylene glycol and hexafluoropropylene oxide is 1: 0.20; The first step before this hexafluoropropylene oxide gas mixes in proportion with ethylene glycol, and mixing temperature controls to be 25 DEG C, and it is 2.0h that control hexafluoropropylene oxide gas passes into the time.Then mix with terephthalic acid (TPA) in proportion and feed intake, under monomer protection, esterification system pressure is at 0.8MPa, reaction temperature is at 185 DEG C, and under the condition of reaction 6h, terephthalic acid (TPA) and ethylene glycol react, hexafluoropropylene oxide open loop is simultaneously terephthaldehyde's acid reaction, produces performed polymer; First carry out precondensation at ambient pressure through polycondensation reaction again, reaction temperature, at 280 DEG C, keeps 4h; Then under high temperature, high vacuum condition, carry out aftercondensated, low vacuum is in 60Pa, and reaction temperature is at 270 DEG C, and the reaction time is 5h.Above-mentioned reaction equation as shown in Figure 1.Preparing its surface of polyester of the multi-functional copolyesters of antifouling fire-retardant anti-molten droplet can be 20.1mJ/cm
2, limited oxygen index is 39, and PET conglutination is 0.55dL/g.
The preparation of the multi-functional copolyester fiber of the antifouling fire-retardant anti-molten droplet of second step: by the fluorine-containing antifouling flame retardant polyester master batch of preparation after 120 DEG C of vacuumize 24h, adopt the method that fused mass directly spinning adds online, master batch is added in online adding set, controlling pipeline fluid flow and online adding set flow ratio in fused mass directly spinning is 1: 0.5, adopt melt hollow spinneret plate, then the spinneret melt spinning being hollow shape through spinnerets cross section is shaped, cooling, drawing-off and 2.5 times prepare antifouling fire-retardant polyester fibre after stretching; Preparing its surface energy of antifouling fire-retardant polyester fibre is 20.1mJ/cm
2, limited oxygen index is 37, and fracture strength is 2.8cN/dtex, and elongation at break is 29%.Technological parameter in spinning process is:
Spinning temperature 290 DEG C;
POY spinning speed 4000m/min;
Lateral blowing temperature 28 DEG C;
Air-supply relative humidity 80%;
Wind speed 0.4m/s.
Embodiment 2
The preparation of the multi-functional copolyesters master batch of the antifouling fire-retardant anti-molten droplet of the first step: terephthalic acid (TPA), ethylene glycol, hexafluoropropylene oxide are raw material, be 1: 1.25 by the mol ratio of terephthalic acid (TPA) and ethylene glycol, and the mol ratio of ethylene glycol and hexafluoropropylene oxide is 1: 0.05; The first step before this hexafluoropropylene oxide gas mixes in proportion with ethylene glycol, and mixing temperature controls to be 45 DEG C, and it is 0.5h that control hexafluoropropylene oxide gas passes into the time.Then mix with terephthalic acid (TPA) in proportion and feed intake, under monomer protection, esterification system pressure is at 0.5MPa, reaction temperature is at 160 DEG C, and under the condition of reaction 10h, terephthalic acid (TPA) and ethylene glycol react, hexafluoropropylene oxide open loop is simultaneously terephthaldehyde's acid reaction, produces performed polymer; First carry out precondensation at ambient pressure through polycondensation reaction again, reaction temperature, at 260 DEG C, keeps 6h; Then under high temperature, high vacuum condition, carry out aftercondensated, low vacuum is in 60Pa, and reaction temperature is at 290 DEG C, and the reaction time is 3h.Above-mentioned reaction equation as shown in Figure 1.Preparing its surface of polyester of antifouling flame retardant polyester can be 24.0mJ/cm
2, limited oxygen index 36, PET conglutination 0.65dL/g.
The preparation of the multi-functional copolyester fiber of the antifouling fire-retardant anti-molten droplet of second step: by the fluorine-containing antifouling flame retardant polyester master batch of preparation after 120 DEG C of vacuumize 24h, adopt the method that fused mass directly spinning adds online, master batch is added in online adding set, controlling pipeline fluid flow and online adding set flow ratio in fused mass directly spinning is 1: 20, adopt 8 font spinneretss, then prepare antifouling fire-retardant polyester fibre after spinneret melt spinning shaping, cooling, drawing-off and 1 times of stretching; Preparing its surface energy of antifouling fire-retardant polyester fibre is 25.0mJ/cm
2, limited oxygen index is 33, and fracture strength is 3.5cN/dtex, and elongation at break is 20%.Technological parameter in spinning process is:
Spinning temperature 260 DEG C;
POY spinning speed 3000m/min;
Lateral blowing temperature 26 DEG C;
Air-supply relative humidity 70%;
Wind speed 0.5m/s.
Embodiment 3
The preparation of the multi-functional copolyesters master batch of the antifouling fire-retardant anti-molten droplet of the first step: be raw material by terephthalic acid (TPA), ethylene glycol, hexafluoropropylene oxide, be 1: 1.5 by the mol ratio of terephthalic acid (TPA) and ethylene glycol, and the mol ratio of ethylene glycol and hexafluoropropylene oxide is 1: 0.10; The first step before this hexafluoropropylene oxide gas mixes in proportion with ethylene glycol, and mixing temperature controls to be 45 DEG C, and it is 1.0h that control hexafluoropropylene oxide gas passes into the time.Then mix with terephthalic acid (TPA) in proportion and feed intake, under monomer protection, esterification system pressure is at 0.7MPa, reaction temperature is at 165 DEG C, and under the condition of reaction 8h, terephthalic acid (TPA) and ethylene glycol react, hexafluoropropylene oxide open loop is simultaneously terephthaldehyde's acid reaction, produces performed polymer; First carry out precondensation at ambient pressure through polycondensation reaction again, reaction temperature, at 280 DEG C, keeps 6h; Then under high temperature, high vacuum condition, carry out aftercondensated, low vacuum is in 60Pa, and reaction temperature is at 290 DEG C, and the reaction time is 4h.Above-mentioned reaction equation as shown in Figure 1.Prepare its surface of polyester energy of antifouling flame retardant polyester 22.0mJ/cm
2, limited oxygen index 38, PET conglutination 0.60dL/g.
The preparation of the multi-functional copolyester fiber of the antifouling fire-retardant anti-molten droplet of second step: by described prepared fluorine-containing antifouling flame retardant polyester master batch after 120 DEG C of vacuumize 24h, adopt the method that fused mass directly spinning adds online, master batch is added in online adding set, controlling pipeline fluid flow and online adding set flow ratio in fused mass directly spinning is 1: 10, adopt melt " ten " font spinnerets, then the spinneret melt spinning be " ten " word shape through spinnerets cross section is shaped, cooling, prepare antifouling fire-retardant polyester fibre after drawing-off and 2.5 times of stretchings; Preparing its surface energy of antifouling fire-retardant polyester fibre is 24.1mJ/cm
2, limited oxygen index is 34, and fracture strength is 3.2cN/dtex, and elongation at break is 23%.Technological parameter in spinning process is:
Spinning temperature 285 DEG C;
POY spinning speed 3500m/min;
Lateral blowing temperature 28 DEG C;
Air-supply relative humidity 80%;
Wind speed 0.5m/s.
Fig. 2 be the arrangement of its all kinds of carbon atom of nuclear magnetic resonance of carbon collection of illustrative plates of the antifouling fire-retardant anti-molten droplet multi-functional copolyesters master batch of above-mentioned preparation as shown in FIG., and the chemical shift that in collection of illustrative plates, e (δ=129.3ppm), d (δ=111.2ppm) and f (δ=106.0ppm) are corresponding illustrates that in hexafluoropropylene oxide, fluorine-containing functional group take part in copolyreaction, and polymerization in the polymer.
Embodiment 4
The preparation of the multi-functional copolyesters master batch of the antifouling fire-retardant anti-molten droplet of the first step: be raw material by terephthalic acid (TPA), ethylene glycol, hexafluoropropylene oxide, be 1: 1.35 by the mol ratio of terephthalic acid (TPA) and ethylene glycol, and the mol ratio of ethylene glycol and hexafluoropropylene oxide is 1: 0.15; The first step before this hexafluoropropylene oxide gas mixes in proportion with ethylene glycol, and mixing temperature controls to be 25 DEG C, and it is 2.0h that control hexafluoropropylene oxide gas passes into the time.Then mix with terephthalic acid (TPA) in proportion and feed intake, under monomer protection, esterification system pressure is at 0.6MPa, reaction temperature is at 185 DEG C, and under the condition of reaction 7h, terephthalic acid (TPA) and ethylene glycol react, hexafluoropropylene oxide open loop is simultaneously terephthaldehyde's acid reaction, produces performed polymer; First carry out precondensation at ambient pressure through polycondensation reaction again, reaction temperature, at 265 DEG C, keeps 5h; Then under high temperature, high vacuum condition, carry out aftercondensated, low vacuum is in 60Pa, and reaction temperature is at 270 DEG C, and the reaction time is 5h.Above-mentioned reaction equation as shown in Figure 1.Prepare its surface of polyester energy of antifouling flame retardant polyester 21.5mJ/cm
2, limited oxygen index 38, PET conglutination is 0.58dL/g.
The preparation of the multi-functional copolyester fiber of the antifouling fire-retardant anti-molten droplet of second step: by prepared fluorine-containing antifouling flame retardant polyester master batch after 120 DEG C of vacuumize 24h, adopt the method that fused mass directly spinning adds online, master batch is added in online adding set, controlling pipeline fluid flow and online adding set flow ratio in fused mass directly spinning is 1: 0.5, adopt " U " font spinnerets, then the spinneret melt spinning be " U " word shape through spinnerets cross section is shaped, cooling, prepare antifouling fire-retardant polyester fibre after drawing-off and 2.5 times of stretchings; Preparing its surface energy of antifouling fire-retardant polyester fibre is 20.1mJ/cm
2, limited oxygen index is 37, and fracture strength is 3.0cN/dtex, and elongation at break is 28%.Technological parameter in spinning process is:
Spinning temperature 290 DEG C;
POY spinning speed 3800m/min;
Lateral blowing temperature 28 DEG C;
Air-supply relative humidity 70%;
Wind speed 0.5m/s.
Embodiment 5
The preparation of the multi-functional copolyesters master batch of the antifouling fire-retardant anti-molten droplet of the first step: be raw material by terephthalic acid (TPA), ethylene glycol, hexafluoropropylene oxide, be 1: 1.5 by the mol ratio of terephthalic acid (TPA) and ethylene glycol, and the mol ratio of ethylene glycol and hexafluoropropylene oxide is 1: 0.20; The first step before this hexafluoropropylene oxide gas mixes in proportion with ethylene glycol, and mixing temperature controls to be 15 DEG C, and it is 3.0h that control hexafluoropropylene oxide gas passes into the time.Then mix with terephthalic acid (TPA) in proportion and feed intake, under monomer protection, esterification system pressure is at 0.8MPa, reaction temperature is at 170 DEG C, and under the condition of reaction 9h, terephthalic acid (TPA) and ethylene glycol react, hexafluoropropylene oxide open loop is simultaneously terephthaldehyde's acid reaction, produces performed polymer; First carry out precondensation at ambient pressure through polycondensation reaction again, reaction temperature, at 260 DEG C, keeps 5.5h; Then under high temperature, high vacuum condition, carry out aftercondensated, low vacuum is in 60Pa, and reaction temperature is at 275 DEG C, and the reaction time is 3.5h.Above-mentioned reaction equation as shown in Figure 1.Preparing its surface of polyester of antifouling flame retardant polyester can be 20.8mJ/cm
2, limited oxygen index is 39, and PET conglutination is 0.56dL/g.
The preparation of the multi-functional copolyester fiber of the antifouling fire-retardant anti-molten droplet of second step: by prepared fluorine-containing antifouling flame retardant polyester master batch after 120 DEG C of vacuumize 24h, adopt the method that fused mass directly spinning adds online, master batch is added in online adding set, controlling pipeline fluid flow and online adding set flow ratio in fused mass directly spinning is 1: 10, adopt melt " one " font spinnerets, then prepare antifouling fire-retardant polyester fibre after spinneret melt spinning shaping, cooling, drawing-off and 2.0 times of stretchings; Preparing its surface energy of antifouling fire-retardant polyester fibre is 23.1mJ/cm
2, limited oxygen index is 34, and fracture strength is 3.3cN/dtex, and elongation at break is 25%.Technological parameter in spinning process:
Spinning temperature 290 DEG C;
POY spinning speed 3800m/min;
Lateral blowing temperature 28 DEG C;
Air-supply relative humidity 70%;
Wind speed 0.5m/s.
Compared with prior art, the invention has the advantages that:
The present invention realizes fluorine-containing comonomer with modification by copolymerization and is introduced in polyester segment, and then prepares antifouling fire-retardant anti-molten droplet function copolyester fiber with fluorine-containing polyester master particle through online mode of adding spinning; By having the high activity hexafluoropropylene oxide can reacted with binary acid, realizing the fluorine-containing functional group introducing low-surface-energy, fire retardation in polyester segment, avoiding fluorocarbon material in prior art and being difficult to the problem such as compatible with conventional polymer such as polyester; Simultaneously online addition manner carries out spinning, has functionalization, differential easy to implement; The multi-functional copolyester fiber of preparation had both improved the fire-retardant of polyester fiber and molten drop problem, gives copolyester fiber simultaneously have excellent low-surface-energy containing fluorine structure.Fluorochemical monomer and resin is adopted to carry out method that is blended and coating relatively at present, because the fluorine-containing functional group of the present invention is that copolymerization is in polyester molecule segment, with the copolyesters of fluorine-containing functional group for master batch, through adding melt spinning online, achieve the compatible of fluorine-containing polyester and normal polyester, therefore can spinning, the fluorine-containing functional group of copolymerization is simultaneously connected in polyester segment, does not therefore move after washing, and few on the feel impact of fabric, and coating processing fabric feeling is poor, flexibility is poor.Process fiber sample according to textiles Washing (GB/T3921-1997), test the fire-retardant of sample and antifouling property after then washing 20 times, result of the test is as shown in table 1.
Performance after the washing of table 1 sample
Claims (13)
1. the preparation method of the multi-functional copolyesters of antifouling fire-retardant anti-molten droplet, it is characterized in that, raw material adopts terephthalic acid (TPA), ethylene glycol, hexafluoropropylene oxide, first being passed in ethylene glycol solution by hexafluoropropylene oxide gas makes hexafluoropropylene oxide first carry out ring-opening reaction, then mix with terephthalic acid (TPA) terephthalic acid (TPA), esterification is carried out by the hexafluoropropylene oxide of terephthalic acid (TPA) and ethylene glycol and open loop under first step pressurized conditions, second step is first being heated, precondensation is carried out under normal pressure, heating again, finishing reaction is carried out under vacuum condition, prepare and antifoulingly fire-retardantly put the multi-functional copolyesters of molten drop.
2. the preparation method of the multi-functional copolyesters of antifouling fire-retardant anti-molten droplet as claimed in claim 1, is characterized in that, described hexafluoropropylene oxide and glycol reaction temperature are 15 ~ 45 DEG C, and it is 0.5h ~ 3.0h that hexafluoropropylene oxide passes into time controling.
3. the preparation method of the multi-functional copolyesters of antifouling fire-retardant anti-molten droplet as claimed in claim 1, it is characterized in that, the mol ratio of described terephthalic acid (TPA) and ethylene glycol is 1: 1.25 ~ 1.67, and the mol ratio of ethylene glycol and hexafluoropropylene oxide is 1: 0.05 ~ 1: 0.20.
4. the preparation method of the multi-functional copolyesters of antifouling fire-retardant anti-molten droplet as claimed in claim 1; it is characterized in that, the reaction condition of the esterification of the described first step is: under nitrogen protection, and pressure is 0.5 ~ 0.8MPa; reaction temperature is 160 ~ 185 DEG C, and the reaction time is 6 ~ 10h.
5. the preparation method of the multi-functional copolyesters of antifouling fire-retardant anti-molten droplet as claimed in claim 1, is characterized in that, the reaction condition of the prepolymerization reaction of described second step is: reaction temperature is 260 ~ 280 DEG C, and the reaction time is 4 ~ 6h.
6. the preparation method of the multi-functional copolyesters of antifouling fire-retardant anti-molten droplet as claimed in claim 1, is characterized in that, the reaction condition of the finishing reaction of described second step is: low vacuum is in 60Pa, and reaction temperature is 270 ~ 290 DEG C, and the reaction time is 3 ~ 5h.
7. the preparation method of the multi-functional copolyester fiber of antifouling fire-retardant anti-molten droplet, it is characterized in that, adopt the antifouling fire-retardant multi-functional copolyesters of molten drop of putting according to claim 1 as master batch, adopt the method that fused mass directly spinning adds online, take normal polyester as pipeline melt, added to by master batch in online adding set, control melt flow and add flow online, melt prepares antifouling fire-retardant polyester fibre again after profile spinneret spinning technique, cooling, drawing-off and 1 ~ 3 times of stretching.
8. the preparation method of the multi-functional copolyester fiber of antifouling fire-retardant anti-molten droplet as claimed in claim 7, is characterized in that, described antifouling fire-retardant put the multi-functional copolyesters of molten drop before use must at 120 DEG C dry 24h.
9. the preparation method of the multi-functional copolyester fiber of antifouling fire-retardant anti-molten droplet as claimed in claim 7, it is characterized in that, the mass ratio of described master batch and normal polyester is 1: 0.5 ~ 20, and the inherent viscosity of the multi-functional copolyesters master batch of described antifouling fire-retardant anti-molten droplet is 0.56 ~ 0.65dL/g.
10. the preparation method of the multi-functional copolyester fiber of antifouling fire-retardant anti-molten droplet as claimed in claim 7, is characterized in that, the cross sectional shape of described abnormal-shape spinneret plate is for being hollow, U-shaped, cross, 8 fonts or yi word pattern.
The preparation method of the multi-functional copolyester fiber of 11. antifouling fire-retardant anti-molten droplet as claimed in claim 7, it is characterized in that, the technological parameter in described spinning process is: in fused mass directly spinning, pipeline fluid flow and online adding set flow ratio are 1: 0.5 ~ 20; Spinning temperature is 260 ~ 290 DEG C; POY spinning speed is 3000 ~ 4000m/min; Lateral blowing temperature is 26 ~ 28 DEG C; Air-supply relative humidity is 70 ~ 80%; Wind speed is 0.4 ~ 0.5m/s.
The multi-functional copolyester fiber of 12. antifouling fire-retardant anti-molten droplet according to claim 7, is characterized in that, the multi-functional copolyester fiber surface energy of described antifouling fire-retardant anti-molten droplet is not more than 24mJ/cm
2, limited oxygen index is not less than 32, and fracture strength is not less than 2.8cN/dtex, and elongation at break is not less than 15%.
The multi-functional copolyester fiber of 13. antifouling fire-retardant anti-molten droplet as claimed in claim 12, is characterized in that, the cross section of described antifouling fire-retardant polyester fibre is hollow, U-shaped, cross, 8 fonts or yi word pattern.
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Effective date of registration: 20210521 Address after: Room 1115, Zhongfu building, 99 Jianguo Road, Chaoyang District, Beijing 100020 Patentee after: HI-TECH FIBER Group Corp. Patentee after: DONGHUA University Address before: 315336 Binhai 4th Road, Hangzhou Bay New Area, Cixi City, Ningbo City, Zhejiang Province Patentee before: HENGTIAN BIO-BASED MATERIALS ENGINEERING TECHNOLOGY (NINGBO) Co.,Ltd. Patentee before: DONGHUA University |