CN103469336A - Fluorine-containing polytrimethylene terephthalate (PTT) polyester polyester pre-oriented yarn (POY) fibers and preparation method thereof - Google Patents
Fluorine-containing polytrimethylene terephthalate (PTT) polyester polyester pre-oriented yarn (POY) fibers and preparation method thereof Download PDFInfo
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- CN103469336A CN103469336A CN201310447068XA CN201310447068A CN103469336A CN 103469336 A CN103469336 A CN 103469336A CN 201310447068X A CN201310447068X A CN 201310447068XA CN 201310447068 A CN201310447068 A CN 201310447068A CN 103469336 A CN103469336 A CN 103469336A
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- fluorine
- ptt polyester
- containing ptt
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- polyester
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- 229920000728 polyester Polymers 0.000 title claims abstract description 178
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 165
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 239000011737 fluorine Substances 0.000 title claims abstract description 157
- 239000000835 fiber Substances 0.000 title claims abstract description 120
- 229920002215 polytrimethylene terephthalate Polymers 0.000 title claims abstract description 106
- -1 polytrimethylene terephthalate Polymers 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- WFNRNCNCXRGUKN-UHFFFAOYSA-N 2,3,5,6-tetrafluoroterephthalic acid Chemical compound OC(=O)C1=C(F)C(F)=C(C(O)=O)C(F)=C1F WFNRNCNCXRGUKN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000001816 cooling Methods 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000003112 inhibitor Substances 0.000 claims abstract description 10
- 238000006068 polycondensation reaction Methods 0.000 claims description 110
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 104
- 230000032050 esterification Effects 0.000 claims description 100
- 238000005886 esterification reaction Methods 0.000 claims description 100
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 229920000570 polyether Polymers 0.000 claims description 40
- 239000002253 acid Substances 0.000 claims description 32
- 239000003921 oil Substances 0.000 claims description 32
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 25
- 230000035484 reaction time Effects 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- 150000002148 esters Chemical class 0.000 claims description 20
- 239000002202 Polyethylene glycol Substances 0.000 claims description 19
- 229920001223 polyethylene glycol Polymers 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 17
- 239000003381 stabilizer Substances 0.000 claims description 16
- 229910019142 PO4 Inorganic materials 0.000 claims description 14
- 239000010452 phosphate Substances 0.000 claims description 14
- 239000000839 emulsion Substances 0.000 claims description 12
- 239000011654 magnesium acetate Substances 0.000 claims description 12
- 229940069446 magnesium acetate Drugs 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- 238000004513 sizing Methods 0.000 claims description 12
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 9
- QZRMKGRPCTVXBS-UHFFFAOYSA-N 2,6,8-trimethylnonan-4-yl dihydrogen phosphate Chemical compound CC(C)CC(C)CC(CC(C)C)OP(O)(O)=O QZRMKGRPCTVXBS-UHFFFAOYSA-N 0.000 claims description 9
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 9
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000005642 Oleic acid Substances 0.000 claims description 9
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 9
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 9
- 239000001103 potassium chloride Substances 0.000 claims description 9
- 235000011164 potassium chloride Nutrition 0.000 claims description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 claims description 8
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- 229940070765 laurate Drugs 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims description 7
- 238000007664 blowing Methods 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 7
- 230000000171 quenching effect Effects 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 6
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 5
- BINACNSGGVXHDR-UHFFFAOYSA-N 1,1,1,2,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoro-3-(1,1,2,2,2-pentafluoroethyl)non-2-ene Chemical group C(=C(C(F)(F)F)F)(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)C(C(F)(F)F)(F)F BINACNSGGVXHDR-UHFFFAOYSA-N 0.000 claims description 4
- CRTKHIYQIPONDX-UHFFFAOYSA-N FC(C(C(F)(F)F)(F)F)(C(C(C(C(F)(F)F)(F)F)=C(C(F)(F)F)F)(F)F)F Chemical group FC(C(C(F)(F)F)(F)F)(C(C(C(C(F)(F)F)(F)F)=C(C(F)(F)F)F)(F)F)F CRTKHIYQIPONDX-UHFFFAOYSA-N 0.000 claims description 4
- 239000005639 Lauric acid Substances 0.000 claims description 4
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 4
- 125000001449 isopropyl group Chemical class [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 4
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical group CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 claims description 3
- TYWMIZZBOVGFOV-UHFFFAOYSA-N tetracosanyl alcohol Natural products CCCCCCCCCCCCCCCCCCCCCCCCO TYWMIZZBOVGFOV-UHFFFAOYSA-N 0.000 claims description 3
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 208000011580 syndromic disease Diseases 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 abstract description 22
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 11
- 230000003373 anti-fouling effect Effects 0.000 abstract description 9
- 230000002209 hydrophobic effect Effects 0.000 abstract description 8
- 230000003075 superhydrophobic effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000004804 winding Methods 0.000 abstract description 2
- 238000001125 extrusion Methods 0.000 abstract 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 19
- 239000000047 product Substances 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 150000001991 dicarboxylic acids Chemical class 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 238000009987 spinning Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 238000005453 pelletization Methods 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 239000004811 fluoropolymer Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 238000009941 weaving Methods 0.000 description 3
- 0 *C(C(C(O)=O)=C(C(F)=C(C1)C(*)=O)F)=C1F Chemical compound *C(C(C(O)=O)=C(C(F)=C(C1)C(*)=O)F)=C1F 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004812 Fluorinated ethylene propylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 229960005082 etohexadiol Drugs 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- LTHCSWBWNVGEFE-UHFFFAOYSA-N octanamide Chemical compound CCCCCCCC(N)=O LTHCSWBWNVGEFE-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920009441 perflouroethylene propylene Polymers 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- 210000004243 sweat Anatomy 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Artificial Filaments (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to fluorine-containing polytrimethylene terephthalate (PTT) polyester polyester pre-oriented yarn (POY) fibers and a preparation method thereof. The preparation method comprises fluorine-containing PTT polyester melt preparation and fluorine-containing PTT polyester POY fiber preparation, and concretely comprises the following steps of 1, adding an inhibitor into tetrafluoroterephthalic acid and 1,3-propylene glycol as raw materials, and preparing the mixture into fluorine-containing PTT polyester melt, and 2, carrying out direct extrusion on the fluorine-containing PTT polyester melt or carrying out slicing and then screw melt extrusion on the slices, and carrying cooling, oil coating and winding to obtain the fluorine-containing PTT polyester POY fibers. The novel fluorine-containing PTT polyester POY fibers have monofilament fineness of 0.5-3.0dtex, fiber breaking strength of 1.8-2.5cN/dtex and breaking elongation of 100-150%. Through use of fluorine atoms, super-hydrophobic, hydrophobic, oleophobic and antifouling performances of the polyester POY fibers are improved. The fluorine-containing PTT polyester POY fibers have a wide application prospect in manufacture of waterproof and antifouling working clothes and special industry working clothes.
Description
Technical field
The present invention relates to a kind of fluorine-containing PTT polyester POY fiber and preparation method thereof, particularly relate to fluorine-containing PTT polyester POY fiber that a kind of benzene ring hydrogen replaced by fluorine and preparation method thereof.
Background technology
Polyester is one of the most widely used synthetic high polymer of the current mankind; just synthesized phthalic acid glycol ester (PET) forties as far back as twentieth century; and find that it has excellent performance, and be widely used in the fields such as weaving, packing, health care, automobile, electronic apparatus, security protection, environmental protection.Pre-oriented yarn POY, refer to unstretched but can directly carry out the precursor of stretcher strain processing, requires the POY silk can long storage time, and have certain structural stability and machinability.The POY silk generally not there will be repiece difficulty, finished silk lousiness, low strength and the uniform situation of stained clot-h in process.It is high around volume speed that its technique has spinning, and the sub-hardness of winding reel is high, weight large, the advantage of cheap transportation; And in spinning process, shelf stability is good, suitable DTY processing.
Polytrimethylene terephthalate (PTT) is a kind of new polyester macromolecular material that has development prospect of new research and development after polyethylene terephthalate (PET) and mutual-phenenyl two acid bromide two alcohol ester (PBT), within 1998, by the U.S., is chosen as one of six large petrochemical industry new products.With PET, PBT, compare, PTT has better elasticity, DIMENSIONAL STABILITY and dyeability etc.There is the multiple good characteristics such as uvioresistant, anti-internal stress, low water absorbable, low static and good biological degradability, reusable edible simultaneously, therefore be widely used in the fields such as carpet industry, dress materials, engineering plastics.
Along with social progress, the raising of living standards of the people, need more and more higher to differential, the functionalization of polyester fiber.Therefore also become particularly important of the modification of polyester, the polyester modification purpose, except the conventional polyester performance is optimized, is mainly to give new polyester differential functional characteristic by modified method.Such as: antistatic, fire-retardant, moisture absorbing and sweat releasing, antifouling deodorization etc.At present, the main new varieties of polyester have: antistatic polyester, high-strength wearable polyester, imitative cotton ultra-soft polyester, super-hydrophobicity polyester, anti-soil polyester etc.
At present, by introduce fluorine atom in polymer, thereby improve the surface property of material, as hydro-oleophobicity and soil resistance etc., and give polyester material various functions.Because fluoropolymer has low-surface-energy, low-friction coefficient and non-adhesiveness usually, the dust dirt such as is difficult to adhere at the characteristic, so the anti-soil ABRASION RESISTANCE of fluoropolymer is good.And current fluoropolymer be take the fluoroolefin base polymer as main (such as polytetrafluoroethylene (PTFE), Kynoar, fluorinated ethylene propylene copolymer, ethylene-tetrafluoroethylene copolymer etc.); The research of fluorochemical urethane, fluorochemical polyether, fluorine-containing polyester etc. relatively lags behind.
Many scholars are studied the fluorochemical modified poly ester, and have obtained certain achievement.The mode of fluorochemical modified poly ester is mainly by adding fluorine-containing end-capping reagent at present, or adds the fluorochemicals such as Fluorinated dihydric alcohol, fluorine-containing binary acid to carry out modified poly ester as the 3rd monomer.Adopt adding of fluorine-containing end-capping reagent in Chinese patent CN101139434A, dimethyl isophthalate and butanediol adopt ester-interchange method, add fluorine-containing end-capping reagent N-ethoxy perfluor caprylamide, have prepared the low and polyester material that the stain resistant performance is good of fluorinated volume.Hu Juan (Hu Juan. the MOLECULE DESIGN of fluorine-containing polyester and photoresist waveguide material and performance study [D]. Master's thesis, Jilin: Jilin University, 2007.) utilize the principle of MOLECULE DESIGN, by adding the mode of Fluorinated dihydric alcohol copolymerization, paraphthaloyl chloride, hexafluoro bisphenol-a and fluorine-containing ethohexadiol ternary polymerization have been synthesized to the polyester of novel high fluorinated volume.This polyester has excellent performance and is applied to optical waveguide material.(the Q Z Zhu such as Qingzeng Zhu, C C Han.Synthesis and crystalization behaviors of highly fluorinated aromatic polyesters[J] .Polymer2007 (48): 3624-3631.) by adding the mode modified poly ester of fluorine-containing binary acid copolymerization, 2,3,4,5-ptfe phthalate modification polyethylene glycol phthalate, the crystal property of polyester improves.
Yet the polyester that these are contained to fluorine element is applied to, in weaving and packaging material, certain limitation is arranged, subject matter is that the molecular weight of polyesters that contains fluorine element of prior art is low, can not meet the requirement of spinning and film forming; Prior art is mainly to give its water proof anti-soil function by the fluorine-containing rear Collator Mode of fabric at present, and the problem such as that the shortcoming of this class methods maximum is to be difficult to solve is ageing, durability and ABRASION RESISTANCE, and waste time and energy.
Therefore, develop fluorine-containing polyester fiber for super-hydrophobic, the hydrophobic and oil repellent of weaving and packaging material, the modification of antifouling property, will there is important theory significance and using value.
Summary of the invention
The invention provides a kind of fluorine-containing PTT polyester POY fiber and preparation method thereof, fluorine-containing PTT polyester POY fiber that particularly provides a kind of benzene ring hydrogen to be replaced by fluorine and preparation method thereof.Fluorine-containing PTT polyester of the present invention has been introduced fluorine atom on the main chain of polymer, therefore can well solve this class problem that wastes time and energy.Fluorine-containing PTT polyester described in the present invention is terephthalic acid (TPA) and the 1,3-PD by contain fluorine atoms on phenyl ring, the fluorine-containing polyester obtained through over-churning and polycondensation.By copolymerization method, polyester is carried out to hydrophobic antifouling modification, can fundamentally solve the problems such as ageing, the durability of hydrophobic antifouling polyester and ABRASION RESISTANCE.
The invention provides following technical scheme:
A kind of fluorine-containing PTT polyester POY fiber, be by fluorine-containing PTT polyester fondant directly extrude or make section through screw rod melt extrude, cooling, oil and coiling makes; Described fluorine-containing PTT polyester, refer to the polytrimethylene terephthalate that the benzene ring hydrogen is replaced by fluorine, is the polytetrafluoro propylene glycol ester terephthalate, and its general structure is
N=70～200 wherein.
A kind of fluorine-containing PTT polyester POY fiber as above, the filament number of described fluorine-containing PTT polyester POY fiber is 0.5～3.0dtex; Fracture strength is 1.8～2.5cN/dtex; Elongation at break is 100～130%.
The present invention also provides a kind of preparation method of fluorine-containing PTT polyester POY fiber, be by fluorine-containing PTT polyester fondant through measuring, extrude, cooling, oil and coiling makes fluorine-containing PTT polyester POY fiber.
The described temperature of extruding is 265～285 ℃;
Described cooling wind-warm syndrome is 20～25 ℃;
The described oil applying rate oiled is 0.42～1.5%;
The speed of described coiling is 2700～3200m/min;
Described lateral blowing or the ring quenching of being cooled to, temperature is 20 ℃～25 ℃, and relative humidity is 65% ± 5%, and wind speed is 0.4～0.8m/s;
The described finish oiled is fluorine-containing polyester POY fiber finish, its component by weight:
Component A: atactic polyether, 50～60 parts;
B component: cithrol, 20～32 parts;
Component C: phosphate kalium salt, 10～15 parts;
Component D: perfluoroalkyl acrylate, 2～5 parts;
The finish preparation method:
By atactic polyether, be heated to 40～60 ℃, cithrol, phosphate kalium salt and perfluoroalkyl acrylate are uniformly mixed, then join in atactic polyether, stir 1～2 hour, obtain fluorine-containing polyester fiber POY finish, finish adds water while using and is made into the emulsion that solid content is 8～10wt%.
Described fluorine-containing polyester POY fiber is with in finish, and component A atactic polyether is smooth agent: this material is a kind of in propylene glycol atactic polyether, butanols atactic polyether, laurate atactic polyether, lauryl alcohol atactic polyether and isomerous tridecanol atactic polyether.The good heat resistance of atactic polyether, be fuming few, and coking is few, and flowing temperature is low, good stability, and coefficient of friction is low, and anti-shear ability is strong, and viscosity coefficient is low, can form the highly stable lubricant film with large absorption affinity and bearing capacity in polyester fibre surface.
Described fluorine-containing polyester POY fiber is with in finish, and the B component cithrol is emulsifying agent: this material is a kind of in polyethylene glycol lauric acid monoester, polyethylene glycol laurate dibasic acid esters, polyethylene glycol oleic acid monoester and polyethylene glycol Glycol Oleic Acid Ester.Oil film that cithrol becomes has the performances such as good surface tension, interfacial tension, penetrability, dispersiveness and emulsibility, its form finish can reduce between silk and silk, thread and metal between quiet/kinetic force of friction, for fluorine-containing polyester fiber provides certain antistatic behaviour, improve convergence.
Described fluorine-containing polyester POY fiber is with in finish, and component C phosphate kalium salt is antistatic additive: this material is a kind of in 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, isomerous tridecanol polyoxyethylene ether phosphate kalium salt and ten tetracosanol phosphate kalium salts.In spinning process, easily produce a large amount of static, the generation that the flatness by fiber surface reduces static content is inadequate, also needs to add the antistatic additive of superior performance.Phosphate kalium salt is a kind of good antistatic additive, it is a kind of anion surfactant, consists of hydrophobic grouping energy and polyester fibre surface combination hydrophobic group and hydrophilic radical, the hydrophilic radical phosphate group upwards, can form the continuous moisture film of " interfacial agent-water ".Can effectively fall low-fiber coefficient of friction, increase the dielectric constant between friction piece, prevent that static from occurring.
Described fluorine-containing polyester POY fiber is with in finish, and component D perfluoroalkyl acrylate is additive: this material is a kind of in perfluoro butyl ethyl propylene acid esters, perfluoro hexyl ethyl propylene acid esters, perfluoro capryl ethyl propylene acid esters, perfluoro butyl ethyl-methyl acrylate, perfluoro hexyl ethyl-methyl acrylate and perfluoro capryl ethyl-methyl acrylate.Its effect is the surface tension that suitably reduces finish, makes it be easy to form uniform continuous oil film.Fluorinated acrylate has lower surface energy, and appropriate interpolation can be lowered the surface tension of finish, makes the wettability of finish and penetrability greatly increase, and is easy to the wetting of fiber and sprawls, and forms uniform oil film.
Described fluorine-containing PTT polyester, refer to the polytrimethylene terephthalate that the benzene ring hydrogen is replaced by fluorine, is the polytetrafluoro propylene glycol ester terephthalate, and its general structure is
N=70～200 wherein.
Described fluorine-containing PTT polyester fondant refers to the fluorine-containing PTT polyester after melting, and the preparation method of described fluorine-containing PTT polyester is divided into esterification and polycondensation reaction two steps; Concrete steps are:
Described esterification:
Adopt tetrafluoro terephthalic acid (TPA) and 1,3-PD as raw material, add inhibitor, carry out esterification after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and pressure is controlled at normal pressure～0.3MPa, and temperature is at 250～260 ℃, and what esterification water quantity of distillate reached theoretical value is the esterification terminal more than 90%;
Described inhibitor is a kind of in magnesia, silica, calcium oxide, zinc oxide and manganese oxide; There is fluorine atom on phenyl ring due to dicarboxylic acids used, the electronegativity of fluorine atom is large, conjugation at esterification stage fluorine atom makes the acidity of dicarboxylic acids strengthen, cause the activity of carboxyl in dicarboxylic acids to increase simultaneously, make reaction speed accelerate, and the reaction speed increase easily makes side reaction produce, these side reaction products have larger impact to follow-up polycondensation reaction, particularly generate the end-blocking product of alkene and aldehyde, restricted the increase of molecular weight of product; From experimental result, if do not add inhibitor, synthetic molecular weight of polyesters is on the low side, can not meet the demand of spinning and film forming; Adding for controlling the speed in esterification stage of inhibitor, reduced side reaction, improved the molecular weight of product, makes and meet spinning requirement.
Usually, it in the polyester esterification process, is the hydrogen ion that ionizes out by the dicarboxylic acids used catalyst as esterification, carry out self-catalyzed reaction, temperature by regulating esterification, pressure and micromolecularly eject the speed of controlling its esterification, however the prerequisite of carrying out esterification is just can carry out esterification under certain reaction temperature and pressure.In the situation that temperature is too low or pressure is inadequate, esterification can not carry out or speed extremely slow, thereby affect follow-up technique.If the little molecule in esterification is failed timely discharge and is easily caused unnecessary side reaction.In building-up process, conjugation due to fluorine, at esterification stage fluorine atom, make the acidity of dicarboxylic acids strengthen, cause the activity of carboxyl in dicarboxylic acids to increase simultaneously, make reaction speed accelerate, side reaction increases, be difficult to control, and then affect the growth of molecular weight of product, thus add inhibitor, by selecting metal oxide used to regulate.Described metal oxide can dissociate by following two kinds of modes:
Here M is metal ion, if the electronegativity of M is quite large, the duplet of oxonium ion is had to stronger attraction, so just can make O-H key weaken, and is conducive to reaction from solution; On the contrary, if the electronegativity of M is little, so just will generate the alkali center.M-O-H is similar with amphoteric compound, and when having alkaline matter to exist, reaction will be undertaken by the mode of acid dissociation; And, when acidic materials exist, by the mode of alkali formula ionization, undertaken.The M-O of back reaction from acid dissociation mode and alkali formula ionization mode
-and M
+visible, M
+as acid centre, its intensity only has direct relation with the electronegativity of metal ion, and M-O
-in the O ion relevant with the negative charge density on oxygen as the intensity at alkali center, negative charge density is larger, intensity is also larger.Negative charge density on visible oxonium ion and metal ion electronegativity have close relationship, and the metal ion electronegativity is less, and negative charge density is just larger.So, the acid and alkalescence of metal oxide has just all connected with the electronegativity of metal ion, and the oxide that the electronegativity of metal ion is large is mainly acid, and what electronegativity was little is alkalescence.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig;
The described polycondensation reaction low vacuum stage, add catalyst and stabilizing agent in esterification products, under the condition of negative pressure, start polycondensation reaction, this staged pressure steadily is evacuated to below absolute pressure 500Pa by normal pressure, temperature is controlled at 260～270 ℃, and the reaction time is 30～50 minutes;
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continue to vacuumize, and makes reaction pressure be down to absolute pressure and be less than 100Pa, and reaction temperature is controlled at 260～275 ℃, 3～4 hours reaction time.Polycondensation reaction is with reactor stirring motor power or the in-line viscometer reading judgement reaction end that is as the criterion.
As preferred technical scheme:
The preparation method of a kind of fluorine-containing PTT polyester POY fiber as above, the mol ratio of described 1,3-PD and tetrafluoro terephthalic acid (TPA) is 1.3～2.0:1.
The preparation method of a kind of tetrafluoro PPT polyester POY fiber as above, described catalyst is selected from a kind of in butyl titanate-magnesium acetate, metatitanic acid four isopropyl esters-magnesium acetate, tetraethyl titanate-magnesium acetate, stannous acetate, dibutyltin diacetate, and catalyst amount is 0.01%～0.05% of described tetrafluoro terephthalic acid (TPA) weight.
The preparation method of a kind of fluorine-containing PTT polyester POY fiber as above, described stabilizing agent is selected from a kind of in triphenyl phosphate, trimethyl phosphate and Trimethyl phosphite, and stabilizing agent dosage is 0.01%～0.05% of described tetrafluoro terephthalic acid (TPA) weight.
The preparation method of a kind of fluorine-containing PTT polyester POY fiber as above, the addition of described inhibitor is 0.01%～0.05% of described tetrafluoro terephthalic acid (TPA) weight.
Esterification of the present invention is in the stage, reaction end actual water quantity of distillate produced in esterification reach theoretical value 90% with on grasp.The quantity of distillate that theoretical value is gained water while pressing the chemical equation complete reaction.Due to esterification this as reversible reaction, moreover raw material has residually in conveyance conduit, and, along with the carrying out of reaction, the viscosity of system increases, the shipwreck that can cause esterification to produce is therefrom to discharge.
In polycondensation reaction high vacuum stage of Fig of the present invention, the numerical value that reaction end reaches setting by reactor beater motor power and in-line viscometer calculation value is grasped.The setting numerical value of its reactor beater motor power of different devices and in-line viscometer calculation value is not necessarily identical, and setting determining of numerical value can obtain by the analysis to polyester slice.
The filament number of the novel fluorine PTT polyester POY fiber of gained of the present invention is 0.5～3.0dtex; Fracture strength is 1.8～2.5cN/dtex; Elongation at break is 100～130%.Due to the introducing of fluorine atom, improved super-hydrophobic, hydrophobic and oil repellent, the antifouling aspect performance of polyester material, at waterproof garment, in the Work Clothes manufacture of the Work Clothes born dirty and some special industry, huge prospect is arranged.
Beneficial effect:
1, gained novel fluorine PTT polyester POY fiber contain fluorine atoms; strong electronegativity due to fluorine; high C-F bond energy and to make the copolyesters POY fiber finally made have to the shielding protection effect of carbochain well heat-resisting, ageing-resistant, resistance to chemical attack and low electric capacity; low combustible; the performances such as low-refraction also have some special electric property, as low-k simultaneously; the advantages such as high-insulativity, expanded range of application.
2, gained novel fluorine PTT polyester POY fiber has certain structural stability and machinability.
3, gained novel fluorine PTT polyester POY fiber is introduced fluorine atom by employing, thereby has hydrophobic antifouling characteristic.
4, gained novel fluorine PTT polyester POY fiber is by adopting modification by copolymerization, fundamentally solved the problems such as ageing, the durability of hydrophobic antifouling polyester and ABRASION RESISTANCE.
The specific embodiment
Below in conjunction with the specific embodiment, further set forth the present invention.Should be understood that these embodiment only are not used in and limit the scope of the invention for the present invention is described.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
A kind of fluorine-containing PTT polyester POY fiber, be by fluorine-containing PTT polyester fondant through measuring, extrude, cooling, oil and coiling makes; The polytrimethylene terephthalate that described fluorine-containing PTT polyester benzene ring hydrogen is replaced by fluorine, be the polytetrafluoro propylene glycol ester terephthalate, and its general structure is
N=70～200 wherein.
A kind of fluorine-containing PTT polyester POY fiber as above, the filament number of described fluorine-containing PTT polyester POY fiber is 0.5～3.0dtex; Fracture strength is 1.8～2.5cN/dtex; Elongation at break is 100～130%.
Embodiment 1
A kind of preparation method of fluorine-containing PTT polyester, be divided into esterification and polycondensation reaction two steps.Concrete steps are:
Described esterification:
Adopt 1,3 propylene glycol that mol ratio is 1.3:1 and tetrafluoro terephthalic acid (TPA) as raw material, add 0.05% magnesia of tetrafluoro terephthalic acid (TPA) weight simultaneously, carry out esterification after being made into uniform sizing material; Esterification is in nitrogen atmosphere, and pressure is controlled at 0.3MPa, and temperature is controlled at 260 ℃, and it is the esterification terminal that esterification water quantity of distillate reaches 90% of theoretical value.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, 0.01% the stabilizing agent triphenyl phosphate that adds 0.01% catalyst metatitanic acid four butyl esters of tetrafluoro terephthalic acid (TPA) weight-magnesium acetate and tetrafluoro terephthalic acid (TPA) weight in esterification products, start polycondensation reaction under the condition of negative pressure, this staged pressure steadily is evacuated to absolute pressure by normal pressure and is less than 500Pa, temperature is controlled at 265 ℃, and the reaction time is 50 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continue to vacuumize, and makes reaction pressure be down to absolute pressure and be less than 100Pa, and reaction temperature is controlled at 270 ℃, 4 hours reaction time.Polycondensation reaction is with reactor stirring motor power or the in-line viscometer reading judgement reaction end that is as the criterion.
The method for preparing the POY fiber:
Be by described fluorine-containing PTT polyester fondant directly extrude, cooling, oil and coiling makes the POY fiber; Wherein, the described temperature of extruding is 265 ℃; Described to be cooled to lateral blowing cooling, and temperature is 25 ℃, and relative humidity is 60%, and wind speed is 0.4m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 8wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 60 parts of propylene glycol atactic polyethers, be heated to 60 ℃, 20 parts of polyethylene glycol lauric acid monoesters, 15 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluoro butyl ethyl propylene acid esters are uniformly mixed, then join in the propylene glycol atactic polyether, stir 1 hour, obtain fluorine-containing polyester fiber POY finish; The described oil applying rate oiled is 0.42%; The speed of described coiling is 2700m/min; Finally make fluorine-containing PTT polyester POY fiber, filament number is 3.0dtex; Fracture strength is 1.8cN/dtex; Elongation at break is 130%.
Embodiment 2
A kind of preparation method of fluorine-containing PTT polyester, be divided into esterification and polycondensation reaction two steps.Concrete steps are:
Described esterification:
Adopt 1,3 propylene glycol that mol ratio is 1.4:1 and tetrafluoro terephthalic acid (TPA) as raw material, add 0.04% manganese oxide of tetrafluoro terephthalic acid (TPA) weight simultaneously, carry out esterification after being made into uniform sizing material; Esterification is in nitrogen atmosphere, and pressure is controlled at 0.3MPa, and temperature is controlled at 260 ℃, and it is the esterification terminal that esterification water quantity of distillate reaches 90% of theoretical value.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, 0.02% the stabilizing agent triphenyl phosphate that adds 0.02% catalyst metatitanic acid four isopropyl esters of tetrafluoro terephthalic acid (TPA) weight-magnesium acetate and tetrafluoro terephthalic acid (TPA) weight in esterification products, start polycondensation reaction under the condition of negative pressure, this staged pressure steadily is evacuated to absolute pressure by normal pressure and is less than 400Pa, temperature is controlled at 265 ℃, and the reaction time is 50 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continue to vacuumize, and makes reaction pressure be down to absolute pressure and be less than 100Pa, and reaction temperature is controlled at 270 ℃, 4 hours reaction time.Polycondensation reaction is with reactor stirring motor power or the in-line viscometer reading judgement reaction end that is as the criterion.
The method for preparing the POY fiber:
Be by described fluorine-containing PTT polyester fondant directly extrude, cooling, oil and coiling makes the POY fiber; Wherein, the described temperature of extruding is 285 ℃; Described to be cooled to lateral blowing cooling, and temperature is 20 ℃, and relative humidity is 70%, and wind speed is 0.8m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 9wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 50 parts of butanols atactic polyethers, be heated to 40 ℃, 32 parts of polyethylene glycol laurate dibasic acid esters, 15 parts of isomerous tridecanol polyoxyethylene ether phosphate kalium salts and 3 parts of perfluoro hexyl ethyl propylene acid esters are uniformly mixed, then join in the butanols atactic polyether, stir 2 hours, obtain fluorine-containing polyester fiber POY finish; The described oil applying rate oiled is 1.5%; The speed of described coiling is 2800m/min; Finally make fluorine-containing PTT polyester POY fiber, filament number is 2.0dtex; Fracture strength is 2.0cN/dtex; Elongation at break is 125%.
Embodiment 3
A kind of preparation method of fluorine-containing PTT polyester, be divided into esterification and polycondensation reaction two steps.Concrete steps are:
Described esterification:
Adopt 1,3 propylene glycol that mol ratio is 1.6:1 and tetrafluoro terephthalic acid (TPA) as raw material, add 0.03% zinc oxide of tetrafluoro terephthalic acid (TPA) weight simultaneously, carry out esterification after being made into uniform sizing material; Esterification is in nitrogen atmosphere, and pressure is controlled at 0.2MPa, and temperature is controlled at 255 ℃, and it is the esterification terminal that esterification water quantity of distillate reaches 90% of theoretical value.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, 0.03% the stabilizing agent trimethyl phosphate that adds catalyst metatitanic acid tetra-ethyl ester-magnesium acetate of 0.03% of tetrafluoro terephthalic acid (TPA) weight and tetrafluoro terephthalic acid (TPA) weight in esterification products, start polycondensation reaction under the condition of negative pressure, this staged pressure steadily is evacuated to absolute pressure by normal pressure and is less than 400Pa, temperature is controlled at 260 ℃, and the reaction time is 45 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continue to vacuumize, and makes reaction pressure be down to absolute pressure and be less than 80Pa, and reaction temperature is controlled at 270 ℃, 3.5 hours reaction time.Polycondensation reaction is with reactor stirring motor power or the in-line viscometer reading judgement reaction end that is as the criterion.
The method for preparing the POY fiber:
Be by described fluorine-containing PTT polyester fondant directly extrude, cooling, oil and coiling makes the POY fiber; Wherein, the described temperature of extruding is 275 ℃; Described to be cooled to lateral blowing cooling, and temperature is 22 ℃, and relative humidity is 65%, and wind speed is 0.6m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 10wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 58 parts of laurate atactic polyethers, be heated to 60 ℃, 30 parts of polyethylene glycol oleic acid monoesters, 10 part of ten tetracosanol phosphate kalium salt and 2 parts of perfluoro capryl ethyl propylene acid esters are uniformly mixed, then join in the propylene glycol atactic polyether, stir 1 hour, obtain fluorine-containing polyester fiber POY finish; The described oil applying rate oiled is 0.96%; The speed of described coiling is 2900m/min; Finally make fluorine-containing PTT polyester POY fiber, filament number is 1.5dtex; Fracture strength is 2.2cN/dtex; Elongation at break is 120%.
Embodiment 4
A kind of preparation method of fluorine-containing PTT polyester, be divided into esterification and polycondensation reaction two steps.Concrete steps are:
Described esterification:
Adopt 1,3 propylene glycol that mol ratio is 1.8:1 and tetrafluoro terephthalic acid (TPA) as raw material, add 0.02% calcium oxide of tetrafluoro terephthalic acid (TPA) weight simultaneously, carry out esterification after being made into uniform sizing material; Esterification is in nitrogen atmosphere, and pressure is controlled at 0.2MPa, and temperature is controlled at 250 ℃, and it is the esterification terminal that esterification water quantity of distillate reaches 90% of theoretical value.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, 0.04% the stabilizing agent trimethyl phosphate that adds the inferior tin of 0.04% catalyst acetic acid of tetrafluoro terephthalic acid (TPA) weight and tetrafluoro terephthalic acid (TPA) weight in esterification products, start polycondensation reaction under the condition of negative pressure, this staged pressure steadily is evacuated to absolute pressure by normal pressure and is less than 300Pa, temperature is controlled at 270 ℃, and the reaction time is 40 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continue to vacuumize, and makes reaction pressure be down to absolute pressure and be less than 60Pa, and reaction temperature is controlled at 275 ℃, 3 hours reaction time.Polycondensation reaction is with reactor stirring motor power or the in-line viscometer reading judgement reaction end that is as the criterion.
The method for preparing the POY fiber:
Be by described fluorine-containing PTT polyester fondant directly extrude, cooling, oil and coiling makes the POY fiber; Wherein, the described temperature of extruding is 265 ℃; Described to be cooled to lateral blowing cooling, and temperature is 25 ℃, and relative humidity is 60%, and wind speed is 0.4m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 8wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 50 parts of lauryl alcohol atactic polyethers, be heated to 50 ℃, 32 parts of polyethylene glycol Glycol Oleic Acid Ester, 13 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluoro butyl ethyl-methyl acrylate are uniformly mixed, then join in the propylene glycol atactic polyether, stir 1 hour, obtain fluorine-containing polyester fiber POY finish; The described oil applying rate oiled is 1.5%; The speed of described coiling is 3000m/min; Finally make fluorine-containing PTT polyester POY fiber, filament number is 1.5dtex; Fracture strength is 2.3cN/dtex; Elongation at break is 110%.
Embodiment 5
A kind of preparation method of fluorine-containing PTT polyester, be divided into esterification and polycondensation reaction two steps.Concrete steps are:
Described esterification:
Adopt 1,3 propylene glycol that mol ratio is 2.0:1 and tetrafluoro terephthalic acid (TPA) as raw material, add 0.01% silica of tetrafluoro terephthalic acid (TPA) weight simultaneously, carry out esterification after being made into uniform sizing material; Esterification is in nitrogen atmosphere, and pressure is controlled at normal pressure, and temperature is controlled at 255 ℃, and it is the esterification terminal that esterification water quantity of distillate reaches 90% of theoretical value.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, 0.05% the stabilizing agent Trimethyl phosphite that adds 0.05% catalyst dibutyltin diacetate of tetrafluoro terephthalic acid (TPA) weight and tetrafluoro terephthalic acid (TPA) weight in esterification products, start polycondensation reaction under the condition of negative pressure, this staged pressure steadily is evacuated to absolute pressure by normal pressure and is less than 300Pa, temperature is controlled at 265 ℃, and the reaction time is 30 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continue to vacuumize, and makes reaction pressure be down to absolute pressure and be less than 50Pa, and reaction temperature is controlled at 275 ℃, 3 hours reaction time.Polycondensation reaction is with reactor stirring motor power or the in-line viscometer reading judgement reaction end that is as the criterion.
The method for preparing the POY fiber:
Be by described fluorine-containing PTT polyester fondant directly extrude, cooling, oil and coiling makes the POY fiber; Wherein, the described temperature of extruding is 285 ℃; Described to be cooled to lateral blowing cooling, and temperature is 20 ℃, and relative humidity is 70%, and wind speed is 0.8m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 8wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 55 parts of isomerous tridecanol atactic polyethers, be heated to 55 ℃, 25 parts of polyethylene glycol laurate dibasic acid esters, 15 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluoro hexyl ethyl-methyl acrylate are uniformly mixed, then join in the propylene glycol atactic polyether, stir 2 hours, obtain fluorine-containing polyester fiber POY finish; The described oil applying rate oiled is 0.42%; The speed of described coiling is 3200m/min; Finally make fluorine-containing PTT polyester POY fiber, filament number is 0.5dtex; Fracture strength is 2.5cN/dtex; Elongation at break is 100%.
Embodiment 6
A kind of preparation method of fluorine-containing PTT polyester, be divided into esterification and polycondensation reaction two steps.Concrete steps are:
Described esterification:
Adopt 1,3 propylene glycol that mol ratio is 1.3:1 and tetrafluoro terephthalic acid (TPA) as raw material, add 0.01% magnesia of tetrafluoro terephthalic acid (TPA) weight simultaneously, carry out esterification after being made into uniform sizing material; Esterification is in nitrogen atmosphere, and pressure is controlled at 0.3MPa, and temperature is controlled at 260 ℃, and it is the esterification terminal that esterification water quantity of distillate reaches 90% of theoretical value.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, 0.01% the stabilizing agent triphenyl phosphate that adds 0.01% catalyst metatitanic acid four butyl esters of tetrafluoro terephthalic acid (TPA) weight-magnesium acetate and tetrafluoro terephthalic acid (TPA) weight in esterification products, start polycondensation reaction under the condition of negative pressure, this staged pressure steadily is evacuated to absolute pressure by normal pressure and is less than 500Pa, temperature is controlled at 265 ℃, and the reaction time is 50 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continue to vacuumize, and makes reaction pressure be down to absolute pressure and be less than 100Pa, and reaction temperature is controlled at 270 ℃, 4 hours reaction time.Polycondensation reaction is with reactor stirring motor power or the in-line viscometer reading judgement reaction end that is as the criterion.Discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, obtain fluorine-containing PTT polyester slice.
The method for preparing the POY fiber:
Be by described fluorine-containing PTT polyester slice through screw rod melt extrude, cooling, oil and coiling makes the POY fiber; Wherein, the described temperature of extruding is 265 ℃; The described ring quenching that is cooled to, temperature is 25 ℃, and relative humidity is 60%, and wind speed is 0.4m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 8wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 60 parts of propylene glycol atactic polyethers, be heated to 45 ℃, 20 parts of polyethylene glycol oleic acid monoesters, 15 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluoro capryl ethyl-methyl acrylate are uniformly mixed, then join in the propylene glycol atactic polyether, stir 1 hour, obtain fluorine-containing polyester fiber POY finish; The described oil applying rate oiled is 0.42%; The speed of described coiling is 2700m/min; Finally make fluorine-containing PTT polyester POY fiber, filament number is 3.0dtex; Fracture strength is 1.8cN/dtex; Elongation at break is 130%.
Embodiment 7
A kind of preparation method of fluorine-containing PTT polyester, be divided into esterification and polycondensation reaction two steps.Concrete steps are:
Described esterification:
Adopt 1,3 propylene glycol that mol ratio is 1.4:1 and tetrafluoro terephthalic acid (TPA) as raw material, add 0.05% silica of tetrafluoro terephthalic acid (TPA) weight simultaneously, carry out esterification after being made into uniform sizing material; Esterification is in nitrogen atmosphere, and pressure is controlled at 0.3MPa, and temperature is controlled at 260 ℃, and it is the esterification terminal that esterification water quantity of distillate reaches 90% of theoretical value.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, 0.02% the stabilizing agent triphenyl phosphate that adds 0.02% catalyst metatitanic acid four isopropyl esters of tetrafluoro terephthalic acid (TPA) weight-magnesium acetate and tetrafluoro terephthalic acid (TPA) weight in esterification products, start polycondensation reaction under the condition of negative pressure, this staged pressure steadily is evacuated to absolute pressure by normal pressure and is less than 400Pa, temperature is controlled at 265 ℃, and the reaction time is 50 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continue to vacuumize, and makes reaction pressure be down to absolute pressure and be less than 100Pa, and reaction temperature is controlled at 270 ℃, 4 hours reaction time.Polycondensation reaction is with reactor stirring motor power or the in-line viscometer reading judgement reaction end that is as the criterion.Discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, obtain fluorine-containing PTT polyester slice.
The method for preparing the POY fiber:
Be by described fluorine-containing PTT polyester slice through screw rod melt extrude, cooling, oil and coiling makes the POY fiber; Wherein, the described temperature of extruding is 285 ℃; The described ring quenching that is cooled to, temperature is 20 ℃, and relative humidity is 70%, and wind speed is 0.8m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 8wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 50 parts of butanols atactic polyethers, be heated to 40 ℃, 32 parts of polyethylene glycol laurate dibasic acid esters, 15 parts of isomerous tridecanol polyoxyethylene ether phosphate kalium salts and 3 parts of perfluoro hexyl ethyl propylene acid esters are uniformly mixed, then join in the butanols atactic polyether, stir 2 hours, obtain fluorine-containing polyester fiber POY finish; The described oil applying rate oiled is 1.5%; The speed of described coiling is 2800m/min; Finally make fluorine-containing PTT polyester POY fiber, filament number is 2.0dtex; Fracture strength is 2.0cN/dtex; Elongation at break is 125%.
Embodiment 8
A kind of preparation method of fluorine-containing PTT polyester, be divided into esterification and polycondensation reaction two steps.Concrete steps are:
Described esterification:
Adopt 1,3 propylene glycol that mol ratio is 1.6:1 and tetrafluoro terephthalic acid (TPA) as raw material, add 0.04% calcium oxide of tetrafluoro terephthalic acid (TPA) weight simultaneously, carry out esterification after being made into uniform sizing material; Esterification is in nitrogen atmosphere, and pressure is controlled at 0.2MPa, and temperature is controlled at 255 ℃, and it is the esterification terminal that esterification water quantity of distillate reaches 90% of theoretical value.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, 0.03% the stabilizing agent trimethyl phosphate that adds catalyst metatitanic acid tetra-ethyl ester-magnesium acetate of 0.03% of tetrafluoro terephthalic acid (TPA) weight and tetrafluoro terephthalic acid (TPA) weight in esterification products, start polycondensation reaction under the condition of negative pressure, this staged pressure steadily is evacuated to absolute pressure by normal pressure and is less than 400Pa, temperature is controlled at 260 ℃, and the reaction time is 45 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continue to vacuumize, and makes reaction pressure be down to absolute pressure and be less than 80Pa, and reaction temperature is controlled at 270 ℃, 3.5 hours reaction time.Polycondensation reaction is with reactor stirring motor power or the in-line viscometer reading judgement reaction end that is as the criterion.Discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, obtain fluorine-containing PTT polyester slice.
The method for preparing the POY fiber:
Be by described fluorine-containing PTT polyester slice through screw rod melt extrude, cooling, oil and coiling makes the POY fiber; Wherein, the described temperature of extruding is 275 ℃; The described ring quenching that is cooled to, temperature is 22 ℃, and relative humidity is 65%, and wind speed is 0.6m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 8wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 60 parts of propylene glycol atactic polyethers, be heated to 60 ℃, 20 parts of polyethylene glycol lauric acid monoesters, 15 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluoro butyl ethyl propylene acid esters are uniformly mixed, then join in the propylene glycol atactic polyether, stir 1 hour, obtain fluorine-containing polyester fiber POY finish; The described oil applying rate oiled is 0.96%; The speed of described coiling is 2900m/min; Finally make fluorine-containing PTT polyester POY fiber, filament number is 1.5dtex; Fracture strength is 2.2cN/dtex; Elongation at break is 120%.
Embodiment 9
A kind of preparation method of fluorine-containing PTT polyester, be divided into esterification and polycondensation reaction two steps.Concrete steps are:
Described esterification:
Adopt 1,3 propylene glycol that mol ratio is 1.8:1 and tetrafluoro terephthalic acid (TPA) as raw material, add 0.03% zinc oxide of tetrafluoro terephthalic acid (TPA) weight simultaneously, carry out esterification after being made into uniform sizing material; Esterification is in nitrogen atmosphere, and pressure is controlled at 0.2MPa, and temperature is controlled at 250 ℃, and it is the esterification terminal that esterification water quantity of distillate reaches 90% of theoretical value.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, 0.04% the stabilizing agent trimethyl phosphate that adds the inferior tin of 0.04% catalyst acetic acid of tetrafluoro terephthalic acid (TPA) weight and tetrafluoro terephthalic acid (TPA) weight in esterification products, start polycondensation reaction under the condition of negative pressure, this staged pressure steadily is evacuated to absolute pressure by normal pressure and is less than 300Pa, temperature is controlled at 270 ℃, and the reaction time is 40 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continue to vacuumize, and makes reaction pressure be down to absolute pressure and be less than 60Pa, and reaction temperature is controlled at 275 ℃, 3 hours reaction time.Polycondensation reaction is with reactor stirring motor power or the in-line viscometer reading judgement reaction end that is as the criterion.Discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, obtain fluorine-containing PTT polyester slice.
The method for preparing the POY fiber:
Be by described fluorine-containing PTT polyester slice through screw rod melt extrude, cooling, oil and coiling makes the POY fiber; Wherein, the described temperature of extruding is 265 ℃; The described ring quenching that is cooled to, temperature is 25 ℃, and relative humidity is 60%, and wind speed is 0.4m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 8wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 50 parts of lauryl alcohol atactic polyethers, be heated to 50 ℃, 32 parts of polyethylene glycol Glycol Oleic Acid Ester, 13 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluoro butyl ethyl-methyl acrylate are uniformly mixed, then join in the propylene glycol atactic polyether, stir 1 hour, obtain fluorine-containing polyester fiber POY finish; The described oil applying rate oiled is 1.5%; The speed of described coiling is 3000m/min; Finally make fluorine-containing PTT polyester POY fiber, filament number is 1.5dtex; Fracture strength is 2.3cN/dtex; Elongation at break is 110%.
Embodiment 10
A kind of preparation method of fluorine-containing PTT polyester, be divided into esterification and polycondensation reaction two steps.Concrete steps are:
Described esterification:
Adopt 1,3 propylene glycol that mol ratio is 2.0:1 and tetrafluoro terephthalic acid (TPA) as raw material, add 0.01% manganese oxide of tetrafluoro terephthalic acid (TPA) weight simultaneously, carry out esterification after being made into uniform sizing material; Esterification is in nitrogen atmosphere, and pressure is controlled at normal pressure, and temperature is controlled at 255 ℃, and it is the esterification terminal that esterification water quantity of distillate reaches 90% of theoretical value.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, 0.05% the stabilizing agent Trimethyl phosphite that adds 0.05% catalyst dibutyltin diacetate of tetrafluoro terephthalic acid (TPA) weight and tetrafluoro terephthalic acid (TPA) weight in esterification products, start polycondensation reaction under the condition of negative pressure, this staged pressure steadily is evacuated to absolute pressure by normal pressure and is less than 300Pa, temperature is controlled at 265 ℃, and the reaction time is 30 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continue to vacuumize, and makes reaction pressure be down to absolute pressure and be less than 50Pa, and reaction temperature is controlled at 275 ℃, 3 hours reaction time.Polycondensation reaction is with reactor stirring motor power or the in-line viscometer reading judgement reaction end that is as the criterion.Discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, obtain fluorine-containing PTT polyester slice.
The method for preparing the POY fiber:
Be by described fluorine-containing PTT polyester slice through screw rod melt extrude, cooling, oil and coiling makes the POY fiber; Wherein, the described temperature of extruding is 285 ℃; The described ring quenching that is cooled to, temperature is 20 ℃, and relative humidity is 70%, and wind speed is 0.8m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 8wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 60 parts of propylene glycol atactic polyethers, be heated to 45 ℃, 20 parts of polyethylene glycol oleic acid monoesters, 15 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluoro capryl ethyl-methyl acrylate are uniformly mixed, then join in the propylene glycol atactic polyether, stir 1 hour, obtain fluorine-containing polyester fiber POY finish; The described oil applying rate oiled is 0.42%; The speed of described coiling is 3200m/min; Finally make fluorine-containing PTT polyester POY fiber, filament number is 0.5dtex; Fracture strength is 2.5cN/dtex; Elongation at break is 100%.
Claims (10)
1. a fluorine-containing PTT polyester POY fiber is characterized in that: described fluorine-containing PTT polyester POY fiber be by fluorine-containing PTT polyester fondant through measuring, extrude, cooling, oil and coiling makes; The polytrimethylene terephthalate that described fluorine-containing PTT polyester benzene ring hydrogen is replaced by fluorine, be the polytetrafluoro propylene glycol ester terephthalate, and its general structure is
N=70～200 wherein.
2. a kind of fluorine-containing PTT polyester POY fiber according to claim 1, is characterized in that, the filament number of described fluorine-containing PTT polyester POY fiber is 0.5～3.0dtex; Fracture strength is 1.8～2.5cN/dtex; Elongation at break is 100～130%.
3. the preparation method of a kind of fluorine-containing PTT polyester POY fiber as claimed in claim 1 is characterized in that: by fluorine-containing PTT polyester fondant through measuring, extrude, cooling, the step that oils and reel, make fluorine-containing PTT polyester POY fiber;
The described temperature of extruding is 265～285 ℃;
Described cooling wind-warm syndrome is 20～25 ℃;
The described oil applying rate oiled is 0.42～1.5%;
The speed of described coiling is 2700～3200m/min;
The described finish oiled is fluorine-containing polyester POY fiber finish, its component by weight:
Atactic polyether, 50～60 parts;
Cithrol, 20～32 parts;
Phosphate kalium salt, 10～15 parts;
Perfluoroalkyl acrylate, 2～5 parts;
The preparation method of finish:
By atactic polyether, be heated to 40～60 ℃, cithrol, phosphate kalium salt and perfluoroalkyl acrylate are uniformly mixed, then join in atactic polyether, stir 1～2 hour, obtain fluorine-containing polyester POY fiber finish, finish adds water while using and is made into the emulsion that solid content is 8～10wt%;
Described fluorine-containing PTT polyester fondant refers to the fluorine-containing PTT polyester after melting, and the preparation method of described fluorine-containing PTT polyester is divided into esterification and polycondensation reaction two steps; Concrete steps are:
Described esterification:
Adopt tetrafluoro terephthalic acid (TPA) and 1,3-PD as raw material, add inhibitor, carry out esterification after being made into uniform sizing material, obtain esterification products; Esterification is pressurizeed in nitrogen atmosphere, and pressure is controlled at normal pressure～0.3MPa, and temperature is at 250～260 ℃, and what esterification water quantity of distillate reached theoretical value is the esterification terminal more than 90%;
Described inhibitor is a kind of in magnesia, silica, calcium oxide, zinc oxide and manganese oxide;
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, add catalyst and stabilizing agent in esterification products, under the condition of negative pressure, start polycondensation reaction, this staged pressure steadily is evacuated to below absolute pressure 500Pa by normal pressure, temperature is controlled at 260～270 ℃, and the reaction time is 30～50 minutes;
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continue to vacuumize, and makes reaction pressure be down to absolute pressure and be less than 100Pa, and reaction temperature is controlled at 260～275 ℃, 3～4 hours reaction time.
4. the preparation method of a kind of fluorine-containing PTT polyester POY fiber according to claim 3, is characterized in that, described lateral blowing or the ring quenching of being cooled to, and temperature is 20 ℃～25 ℃, and relative humidity is 65% ± 5%, and wind speed is 0.4～0.8m/s.
5. the preparation method of a kind of fluorine-containing PTT polyester POY fiber according to claim 3, is characterized in that, the mol ratio of described 1,3-PD and tetrafluoro terephthalic acid (TPA) is 1.3～2.0:1.
6. the preparation method of a kind of fluorine-containing PTT polyester POY fiber according to claim 3, it is characterized in that, described catalyst is selected from a kind of in butyl titanate-magnesium acetate, metatitanic acid four isopropyl esters-magnesium acetate, tetraethyl titanate-magnesium acetate, stannous acetate, dibutyltin diacetate, and catalyst amount is 0.01%～0.05% of described tetrafluoro terephthalic acid (TPA) weight.
7. the preparation method of a kind of fluorine-containing PTT polyester POY fiber according to claim 3, it is characterized in that, described stabilizing agent is selected from a kind of in triphenyl phosphate, trimethyl phosphate and Trimethyl phosphite, and stabilizing agent dosage is 0.01%～0.05% of described tetrafluoro terephthalic acid (TPA) weight.
8. the preparation method of a kind of fluorine-containing PTT polyester POY fiber according to claim 3, is characterized in that, the addition of described inhibitor is 0.01%～0.05% of described tetrafluoro terephthalic acid (TPA) weight.
9. the preparation method of a kind of fluorine-containing PTT polyester POY fiber according to claim 3, is characterized in that, described fluorine-containing PTT polyester fondant is directly obtained or obtained through the screw rod melting by fluorine-containing PTT polyester slice by polymerization.
10. the preparation method of a kind of fluorine-containing PTT polyester POY fiber according to claim 3, it is characterized in that, described atactic polyether is a kind of in propylene glycol atactic polyether, butanols atactic polyether, laurate atactic polyether, lauryl alcohol atactic polyether and isomerous tridecanol atactic polyether; Described cithrol is a kind of in polyethylene glycol lauric acid monoester, polyethylene glycol laurate dibasic acid esters, polyethylene glycol oleic acid monoester and polyethylene glycol Glycol Oleic Acid Ester; Described phosphate kalium salt is a kind of in 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, isomerous tridecanol polyoxyethylene ether phosphate kalium salt and ten tetracosanol phosphate kalium salts; Described perfluoroalkyl acrylate is a kind of in perfluoro butyl ethyl propylene acid esters, perfluoro hexyl ethyl propylene acid esters, perfluoro capryl ethyl propylene acid esters, perfluoro butyl ethyl-methyl acrylate, perfluoro hexyl ethyl-methyl acrylate and perfluoro capryl ethyl-methyl acrylate.
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