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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- Prior art keywords
- fluorine
- reaction
- ptt polyester
- containing ptt
- poy fiber
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- 229920000728 polyester Polymers 0.000 title claims abstract description 175
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 166
- 239000011737 fluorine Substances 0.000 title claims abstract description 162
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 161
- 239000000835 fiber Substances 0.000 title claims abstract description 117
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 229920002215 polytrimethylene terephthalate Polymers 0.000 title claims description 96
- -1 polytrimethylene terephthalate Polymers 0.000 title claims description 49
- 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 45
- 238000004804 winding Methods 0.000 claims abstract description 29
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims abstract description 16
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 12
- 239000003112 inhibitor Substances 0.000 claims abstract description 9
- 238000006068 polycondensation reaction Methods 0.000 claims description 110
- 238000005886 esterification reaction Methods 0.000 claims description 87
- 238000006243 chemical reaction Methods 0.000 claims description 58
- 238000001816 cooling Methods 0.000 claims description 46
- 239000003921 oil Substances 0.000 claims description 45
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 42
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 40
- 229920000570 polyether Polymers 0.000 claims description 40
- 230000032050 esterification Effects 0.000 claims description 28
- 239000002202 Polyethylene glycol Substances 0.000 claims description 26
- 229920001223 polyethylene glycol Polymers 0.000 claims description 26
- 230000035484 reaction time Effects 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- 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
- 239000002002 slurry Substances 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 12
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 12
- 238000007664 blowing Methods 0.000 claims description 11
- GWTCIAGIKURVBJ-UHFFFAOYSA-L dipotassium;dodecyl phosphate Chemical group [K+].[K+].CCCCCCCCCCCCOP([O-])([O-])=O GWTCIAGIKURVBJ-UHFFFAOYSA-L 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001125 extrusion Methods 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
- 239000000203 mixture Substances 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
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 7
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 229930195729 fatty acid Natural products 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000008041 oiling agent Substances 0.000 claims description 6
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims description 5
- VPKQPPJQTZJZDB-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOC(=O)C=C VPKQPPJQTZJZDB-UHFFFAOYSA-N 0.000 claims description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 5
- 229940087291 tridecyl alcohol Drugs 0.000 claims description 5
- KUGVQHLGVGPAIZ-UHFFFAOYSA-N 1,1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F KUGVQHLGVGPAIZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005639 Lauric acid Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 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
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 claims description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 4
- 229940070765 laurate Drugs 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 4
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 4
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- STYXVTBFUKQEKM-UHFFFAOYSA-N 1,1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F STYXVTBFUKQEKM-UHFFFAOYSA-N 0.000 claims description 3
- XEUCQOBUZPQUMQ-UHFFFAOYSA-N Glycolone Chemical compound COC1=C(CC=C(C)C)C(=O)NC2=C1C=CC=C2OC XEUCQOBUZPQUMQ-UHFFFAOYSA-N 0.000 claims description 2
- UWIULCYKVGIOPW-UHFFFAOYSA-N Glycolone Natural products CCOC1=C(CC=CC)C(=O)N(C)c2c(O)cccc12 UWIULCYKVGIOPW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims 2
- 239000005642 Oleic acid Substances 0.000 claims 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims 1
- QSLLXQPOVJSDAY-UHFFFAOYSA-L dipotassium;tetradecyl phosphate Chemical compound [K+].[K+].CCCCCCCCCCCCCCOP([O-])([O-])=O QSLLXQPOVJSDAY-UHFFFAOYSA-L 0.000 claims 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 claims 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims 1
- 235000011285 magnesium acetate Nutrition 0.000 claims 1
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 230000003373 anti-fouling effect Effects 0.000 abstract description 12
- 230000003075 superhydrophobic effect Effects 0.000 abstract description 4
- 239000005871 repellent Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000155 melt Substances 0.000 abstract 1
- 229940035437 1,3-propanediol Drugs 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 9
- 238000009987 spinning Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 238000005266 casting Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 238000005453 pelletization Methods 0.000 description 5
- MUHFRORXWCGZGE-KTKRTIGZSA-N 2-hydroxyethyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCO MUHFRORXWCGZGE-KTKRTIGZSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical class CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000005690 diesters Chemical class 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
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 description 3
- 229940033623 potassium lauryl phosphate Drugs 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004753 textile Substances 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
- QUKRIOLKOHUUBM-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOC(=O)C=C QUKRIOLKOHUUBM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- ZBZICERRZIMWGX-UHFFFAOYSA-N 1,1,1,2,3,3,4,4,5,5,6,6,6-tridecafluorohexan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZBZICERRZIMWGX-UHFFFAOYSA-N 0.000 description 1
- PEVRKKOYEFPFMN-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene;1,1,2,2-tetrafluoroethene Chemical compound FC(F)=C(F)F.FC(F)=C(F)C(F)(F)F PEVRKKOYEFPFMN-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- YJLVXRPNNDKMMO-UHFFFAOYSA-N 3,4,5,6-tetrafluorophthalic acid Chemical compound OC(=O)C1=C(F)C(F)=C(F)C(F)=C1C(O)=O YJLVXRPNNDKMMO-UHFFFAOYSA-N 0.000 description 1
- SENMPMXZMGNQAG-UHFFFAOYSA-N 3,4-dihydro-2,5-benzodioxocine-1,6-dione Chemical compound O=C1OCCOC(=O)C2=CC=CC=C12 SENMPMXZMGNQAG-UHFFFAOYSA-N 0.000 description 1
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
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- 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
- 238000004364 calculation method Methods 0.000 description 1
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- 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
- 238000010494 dissociation reaction Methods 0.000 description 1
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- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
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- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
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- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
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- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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Abstract
本发明涉及一种含氟PTT聚酯POY纤维及其制备方法，包括含氟PTT聚酯熔体的制备和含氟PTT聚酯POY纤维的制备；在含氟PTT聚酯熔体的制备工艺中采用四氟对苯二甲酸和1,3-丙二醇作为原料并加入抑制剂制备得到含氟PTT聚酯熔体，将熔体直接挤出或制成切片经螺杆熔融挤出、冷却、上油和卷绕制得含氟PTT聚酯POY纤维。本发明所得的新型含氟PTT聚酯POY纤维单丝纤度为0.5～3.0dtex；断裂强度为1.8～2.5cN/dtex；断裂伸长率为100～130%。由于氟原子的引入，改善了聚酯POY纤维的超疏水、憎水憎油、防污方面性能，在防水服，耐脏的工作服以及某些特殊行业的工作服制造中有巨大的前景。The invention relates to a fluorine-containing PTT polyester POY fiber and a preparation method thereof, comprising the preparation of a fluorine-containing PTT polyester melt and the preparation of a fluorine-containing PTT polyester POY fiber; in the preparation process of a fluorine-containing PTT polyester melt Using tetrafluoroterephthalic acid and 1,3-propanediol as raw materials and adding inhibitors to prepare fluorine-containing PTT polyester melt, the melt is directly extruded or made into slices, melted and extruded by a screw, cooled, oiled and The fluorine-containing PTT polyester POY fiber is obtained by winding. The monofilament fineness of the novel fluorine-containing PTT polyester POY fiber obtained by the invention is 0.5-3.0 dtex; the breaking strength is 1.8-2.5 cN/dtex; and the breaking elongation is 100-130%. Due to the introduction of fluorine atoms, the superhydrophobic, oil-repellent and anti-fouling properties of polyester POY fiber are improved, and it has great prospects in the manufacture of waterproof clothing, dirt-resistant work clothes and work clothes in some special industries.
Description
技术领域technical field
本发明涉及一种含氟PTT聚酯POY纤维及其制备方法，特别是涉及一种苯环上的氢被氟取代的含氟PTT聚酯POY纤维及其制备方法。The invention relates to a fluorine-containing PTT polyester POY fiber and a preparation method thereof, in particular to a fluorine-containing PTT polyester POY fiber in which the hydrogen on the benzene ring is replaced by fluorine and a preparation method thereof.
背景技术Background technique
聚酯是目前人类使用最为广泛的合成高聚物之一，早在二十世纪40年代就合成出了苯二甲酸乙二醇酯（PET），并发现其具有优异的性能，而广泛的应用于纺织、包装、医疗卫生、汽车、电子电器、安全防护、环境保护等领域。预取向丝POY，是指未经拉伸但可直接进行拉伸变形加工的原丝，要求POY丝能够长时间存放，并具有一定的结构稳定性和可加工性。POY丝在加工过程中一般不会出现生头困难、成品丝毛丝、强度偏低以及染色布均匀的情况。其工艺具有纺丝绕卷速度高，绕卷筒子硬度高、重量大、便宜运输的优点；并且纺丝过程中存放稳定性好，适宜DTY加工。Polyester is currently one of the most widely used synthetic polymers. As early as the 1940s, ethylene phthalate (PET) was synthesized and found to have excellent properties, and it is widely used In textile, packaging, medical and health, automobile, electronic appliances, safety protection, environmental protection and other fields. Pre-oriented yarn POY refers to the raw yarn that has not been stretched but can be directly stretched and deformed. It is required that the POY yarn can be stored for a long time and has certain structural stability and processability. During the processing of POY yarn, there are generally no problems such as difficulty in spinning, finished silk wool, low strength and uniform dyed cloth. The process has the advantages of high spinning winding speed, high hardness, heavy weight and cheap transportation; and good storage stability during spinning, suitable for DTY processing.
聚对苯二甲酸丙二醇酯（PTT）是继聚对苯二甲酸乙二醇酯（PET）及对苯二甲酸丁二醇酯（PBT）之后新研发的一种极具发展前途的新型聚酯高分子材料，1998年被美国评为六大石化新产品之一。与PET、PBT相比，PTT具有更好的弹性、尺寸稳定性和染色性等。同时具有抗紫外线、抗内应力、低吸水性、低静电以及良好的生物降解性、可循环利用等多种优良特性，因此广泛应用于地毯工业、服装材料、工程塑料等领域。Polytrimethylene terephthalate (PTT) is a promising new type of polyester newly developed after polyethylene terephthalate (PET) and butylene terephthalate (PBT). Polymer materials were rated as one of the six new petrochemical products by the United States in 1998. Compared with PET and PBT, PTT has better elasticity, dimensional stability and dyeability. At the same time, it has many excellent properties such as anti-ultraviolet, anti-internal stress, low water absorption, low static electricity, good biodegradability, and recyclability, so it is widely used in carpet industry, clothing materials, engineering plastics and other fields.
随着社会的进步，人民生活水平的提高，对聚酯纤维的差别化、功能化需要越来越高。因此聚酯的改性也变得尤为的重要，聚酯改性目的除了对普通聚酯性能进行优化外，主要是通过改性手段赋予新型聚酯差别化的功能性特征。例如：抗静电、阻燃、吸湿排汗、防污防臭等。目前，聚酯主要新品种有：抗静电聚酯、高强耐磨聚酯、仿棉超软聚酯、超疏水性聚酯、抗污聚酯等。With the progress of society and the improvement of people's living standards, the demand for the differentiation and functionalization of polyester fibers is getting higher and higher. Therefore, the modification of polyester has become particularly important. The purpose of polyester modification is not only to optimize the performance of ordinary polyester, but also to endow new polyester with differentiated functional characteristics through modification means. For example: antistatic, flame retardant, moisture wicking, antifouling and deodorant, etc. At present, the main new varieties of polyester are: antistatic polyester, high-strength wear-resistant polyester, cotton-like supersoft polyester, superhydrophobic polyester, antifouling polyester, etc.
目前，通过在聚合物中引入氟原子，从而改善材料的表面性能，如疏水疏油性及防污性等，以及赋予聚酯材料各种功能。由于含氟聚合物通常具有低表面能、低摩擦系数和不粘附性，灰尘污物难于附着等特性，因此含氟聚合物的抗污耐磨性好。而当前含氟聚合物以氟代烯烃类聚合物为主（例如：聚四氟乙烯、聚偏氟乙烯、全氟乙烯丙烯共聚物、乙烯-四氟乙烯共聚物等）；含氟聚氨酯、含氟聚醚、含氟聚酯等的研究则相对滞后。At present, by introducing fluorine atoms into polymers, the surface properties of materials, such as hydrophobicity, oil repellency and anti-fouling properties, etc. are improved, and various functions are endowed to polyester materials. Because fluoropolymers usually have low surface energy, low coefficient of friction and non-adhesion, dust and dirt are difficult to adhere to, etc., so fluoropolymers have good anti-fouling and abrasion resistance. The current fluoropolymers are mainly fluoroolefin polymers (such as polytetrafluoroethylene, polyvinylidene fluoride, perfluoroethylene propylene copolymer, ethylene-tetrafluoroethylene copolymer, etc.); Research on fluoropolyethers and fluoropolyesters is relatively lagging behind.
许多学者对含氟化合物改性聚酯进行了研究，并取得了一定的成果。目前含氟化合物改性聚酯的方式主要是通过加入含氟封端剂，或者加入含氟二元醇、含氟二元酸等含氟化合物作为第三单体来改性聚酯。中国专利CN101139434A中采用含氟封端剂的加入，间苯二甲酸二甲酯和丁二醇采用酯交换法，加入含氟封端剂N-羟乙基全氟辛酰胺，制备出了含氟量低而耐沾污性能好的聚酯材料。胡娟（胡娟.含氟聚酯和光刻胶波导材料的分子设计与性能研究[D].硕士论文,吉林:吉林大学,2007.）利用分子设计的原理，通过添加含氟二元醇共聚的方式，将对苯二甲酰氯、六氟双酚A和含氟辛二醇三元共聚合成出了新型高含氟量的聚酯。该聚酯具有优异的性能而被应用于光波导材料。Qingzeng Zhu等（Q Z Zhu,C C Han.Synthesis andcrystalization behaviors of highly fluorinated aromatic polyesters[J].Polymer2007(48):3624-3631.）通过添加含氟二元酸共聚的方式改性聚酯，2,3,4,5-四氟邻苯二甲酸改性聚邻苯二甲酸乙二醇酯，聚酯的结晶性能得到改善。Many scholars have conducted research on fluorine-containing compound-modified polyester, and achieved certain results. At present, polyesters are modified by fluorine-containing compounds mainly by adding fluorine-containing end-capping agents, or by adding fluorine-containing diols, fluorine-containing dibasic acids and other fluorine-containing compounds as the third monomer to modify polyester. In Chinese patent CN101139434A, the addition of fluorine-containing end-capping agent is adopted. Dimethyl isophthalate and butanediol are transesterified, and fluorine-containing end-capping agent N-hydroxyethyl perfluorooctylamide is added to prepare a fluorine-containing end-capping agent. Polyester material with low weight and good stain resistance. Hu Juan (Hu Juan. Molecular design and performance research of fluorine-containing polyester and photoresist waveguide materials [D]. Master's thesis, Jilin: Jilin University, 2007.) Using the principle of molecular design, by adding fluorine-containing diols In the way of copolymerization, terephthaloyl chloride, hexafluorobisphenol A and fluorine-containing octanediol are terpolymerized to form a new type of polyester with high fluorine content. The polyester has excellent properties and is applied to optical waveguide materials. Qingzeng Zhu et al. (Q Z Zhu, C C Han. Synthesis and crystallization behaviors of highly fluorinated aromatic polyesters[J]. Polymer2007(48):3624-3631.) modified polyester by adding fluorine-containing dibasic acid copolymerization, 2 ,3,4,5-tetrafluorophthalic acid modified polyethylene glycol phthalate, the crystallinity of polyester is improved.
然而，将这些含有氟元素的聚酯应用于纺织及包装材料中有一定的局限性，主要问题在于现有技术的含有氟元素的聚酯分子量低，不能满足纺丝和成膜的要求；现有技术目前主要是通过织物的含氟后整理方式来赋予其防水防污功能，而这类方法最大的缺点在于难以解决时效性、耐久性及耐磨性等问题，并且费时费力。However, the application of these fluorine-containing polyesters to textiles and packaging materials has certain limitations. The main problem is that the prior art fluorine-containing polyesters have low molecular weight and cannot meet the requirements of spinning and film formation; At present, the existing technology mainly uses fluorine-containing finishing methods to endow fabrics with waterproof and anti-fouling functions, but the biggest disadvantage of this method is that it is difficult to solve the problems of timeliness, durability and wear resistance, and it is time-consuming and labor-intensive.
因此，开发含氟聚酯纤维用于纺织及包装材料的超疏水、憎水憎油、防污性能的改性，必将具有重要的理论意义和应用价值。Therefore, the development of fluorine-containing polyester fibers for the modification of superhydrophobic, hydrophobic, oil-repellent, and antifouling properties of textile and packaging materials will have important theoretical significance and application value.
发明内容Contents of the invention
本发明提供一种含氟PTT聚酯POY纤维及其制备方法，特别是提供一种苯环上的氢被氟取代的含氟PTT聚酯POY纤维及其制备方法。本发明所述的含氟PTT聚酯在聚合物的主链上引入了氟原子，因此可以很好的解决费时费力这类问题。本发明中所述的含氟PTT聚酯是通过苯环上含氟原子的对苯二甲酸与1,3-丙二醇，经过酯化和缩聚得到的含氟聚酯。通过共聚法对聚酯进行疏水防污改性，可以从根本上解决疏水防污聚酯的时效性、耐久性及耐磨性等问题。The invention provides a fluorine-containing PTT polyester POY fiber and a preparation method thereof, in particular a fluorine-containing PTT polyester POY fiber in which the hydrogen on the benzene ring is replaced by fluorine and a preparation method thereof. The fluorine-containing PTT polyester of the present invention introduces fluorine atoms into the main chain of the polymer, so it can well solve the problems of time-consuming and labor-consuming. The fluorine-containing PTT polyester described in the present invention is a fluorine-containing polyester obtained through esterification and polycondensation of terephthalic acid containing fluorine atoms on the benzene ring and 1,3-propanediol. Hydrophobic and antifouling modification of polyester by copolymerization can fundamentally solve the problems of timeliness, durability and wear resistance of hydrophobic and antifouling polyester.
本发明提供了以下技术方案：The invention provides the following technical solutions:
一种含氟PTT聚酯POY纤维，是由含氟PTT聚酯熔体直接挤出或制成切片经螺杆熔融挤出、冷却、上油和卷绕制得；所述含氟PTT聚酯，是指苯环上的氢被氟取代的聚对苯二甲酸丙二醇酯，为聚四氟对苯二甲酸丙二醇酯，其结构通式为A fluorine-containing PTT polyester POY fiber is obtained by directly extruding fluorine-containing PTT polyester melt or making slices through screw melt extrusion, cooling, oiling and winding; the fluorine-containing PTT polyester, It refers to the poly(trimethylene terephthalate) in which the hydrogen on the benzene ring is replaced by fluorine, which is poly(tetrafluorotrimethylene terephthalate), and its general structural formula is
其中n=70～200。Among them, n=70～200.
如上所述的一种含氟PTT聚酯POY纤维，所述含氟PTT聚酯POY纤维的单丝纤度为0.5～3.0dtex；断裂强度为1.8～2.5cN/dtex；断裂伸长率为100～130%。A kind of fluorine-containing PTT polyester POY fiber as described above, the monofilament fineness of the fluorine-containing PTT polyester POY fiber is 0.5-3.0dtex; the breaking strength is 1.8-2.5cN/dtex; the elongation at break is 100- 130%.
本发明还提供了一种含氟PTT聚酯POY纤维的制备方法，是由含氟PTT聚酯熔体经计量、挤出、冷却、上油和卷绕制得含氟PTT聚酯POY纤维。The invention also provides a preparation method of fluorine-containing PTT polyester POY fiber, which is to prepare fluorine-containing PTT polyester POY fiber by measuring, extruding, cooling, oiling and winding the fluorine-containing PTT polyester melt.
所述挤出的温度为265～285℃；The extrusion temperature is 265-285°C;
所述的冷却的风温为20～25℃；The wind temperature of described cooling is 20～25 ℃;
所述上油的上油率为0.42～1.5%；The oiling rate of the oiling is 0.42～1.5%;
所述卷绕的速度为2700～3200m/min；The winding speed is 2700～3200m/min;
所述的冷却为侧吹风或环吹风冷却，温度为20℃～25℃，相对湿度为65%±5%，风速为0.4～0.8m/s；The cooling is side blowing or ring blowing cooling, the temperature is 20°C-25°C, the relative humidity is 65%±5%, and the wind speed is 0.4-0.8m/s;
所述上油的油剂为含氟聚酯POY纤维用油剂，其组分按重量份计：The oiling agent for oiling is an oiling agent for fluorine-containing polyester POY fibers, and its components are by weight:
组分A：无规聚醚，50～60份；Component A: random polyether, 50-60 parts;
组分B：聚乙二醇脂肪酸酯，20～32份；Component B: polyethylene glycol fatty acid ester, 20-32 parts;
组分C：磷酸酯钾盐，10～15份；Component C: Potassium Phosphate, 10-15 parts;
组分D：全氟烷基丙烯酸酯，2～5份；Component D: perfluoroalkyl acrylate, 2-5 parts;
油剂制备方法：Oil preparation method:
将无规聚醚，加热到40～60℃，把聚乙二醇脂肪酸酯、磷酸酯钾盐和全氟烷基丙烯酸酯搅拌混合均匀，然后加入到无规聚醚中，搅拌1～2个小时，即得到含氟聚酯纤维用POY油剂，油剂使用时加水配成含固量为8～10wt%的乳液。Heat the random polyether to 40-60°C, stir and mix the polyethylene glycol fatty acid ester, phosphate potassium salt and perfluoroalkyl acrylate evenly, then add it to the random polyether, stir for 1-2 Hours, the POY oil for fluorine-containing polyester fibers is obtained. When the oil is used, water is added to form an emulsion with a solid content of 8-10wt%.
所述含氟聚酯POY纤维用油剂中，组分A无规聚醚为平滑剂：该物质为丙二醇无规聚醚、丁醇无规聚醚、月桂酸无规聚醚、十二醇无规聚醚和异构十三醇无规聚醚中的一种。无规聚醚的耐热性好，发烟少，结焦少，流动温度低，稳定性好，摩擦系数低，抗剪切能力强，粘度系数低，能在聚酯纤维表面形成非常稳定的具有大吸附力和承载能力的润滑剂膜。In the oil agent for fluorine-containing polyester POY fibers, component A random polyether is a smoothing agent: the substance is propylene glycol random polyether, butanol random polyether, lauric acid random polyether, lauryl alcohol One of random polyether and isomeric tridecyl alcohol random polyether. Atactic polyether has good heat resistance, less smoke, less coking, low flow temperature, good stability, low friction coefficient, strong shear resistance, low viscosity coefficient, and can form a very stable polymer on the surface of polyester fiber. Lubricant film with high adsorption and load-carrying capacity.
所述含氟聚酯POY纤维用油剂中，组分B聚乙二醇脂肪酸酯为乳化剂：该物质为聚乙二醇月桂酸单酯、聚乙二醇月桂酸双酯、聚乙二醇油酸单酯和聚乙二醇油酸双酯中的一种。聚乙二醇脂肪酸酯所成油膜有着良好的表面张力、界面张力、渗透力、分散性和乳化性等性能，其组成油剂能够减少丝与丝之间、丝与金属之间的静/动摩擦力，为含氟聚酯纤维提供一定的抗静电性，提高集束性。In the oil agent for fluorine-containing polyester POY fibers, component B polyethylene glycol fatty acid ester is an emulsifier: the substance is polyethylene glycol monolaurate, polyethylene glycol diester, polyethylene glycol One of glycol monooleate and polyethylene glycol diester. The oil film formed by polyethylene glycol fatty acid ester has good properties such as surface tension, interfacial tension, penetration, dispersibility and emulsification. Dynamic friction provides certain antistatic properties for fluorine-containing polyester fibers and improves bundling properties.
所述含氟聚酯POY纤维用油剂中，组分C磷酸酯钾盐为抗静电剂：该物质为十二烷基磷酸酯钾盐、异构十三醇聚氧乙烯醚磷酸酯钾盐和十二十四醇磷酸酯钾盐中的一种。在纺丝过程中，易产生大量静电，通过纤维表面的平滑性来减少静电量的产生是不够的，还需要加入性能优越的抗静电剂。磷酸酯钾盐是一种良好的抗静电剂，它是一种阴离子表面活性剂，由疏水集团和亲水基团组成，疏水基团能和聚酯纤维表面结合，亲水基团磷酸基团向上，可形成“界面活性剂-水”的连续水膜。能够有效降低纤维的摩擦系数，增加摩擦体之间的介电常数，防止静电发生。In the oil agent for fluorine-containing polyester POY fibers, component C phosphate potassium salt is an antistatic agent: the substance is potassium lauryl phosphate, isomeric tridecyl polyoxyethylene ether phosphate potassium salt and one of the potassium salts of tetradecyl alcohol phosphate. In the spinning process, a large amount of static electricity is easily generated. It is not enough to reduce the generation of static electricity through the smoothness of the fiber surface. It is also necessary to add an antistatic agent with superior performance. Phosphate potassium salt is a good antistatic agent. It is an anionic surfactant composed of hydrophobic groups and hydrophilic groups. The hydrophobic groups can combine with the surface of polyester fibers, and the hydrophilic groups Upward, a continuous water film of "surfactant-water" can be formed. It can effectively reduce the friction coefficient of fibers, increase the dielectric constant between friction bodies, and prevent static electricity from occurring.
所述含氟聚酯POY纤维用油剂中，组分D全氟烷基丙烯酸酯为添加剂：该物质为全氟丁基乙基丙烯酸酯、全氟己基乙基丙烯酸酯、全氟辛基乙基丙烯酸酯、全氟丁基乙基甲基丙烯酸酯、全氟己基乙基甲基丙烯酸酯和全氟辛基乙基甲基丙烯酸酯中的一种。其作用是适当减少油剂的表面张力，使其易于形成均匀的连续油膜。含氟丙烯酸酯具有较低的表面能，适量添加能够减低油剂的表面张力，使得油剂的润湿性能和渗透力大为增加，易于在纤维的润湿和铺展，形成均匀的油膜。In the oil agent for fluorine-containing polyester POY fibers, component D perfluoroalkyl acrylate is an additive: the substance is perfluorobutyl ethyl acrylate, perfluorohexyl ethyl acrylate, perfluorooctyl ethyl acrylate, One of methacrylate, perfluorobutylethyl methacrylate, perfluorohexylethyl methacrylate and perfluorooctylethyl methacrylate. Its function is to appropriately reduce the surface tension of the oil agent, making it easy to form a uniform continuous oil film. Fluorine-containing acrylate has low surface energy, adding an appropriate amount can reduce the surface tension of the oil, greatly increasing the wetting performance and penetration of the oil, making it easy to wet and spread the fibers and form a uniform oil film.
所述含氟PTT聚酯，是指苯环上的氢被氟取代的聚对苯二甲酸丙二醇酯，为聚四氟对苯二甲酸丙二醇酯，其结构通式为The fluorine-containing PTT polyester refers to polytrimethylene terephthalate in which the hydrogen on the benzene ring is replaced by fluorine, which is polytetrafluorotrimethylene terephthalate, and its general structural formula is
其中n=70～200。Among them, n=70～200.
所述含氟PTT聚酯熔体是指熔融后的含氟PTT聚酯，所述含氟PTT聚酯的制备方法分为酯化反应和缩聚反应两步；具体步骤为：The fluorine-containing PTT polyester melt refers to the melted fluorine-containing PTT polyester, and the preparation method of the fluorine-containing PTT polyester is divided into two steps of esterification reaction and polycondensation reaction; the specific steps are:
所述酯化反应：Described esterification reaction:
采用四氟对苯二甲酸和1,3-丙二醇作为原料，加入抑制剂，配成均匀浆料后进行酯化反应；酯化反应在氮气氛围中加压，压力控制在常压～0.3MPa，温度在250～260℃，酯化水馏出量达到理论值的90%以上为酯化反应终点；Tetrafluoroterephthalic acid and 1,3-propanediol are used as raw materials, and inhibitors are added to prepare a uniform slurry for esterification reaction; the esterification reaction is pressurized in a nitrogen atmosphere, and the pressure is controlled at normal pressure ~ 0.3MPa. The temperature is 250-260 ° C, and the distilled amount of esterification water reaches more than 90% of the theoretical value, which is the end point of the esterification reaction;
所述抑制剂为氧化镁、氧化硅、氧化钙、氧化锌和氧化锰中的一种；由于所用的二元羧酸的苯环上存在氟原子，氟原子的电负性大，在酯化反应阶段氟原子的共轭效应使得二元羧酸的酸性增强，同时导致二元羧酸中羧基的活性增大，使得反应速度加快，而反应速度增加容易使副反应产生，这些副反应产物对后续的缩聚反应有较大的影响，特别是生成烯烃和醛的封端产物，制约了产物分子量的增加；从实验结果来看，如果不加入抑制剂，合成的聚酯分子量偏低，不能满足纺丝和成膜的需求；抑制剂的加入用于控制酯化反应阶段的速度，减少了副反应，提高了产物的分子量，使得满足纺丝要求。Described suppressor is a kind of in magnesium oxide, silicon oxide, calcium oxide, zinc oxide and manganese oxide; Because there is fluorine atom on the benzene ring of dibasic carboxylic acid used, the electronegativity of fluorine atom is big, in esterification The conjugation effect of the fluorine atom in the reaction stage increases the acidity of the dicarboxylic acid, and at the same time increases the activity of the carboxyl group in the dicarboxylic acid, which speeds up the reaction rate, and the increase in the reaction rate is likely to cause side reactions. The follow-up polycondensation reaction has a greater impact, especially the generation of end-capped products of olefins and aldehydes, which restricts the increase in the molecular weight of the product; from the experimental results, if no inhibitor is added, the molecular weight of the synthesized polyester is low, which cannot meet the requirements. Spinning and film-forming requirements; the addition of inhibitors is used to control the speed of the esterification reaction stage, reducing side reactions, increasing the molecular weight of the product, and meeting the spinning requirements.
通常，聚酯酯化过程中是通过所用的二元羧酸电离出的氢离子作为酯化反应的催化剂，进行自催化反应，通过调节酯化反应的温度、压力以及小分子的排出来控制其酯化的速率，然而进行酯化反应的前提是要在一定的反应温度及压力下才可以进行酯化反应。温度过低或者压力不够的情况下，酯化反应不能够进行或者速度极慢，从而影响后续的工艺。若酯化反应中的小分子未能及时排出容易引起不必要的副反应。合成过程中，由于氟的共轭效应，在酯化反应阶段氟原子使得二元羧酸的酸性增强，同时导致二元羧酸中羧基的活性增大，使得反应速度加快，副反应增多，难以控制，进而影响产物分子量的增长，故加入抑制剂，即通过选择所用金属氧化物来调节。所述的金属氧化物可以按如下两种方式解离：Usually, in the polyester esterification process, the hydrogen ion ionized by the dicarboxylic acid used is used as a catalyst for the esterification reaction to carry out a self-catalyzed reaction, and the esterification reaction is controlled by adjusting the temperature, pressure and discharge of small molecules. However, the premise of the esterification reaction is that the esterification reaction can only be carried out under a certain reaction temperature and pressure. When the temperature is too low or the pressure is not enough, the esterification reaction cannot proceed or the speed is extremely slow, thereby affecting the subsequent process. If the small molecules in the esterification reaction are not discharged in time, it is easy to cause unnecessary side reactions. During the synthesis process, due to the conjugation effect of fluorine, the fluorine atom increases the acidity of the dicarboxylic acid in the esterification reaction stage, and at the same time increases the activity of the carboxyl group in the dicarboxylic acid, which makes the reaction speed faster and the side reactions increase. Control, and then affect the growth of the molecular weight of the product, so the addition of inhibitors is adjusted by selecting the metal oxide used. The metal oxide can be dissociated in the following two ways:
这里M为金属离子，如果M的电负性相当大，对氧离子的电子对有较强的吸引力，那么就能使O—H键减弱，有利于反应离解；相反，如果M的电负性小，那么就将生成碱中心。M—O—H和两性化合物相似，当有碱性物质存在时，反应将按酸式电离的方式进行；而当酸性物质存在时，则按碱式电离的方式进行。从酸式电离方式和碱式电离方式中逆反应的M-O-和M+可见，M+作为酸性中心，其强度仅和金属离子的电负性有直接的关系，而M-O-中的O离子作为碱中心的强度则和氧上的负电荷密度有关，负电荷密度愈大，强度也愈大。可见氧离子上的负电荷密度与金属离子电负性有着密切的关系，金属离子电负性越小，负电荷密度就越大。这样一来，金属氧化物的酸性以及碱性就都和金属离子的电负性联系起来了，金属离子的电负性大的氧化物主要是酸性，而电负性小的则是碱性。Here M is a metal ion. If the electronegativity of M is quite large and has a strong attraction to the electron pairs of oxygen ions, then the O—H bond can be weakened, which is conducive to the dissociation of the reaction; on the contrary, if the electronegativity of M If the sex is small, then the base center will be formed. M—O—H is similar to amphoteric compounds. When alkaline substances exist, the reaction will proceed in the form of acid ionization; when acidic substances exist, the reaction will proceed in the form of basic ionization. From the reverse reactions of MO - and M + in the acid ionization mode and base ionization mode, it can be seen that M + acts as an acidic center, and its strength is only directly related to the electronegativity of the metal ion, while the O ion in MO - acts as a base The intensity of the center is related to the negative charge density on the oxygen, the greater the negative charge density, the greater the intensity. It can be seen that the negative charge density on oxygen ions is closely related to the electronegativity of metal ions, the smaller the electronegativity of metal ions, the greater the negative charge density. In this way, the acidity and alkalinity of metal oxides are related to the electronegativity of metal ions. The oxides with high electronegativity of metal ions are mainly acidic, while those with low electronegativity are alkaline.
所述缩聚反应：Described polycondensation reaction:
包括缩聚反应低真空阶段和缩聚反应高真空阶段；Including the low vacuum stage of polycondensation reaction and the high vacuum stage of polycondensation reaction;
所述缩聚反应低真空阶段，在酯化产物中加入催化剂和稳定剂，在负压的条件下开始缩聚反应，该阶段压力由常压平稳抽至绝对压力500Pa以下，温度控制在260～270℃，反应时间为30～50分钟；In the low-vacuum stage of the polycondensation reaction, catalysts and stabilizers are added to the esterification product, and the polycondensation reaction starts under negative pressure conditions. In this stage, the pressure is steadily pumped from normal pressure to below the absolute pressure of 500Pa, and the temperature is controlled at 260-270°C. , the reaction time is 30 to 50 minutes;
所述缩聚反应高真空阶段，经所述缩聚反应低真空阶段后，继续抽真空，使反应压力降至绝对压力小于100Pa，反应温度控制在260～275℃，反应时间3～4小时。缩聚反应以反应釜搅拌电机功率或在线粘度计读数为准判断反应终点。In the high vacuum stage of the polycondensation reaction, after the low vacuum stage of the polycondensation reaction, the vacuum is continued to reduce the reaction pressure to an absolute pressure of less than 100 Pa, the reaction temperature is controlled at 260-275°C, and the reaction time is 3-4 hours. The polycondensation reaction is based on the power of the stirring motor of the reactor or the reading of the online viscometer to judge the end point of the reaction.
作为优选的技术方案：As a preferred technical solution:
如上所述的一种含氟PTT聚酯POY纤维的制备方法，所述的1,3-丙二醇与四氟对苯二甲酸的摩尔比为1.3～2.0:1。According to the above-mentioned preparation method of fluorine-containing PTT polyester POY fibers, the molar ratio of 1,3-propanediol to tetrafluoroterephthalic acid is 1.3-2.0:1.
如上所述的一种四氟PPT聚酯POY纤维的制备方法，所述的催化剂选自钛酸四丁酯—醋酸镁、钛酸四异丙脂—醋酸镁、钛酸四乙酯—醋酸镁、醋酸亚锡、二醋酸二丁基锡中的一种，催化剂用量为所述四氟对苯二甲酸重量的0.01%～0.05%。A kind of preparation method of tetrafluoroPPT polyester POY fiber as mentioned above, described catalyst is selected from tetrabutyl titanate-magnesium acetate, tetraisopropyl titanate-magnesium acetate, tetraethyl titanate-magnesium acetate , stannous acetate, dibutyltin diacetate, the amount of catalyst used is 0.01% to 0.05% of the weight of the tetrafluoroterephthalic acid.
如上所述的一种含氟PTT聚酯POY纤维的制备方法，所述的稳定剂选自磷酸三苯酯、磷酸三甲酯和亚磷酸三甲酯中的一种，稳定剂用量为所述四氟对苯二甲酸重量的0.01%～0.05%。A kind of preparation method of fluorine-containing PTT polyester POY fiber as described above, described stabilizer is selected from a kind of in triphenyl phosphate, trimethyl phosphate and trimethyl phosphite, and stabilizer dosage is described 0.01% to 0.05% of the weight of tetrafluoroterephthalic acid.
如上所述的一种含氟PTT聚酯POY纤维的制备方法，所述抑制剂的加入量为所述四氟对苯二甲酸重量的0.01%～0.05%。According to the method for preparing fluorine-containing PTT polyester POY fibers as described above, the added amount of the inhibitor is 0.01%-0.05% of the weight of the tetrafluoroterephthalic acid.
本发明的酯化反应阶段中，反应终点由酯化中实际产生的水馏出量达到理论值90%以上来掌握。理论值为按化学反应方程式完全反应时所得水的馏出量。由于酯化反应本身为可逆反应，再者原料在输送管道中会有残留，并且随着反应的进行，体系的粘度增加，会导致酯化反应产生的水难以从中排出。In the esterification reaction stage of the present invention, the end point of the reaction is determined by the fact that the amount of water distilled out in the esterification reaches more than 90% of the theoretical value. The theoretical value is the distilled amount of water obtained when the chemical reaction equation is completely reacted. Since the esterification reaction itself is a reversible reaction, and the raw materials will remain in the pipeline, and as the reaction progresses, the viscosity of the system will increase, making it difficult to discharge the water produced by the esterification reaction.
本发明的缩聚反应高真空阶段中，反应终点由反应釜搅拌器马达功率及在线粘度计算值达到设定的数值来掌握。不同的装置其反应釜搅拌器马达功率及在线粘度计算值的设定数值不一定相同，设定数值的确定可以通过对聚酯切片的分析来获得。In the high vacuum stage of the polycondensation reaction of the present invention, the end point of the reaction is determined by the calculated value of the motor power of the reactor stirrer and the online viscosity reaching the set value. The set values of the motor power of the reactor agitator and the online viscosity calculation value of different devices are not necessarily the same, and the determination of the set values can be obtained by analyzing the polyester chips.
本发明所得的新型含氟PTT聚酯POY纤维的单丝纤度为0.5～3.0dtex；断裂强度为1.8～2.5cN/dtex；断裂伸长率为100～130%。由于氟原子的引入，改善了聚酯材料的超疏水、憎水憎油、防污方面性能，在防水服，耐脏的工作服以及某些特殊行业的工作服制造中有巨大的前景。The monofilament fineness of the novel fluorine-containing PTT polyester POY fiber obtained by the invention is 0.5-3.0 dtex; the breaking strength is 1.8-2.5 cN/dtex; and the breaking elongation is 100-130%. Due to the introduction of fluorine atoms, the superhydrophobic, oil-repellent and anti-fouling properties of polyester materials have been improved, and it has great prospects in the manufacture of waterproof clothing, dirt-resistant work clothes and work clothes in some special industries.
有益效果：Beneficial effect:
1、所得新型含氟PTT聚酯POY纤维含氟原子，由于氟的强电负性，高的C-F键能以及对碳链的屏蔽保护作用使得最终制得的共聚酯POY纤维具有很好的耐热，耐老化，耐化学腐蚀及低电容，低可燃性，低折射率等性能，同时还具有某些特殊的电学性能，如低介电常数，高绝缘性等优点，扩展了应用范围。1. The obtained new fluorine-containing PTT polyester POY fiber contains fluorine atoms. Due to the strong electronegativity of fluorine, the high C-F bond energy and the shielding effect on the carbon chain, the final copolyester POY fiber has a good Heat resistance, aging resistance, chemical corrosion resistance and low capacitance, low flammability, low refractive index and other properties, but also has some special electrical properties, such as low dielectric constant, high insulation and other advantages, expanding the scope of application.
2、所得新型含氟PTT聚酯POY纤维具有一定的结构稳定性和可加工性。2. The obtained novel fluorine-containing PTT polyester POY fiber has certain structural stability and processability.
3、所得新型含氟PTT聚酯POY纤维通过采用引入氟原子，从而具有疏水防污的特性。3. The obtained novel fluorine-containing PTT polyester POY fiber has hydrophobic and anti-fouling properties by introducing fluorine atoms.
4、所得新型含氟PTT聚酯POY纤维通过采用共聚改性，从根本上解决了疏水防污聚酯的时效性、耐久性及耐磨性等问题。4. The obtained new fluorine-containing PTT polyester POY fiber is modified by copolymerization, which fundamentally solves the problems of timeliness, durability and wear resistance of hydrophobic and antifouling polyester.
具体实施方式Detailed ways
下面结合具体实施方式，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。The present invention will be further described below in combination with specific embodiments. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.
一种含氟PTT聚酯POY纤维，是由含氟PTT聚酯熔体经计量、挤出、冷却、上油和卷绕制得；所述含氟PTT聚酯苯环上的氢被氟取代的聚对苯二甲酸丙二醇酯，为聚四氟对苯二甲酸丙二醇酯，其结构通式为A fluorine-containing PTT polyester POY fiber, which is obtained by measuring, extruding, cooling, oiling and winding from a fluorine-containing PTT polyester melt; the hydrogen on the benzene ring of the fluorine-containing PTT polyester is replaced by fluorine The polytrimethylene terephthalate is polytetrafluorotrimethylene terephthalate, and its general structural formula is
其中n=70～200。Among them, n=70～200.
如上所述的一种含氟PTT聚酯POY纤维，所述含氟PTT聚酯POY纤维的单丝纤度为0.5～3.0dtex；断裂强度为1.8～2.5cN/dtex；断裂伸长率为100～130%。A kind of fluorine-containing PTT polyester POY fiber as described above, the monofilament fineness of the fluorine-containing PTT polyester POY fiber is 0.5-3.0dtex; the breaking strength is 1.8-2.5cN/dtex; the elongation at break is 100- 130%.
实施例1Example 1
一种含氟PTT聚酯的制备方法，分为酯化反应和缩聚反应两步。具体步骤为：A preparation method of fluorine-containing PTT polyester is divided into two steps of esterification reaction and polycondensation reaction. The specific steps are:
所述酯化反应：Described esterification reaction:
采用摩尔比为1.3:1的1,3丙二醇和四氟对苯二甲酸作为原料，同时加入四氟对苯二甲酸重量的0.05%的氧化镁，配成均匀浆料后进行酯化反应；酯化反应在氮气氛围中，压力控制在0.3MPa，温度控制在260℃，酯化水馏出量达到理论值的90%为酯化反应终点。Using 1,3 propanediol and tetrafluoroterephthalic acid with a molar ratio of 1.3:1 as raw materials, and adding 0.05% magnesium oxide based on the weight of tetrafluoroterephthalic acid at the same time, the esterification reaction is carried out after making a uniform slurry; The reaction is carried out in a nitrogen atmosphere, the pressure is controlled at 0.3MPa, the temperature is controlled at 260°C, and the distilled amount of esterification water reaches 90% of the theoretical value, which is the end point of the esterification reaction.
所述缩聚反应：Described polycondensation reaction:
包括缩聚反应低真空阶段和缩聚反应高真空阶段：Including low vacuum stage of polycondensation reaction and high vacuum stage of polycondensation reaction:
所述缩聚反应低真空阶段，在酯化产物中加入四氟对苯二甲酸重量的0.01%的催化剂钛酸四丁酯—醋酸镁和四氟对苯二甲酸重量的0.01%的稳定剂磷酸三苯酯，在负压的条件下开始缩聚反应，该阶段压力由常压平稳抽至绝对压力小于500Pa，温度控制在265℃，反应时间为50分钟。In the low-vacuum stage of the polycondensation reaction, 0.01% of the catalyst tetrabutyl titanate-magnesium acetate and 0.01% of the tetrafluoroterephthalic acid weight of the tetrafluoroterephthalic acid were added to the esterification product. The polycondensation reaction of phenyl ester starts under the condition of negative pressure. At this stage, the pressure is steadily pumped from normal pressure to an absolute pressure of less than 500Pa, the temperature is controlled at 265°C, and the reaction time is 50 minutes.
所述缩聚反应高真空阶段，经所述缩聚反应低真空阶段后，继续抽真空，使反应压力降至绝对压力小于100Pa，反应温度控制在270℃，反应时间4小时。缩聚反应以反应釜搅拌电机功率或在线粘度计读数为准判断反应终点。In the high vacuum stage of the polycondensation reaction, after the low vacuum stage of the polycondensation reaction, the vacuum is continued to reduce the reaction pressure to an absolute pressure of less than 100 Pa, the reaction temperature is controlled at 270° C., and the reaction time is 4 hours. The polycondensation reaction is based on the power of the stirring motor of the reactor or the reading of the online viscometer to judge the end point of the reaction.
制备POY纤维的方法：Method for preparing POY fiber:
是由所述含氟PTT聚酯熔体直接挤出、冷却、上油和卷绕制得POY纤维；其中，所述挤出的温度为265℃；所述的冷却为侧吹风冷却，温度为25℃，相对湿度为60%，风速为0.4m/s；所述上油采用含有8wt%的含氟聚酯POY纤维用油剂的乳液；含氟聚酯POY纤维用油剂的制备：其组分按重量份计，取60份丙二醇无规聚醚，加热到60℃，将20份聚乙二醇月桂酸单酯、15份十二烷基磷酸酯钾盐和5份全氟丁基乙基丙烯酸酯搅拌混合均匀，然后加入到丙二醇无规聚醚中，搅拌1个小时，即得到含氟聚酯纤维用POY油剂；所述上油的上油率为0.42%；所述卷绕的速度为2700m/min；最终制得含氟PTT聚酯POY纤维，单丝纤度为3.0dtex；断裂强度为1.8cN/dtex；断裂伸长率为130%。The POY fiber is obtained by directly extruding, cooling, oiling and winding the fluorine-containing PTT polyester melt; wherein, the extruding temperature is 265°C; the cooling is side blowing cooling, and the temperature is 25 ℃, relative humidity is 60%, wind speed is 0.4m/s; The described oiling adopts the emulsion that contains the oil agent for fluorine-containing polyester POY fiber of 8wt%; The preparation of oil agent for fluorine-containing polyester POY fiber: its Components in parts by weight, take 60 parts of propylene glycol random polyether, heat to 60°C, mix 20 parts of polyethylene glycol monolaurate, 15 parts of potassium dodecyl phosphate and 5 parts of perfluorobutyl Ethyl acrylate was stirred and mixed evenly, then added to propylene glycol random polyether, and stirred for 1 hour to obtain POY oiling agent for fluorine-containing polyester fibers; the oiling rate of the oiling was 0.42%; the roll The winding speed is 2700m/min; the fluorine-containing PTT polyester POY fiber is finally obtained, the single filament fineness is 3.0dtex; the breaking strength is 1.8cN/dtex; the breaking elongation is 130%.
实施例2Example 2
一种含氟PTT聚酯的制备方法，分为酯化反应和缩聚反应两步。具体步骤为：A preparation method of fluorine-containing PTT polyester is divided into two steps of esterification reaction and polycondensation reaction. The specific steps are:
所述酯化反应：Described esterification reaction:
采用摩尔比为1.4:1的1,3丙二醇和四氟对苯二甲酸作为原料，同时加入四氟对苯二甲酸重量的0.04%的氧化锰，配成均匀浆料后进行酯化反应；酯化反应在氮气氛围中，压力控制在0.3MPa，温度控制在260℃，酯化水馏出量达到理论值的90%为酯化反应终点。1,3 propanediol and tetrafluoroterephthalic acid with a molar ratio of 1.4:1 are used as raw materials, and 0.04% manganese oxide by weight of tetrafluoroterephthalic acid is added at the same time, and the esterification reaction is carried out after making a uniform slurry; The reaction is carried out in a nitrogen atmosphere, the pressure is controlled at 0.3MPa, the temperature is controlled at 260°C, and the distilled amount of esterification water reaches 90% of the theoretical value, which is the end point of the esterification reaction.
所述缩聚反应：Described polycondensation reaction:
包括缩聚反应低真空阶段和缩聚反应高真空阶段：Including low vacuum stage of polycondensation reaction and high vacuum stage of polycondensation reaction:
所述缩聚反应低真空阶段，在酯化产物中加入四氟对苯二甲酸重量的0.02%的催化剂钛酸四异丙脂—醋酸镁和四氟对苯二甲酸重量的0.02%的稳定剂磷酸三苯酯，在负压的条件下开始缩聚反应，该阶段压力由常压平稳抽至绝对压力小于400Pa，温度控制在265℃，反应时间为50分钟。In the low-vacuum stage of the polycondensation reaction, add 0.02% of the catalyst tetraisopropyl titanate-magnesium acetate and 0.02% of the tetrafluoroterephthalic acid weight in the esterification product. Stabilizer phosphoric acid Triphenyl ester, the polycondensation reaction starts under the condition of negative pressure, the pressure is steadily pumped from normal pressure to the absolute pressure less than 400Pa at this stage, the temperature is controlled at 265°C, and the reaction time is 50 minutes.
所述缩聚反应高真空阶段，经所述缩聚反应低真空阶段后，继续抽真空，使反应压力降至绝对压力小于100Pa，反应温度控制在270℃，反应时间4小时。缩聚反应以反应釜搅拌电机功率或在线粘度计读数为准判断反应终点。In the high vacuum stage of the polycondensation reaction, after the low vacuum stage of the polycondensation reaction, the vacuum is continued to reduce the reaction pressure to an absolute pressure of less than 100 Pa, the reaction temperature is controlled at 270° C., and the reaction time is 4 hours. The polycondensation reaction is based on the power of the stirring motor of the reactor or the reading of the online viscometer to judge the end point of the reaction.
制备POY纤维的方法：Method for preparing POY fiber:
是由所述含氟PTT聚酯熔体直接挤出、冷却、上油和卷绕制得POY纤维；其中，所述挤出的温度为285℃；所述的冷却为侧吹风冷却，温度为20℃，相对湿度为70%，风速为0.8m/s；所述上油采用含有9wt%的含氟聚酯POY纤维用油剂的乳液；含氟聚酯POY纤维用油剂的制备：其组分按重量份计，取50份丁醇无规聚醚，加热到40℃，将32份聚乙二醇月桂酸双酯、15份异构十三醇聚氧乙烯醚磷酸酯钾盐和3份全氟己基乙基丙烯酸酯搅拌混合均匀，然后加入到丁醇无规聚醚中，搅拌2个小时，即得到含氟聚酯纤维用POY油剂；所述上油的上油率为1.5%；所述卷绕的速度为2800m/min；最终制得含氟PTT聚酯POY纤维，单丝纤度为2.0dtex；断裂强度为2.0cN/dtex；断裂伸长率为125%。The POY fiber is obtained by directly extruding, cooling, oiling and winding the fluorine-containing PTT polyester melt; wherein, the extruding temperature is 285°C; the cooling is side blowing cooling, and the temperature is 20 ℃, relative humidity is 70%, and wind speed is 0.8m/s; The described oiling adopts the emulsion that contains 9wt% the oil agent for fluorine-containing polyester POY fiber; The preparation of oil agent for fluorine-containing polyester POY fiber: its Components are calculated in parts by weight, take 50 parts of butanol random polyether, heat to 40 ° C, mix 32 parts of polyethylene glycol laurate diester, 15 parts of isomeric tridecyl alcohol polyoxyethylene ether phosphate potassium salt and 3 parts of perfluorohexyl ethyl acrylate were stirred and mixed evenly, then added to butanol random polyether, and stirred for 2 hours to obtain POY oil for fluorine-containing polyester fibers; the oiling rate of the oiling was 1.5%; the winding speed is 2800m/min; the fluorine-containing PTT polyester POY fiber is finally obtained, the single filament fineness is 2.0dtex; the breaking strength is 2.0cN/dtex; the elongation at break is 125%.
实施例3Example 3
一种含氟PTT聚酯的制备方法，分为酯化反应和缩聚反应两步。具体步骤为：A preparation method of fluorine-containing PTT polyester is divided into two steps of esterification reaction and polycondensation reaction. The specific steps are:
所述酯化反应：Described esterification reaction:
采用摩尔比为1.6:1的1,3丙二醇和四氟对苯二甲酸作为原料，同时加入四氟对苯二甲酸重量的0.03%的氧化锌，配成均匀浆料后进行酯化反应；酯化反应在氮气氛围中，压力控制在0.2MPa，温度控制在255℃，酯化水馏出量达到理论值的90%为酯化反应终点。1,3 propanediol and tetrafluoroterephthalic acid with a molar ratio of 1.6:1 are used as raw materials, and 0.03% of the weight of tetrafluoroterephthalic acid is added at the same time. Zinc oxide is made into a uniform slurry and then esterified; The reaction is carried out in a nitrogen atmosphere, the pressure is controlled at 0.2MPa, the temperature is controlled at 255°C, and the distilled amount of esterification water reaches 90% of the theoretical value, which is the end point of the esterification reaction.
所述缩聚反应：Described polycondensation reaction:
包括缩聚反应低真空阶段和缩聚反应高真空阶段：Including low vacuum stage of polycondensation reaction and high vacuum stage of polycondensation reaction:
所述缩聚反应低真空阶段，在酯化产物中加入四氟对苯二甲酸重量的0.03%的催化剂钛酸四乙酯—醋酸镁和四氟对苯二甲酸重量的0.03%的稳定剂磷酸三甲酯，在负压的条件下开始缩聚反应，该阶段压力由常压平稳抽至绝对压力小于400Pa，温度控制在260℃，反应时间为45分钟。In the low vacuum stage of the polycondensation reaction, add 0.03% of the catalyst tetraethyl titanate-magnesium acetate and 0.03% of the tetrafluoroterephthalic acid weight in the esterification product. Methyl ester, polycondensation reaction starts under the condition of negative pressure. At this stage, the pressure is steadily pumped from normal pressure to an absolute pressure of less than 400Pa, the temperature is controlled at 260°C, and the reaction time is 45 minutes.
所述缩聚反应高真空阶段，经所述缩聚反应低真空阶段后，继续抽真空，使反应压力降至绝对压力小于80Pa，反应温度控制在270℃，反应时间3.5小时。缩聚反应以反应釜搅拌电机功率或在线粘度计读数为准判断反应终点。In the high vacuum stage of the polycondensation reaction, after the low vacuum stage of the polycondensation reaction, the vacuum was continued to reduce the reaction pressure to an absolute pressure of less than 80 Pa, the reaction temperature was controlled at 270° C., and the reaction time was 3.5 hours. The polycondensation reaction is based on the power of the stirring motor of the reactor or the reading of the online viscometer to judge the end point of the reaction.
制备POY纤维的方法：Method for preparing POY fiber:
是由所述含氟PTT聚酯熔体直接挤出、冷却、上油和卷绕制得POY纤维；其中，所述挤出的温度为275℃；所述的冷却为侧吹风冷却，温度为22℃，相对湿度为65%，风速为0.6m/s；所述上油采用含有10wt%的含氟聚酯POY纤维用油剂的乳液；含氟聚酯POY纤维用油剂的制备：其组分按重量份计，取58份月桂酸无规聚醚，加热到60℃，将30份聚乙二醇油酸单酯、10份十二十四醇磷酸酯钾盐和2份全氟辛基乙基丙烯酸酯搅拌混合均匀，然后加入到丙二醇无规聚醚中，搅拌1个小时，即得到含氟聚酯纤维用POY油剂；所述上油的上油率为0.96%；所述卷绕的速度为2900m/min；最终制得含氟PTT聚酯POY纤维，单丝纤度为1.5dtex；断裂强度为2.2cN/dtex；断裂伸长率为120%。The POY fiber is obtained by directly extruding, cooling, oiling and winding the fluorine-containing PTT polyester melt; wherein, the extruding temperature is 275°C; the cooling is side blowing cooling, and the temperature is 22 ℃, relative humidity is 65%, and wind speed is 0.6m/s; The described oiling adopts the emulsion that contains 10wt% the oil agent for fluorine-containing polyester POY fiber; The preparation of oil agent for fluorine-containing polyester POY fiber: its Components in parts by weight, take 58 parts of lauric acid random polyether, heat to 60 ° C, add 30 parts of polyethylene glycol monooleate, 10 parts of potassium salt of tetradecyl alcohol phosphate and 2 parts of perfluoro Octyl ethyl acrylate was stirred and mixed evenly, then added to propylene glycol random polyether, and stirred for 1 hour to obtain POY oil for fluorine-containing polyester fibers; the oiling rate of the oiling was 0.96%; The above-mentioned winding speed is 2900m/min; the fluorine-containing PTT polyester POY fiber is finally obtained, the single filament fineness is 1.5dtex; the breaking strength is 2.2cN/dtex; the breaking elongation is 120%.
实施例4Example 4
一种含氟PTT聚酯的制备方法，分为酯化反应和缩聚反应两步。具体步骤为：A preparation method of fluorine-containing PTT polyester is divided into two steps of esterification reaction and polycondensation reaction. The specific steps are:
所述酯化反应：Described esterification reaction:
采用摩尔比为1.8:1的1,3丙二醇和四氟对苯二甲酸作为原料，同时加入四氟对苯二甲酸重量的0.02%的氧化钙，配成均匀浆料后进行酯化反应；酯化反应在氮气氛围中，压力控制在0.2MPa，温度控制在250℃，酯化水馏出量达到理论值的90%为酯化反应终点。1,3 propanediol and tetrafluoroterephthalic acid with a molar ratio of 1.8:1 are used as raw materials, and 0.02% calcium oxide of the weight of tetrafluoroterephthalic acid is added at the same time, and the esterification reaction is carried out after making a uniform slurry; The reaction is carried out in a nitrogen atmosphere, the pressure is controlled at 0.2MPa, the temperature is controlled at 250°C, and the distilled amount of esterification water reaches 90% of the theoretical value, which is the end point of the esterification reaction.
所述缩聚反应：Described polycondensation reaction:
包括缩聚反应低真空阶段和缩聚反应高真空阶段：Including low vacuum stage of polycondensation reaction and high vacuum stage of polycondensation reaction:
所述缩聚反应低真空阶段，在酯化产物中加入四氟对苯二甲酸重量的0.04%的催化剂醋酸亚锡和四氟对苯二甲酸重量的0.04%的稳定剂磷酸三甲酯，在负压的条件下开始缩聚反应，该阶段压力由常压平稳抽至绝对压力小于300Pa，温度控制在270℃，反应时间为40分钟。In the low vacuum stage of the polycondensation reaction, add 0.04% of the catalyst stannous acetate of tetrafluoroterephthalic acid weight and 0.04% of the stabilizer trimethyl phosphate of tetrafluoroterephthalic acid weight in the esterification product, The polycondensation reaction starts under the condition of low pressure, and the pressure at this stage is steadily pumped from normal pressure to an absolute pressure of less than 300Pa, the temperature is controlled at 270°C, and the reaction time is 40 minutes.
所述缩聚反应高真空阶段，经所述缩聚反应低真空阶段后，继续抽真空，使反应压力降至绝对压力小于60Pa，反应温度控制在275℃，反应时间3小时。缩聚反应以反应釜搅拌电机功率或在线粘度计读数为准判断反应终点。In the high vacuum stage of the polycondensation reaction, after the low vacuum stage of the polycondensation reaction, the vacuum is continued to reduce the reaction pressure to an absolute pressure of less than 60 Pa, the reaction temperature is controlled at 275° C., and the reaction time is 3 hours. The polycondensation reaction is based on the power of the stirring motor of the reactor or the reading of the online viscometer to judge the end point of the reaction.
制备POY纤维的方法：Method for preparing POY fiber:
是由所述含氟PTT聚酯熔体直接挤出、冷却、上油和卷绕制得POY纤维；其中，所述挤出的温度为265℃；所述的冷却为侧吹风冷却，温度为25℃，相对湿度为60%，风速为0.4m/s；所述上油采用含有8wt%的含氟聚酯POY纤维用油剂的乳液；含氟聚酯POY纤维用油剂的制备：其组分按重量份计，取50份十二醇无规聚醚，加热到50℃，将32份聚乙二醇油酸双酯、13份十二烷基磷酸酯钾盐和5份全氟丁基乙基甲基丙烯酸酯搅拌混合均匀，然后加入到丙二醇无规聚醚中，搅拌1个小时，即得到含氟聚酯纤维用POY油剂；所述上油的上油率为1.5%；所述卷绕的速度为3000m/min；最终制得含氟PTT聚酯POY纤维，单丝纤度为1.5dtex；断裂强度为2.3cN/dtex；断裂伸长率为110%。The POY fiber is obtained by directly extruding, cooling, oiling and winding the fluorine-containing PTT polyester melt; wherein, the extruding temperature is 265°C; the cooling is side blowing cooling, and the temperature is 25 ℃, relative humidity is 60%, wind speed is 0.4m/s; The described oiling adopts the emulsion that contains the oil agent for fluorine-containing polyester POY fiber of 8wt%; The preparation of oil agent for fluorine-containing polyester POY fiber: its The components are calculated in parts by weight. Take 50 parts of lauryl alcohol random polyether, heat it to 50°C, add 32 parts of polyethylene glycol diester oleate, 13 parts of potassium dodecyl phosphate and 5 parts of perfluorinated Butyl ethyl methacrylate is stirred and mixed evenly, then added to propylene glycol random polyether, and stirred for 1 hour to obtain POY oil for fluorine-containing polyester fibers; the oiling rate of the oiling is 1.5% ; The winding speed is 3000m/min; finally obtained fluorine-containing PTT polyester POY fiber, the single filament fineness is 1.5dtex; the breaking strength is 2.3cN/dtex; the elongation at break is 110%.
实施例5Example 5
一种含氟PTT聚酯的制备方法，分为酯化反应和缩聚反应两步。具体步骤为：A preparation method of fluorine-containing PTT polyester is divided into two steps of esterification reaction and polycondensation reaction. The specific steps are:
所述酯化反应：Described esterification reaction:
采用摩尔比为2.0:1的1,3丙二醇和四氟对苯二甲酸作为原料，同时加入四氟对苯二甲酸重量的0.01%的氧化硅，配成均匀浆料后进行酯化反应；酯化反应在氮气氛围中，压力控制在常压，温度控制在255℃，酯化水馏出量达到理论值的90%为酯化反应终点。1,3 propanediol and tetrafluoroterephthalic acid with a molar ratio of 2.0:1 are used as raw materials, and 0.01% of the weight of tetrafluoroterephthalic acid is added at the same time. Silicon oxide is made into a uniform slurry and then esterified; The reaction is carried out in a nitrogen atmosphere, the pressure is controlled at normal pressure, the temperature is controlled at 255°C, and the esterification water distillation reaches 90% of the theoretical value, which is the end point of the esterification reaction.
所述缩聚反应：Described polycondensation reaction:
包括缩聚反应低真空阶段和缩聚反应高真空阶段：Including low vacuum stage of polycondensation reaction and high vacuum stage of polycondensation reaction:
所述缩聚反应低真空阶段，在酯化产物中加入四氟对苯二甲酸重量的0.05%的催化剂二醋酸二丁基锡和四氟对苯二甲酸重量的0.05%的稳定剂亚磷酸三甲酯，在负压的条件下开始缩聚反应，该阶段压力由常压平稳抽至绝对压力小于300Pa，温度控制在265℃，反应时间为30分钟。In the low vacuum stage of the polycondensation reaction, add 0.05% of the catalyst dibutyltin diacetate and 0.05% of the weight of tetrafluoroterephthalic acid in the esterification product. Stabilizer trimethyl phosphite, The polycondensation reaction starts under the condition of negative pressure, and the pressure in this stage is steadily pumped from normal pressure to an absolute pressure of less than 300Pa, the temperature is controlled at 265°C, and the reaction time is 30 minutes.
所述缩聚反应高真空阶段，经所述缩聚反应低真空阶段后，继续抽真空，使反应压力降至绝对压力小于50Pa，反应温度控制在275℃，反应时间3小时。缩聚反应以反应釜搅拌电机功率或在线粘度计读数为准判断反应终点。In the high vacuum stage of the polycondensation reaction, after the low vacuum stage of the polycondensation reaction, the vacuum is continued to reduce the reaction pressure to an absolute pressure of less than 50 Pa, the reaction temperature is controlled at 275° C., and the reaction time is 3 hours. The polycondensation reaction is based on the power of the stirring motor of the reactor or the reading of the online viscometer to judge the end point of the reaction.
制备POY纤维的方法：Method for preparing POY fiber:
是由所述含氟PTT聚酯熔体直接挤出、冷却、上油和卷绕制得POY纤维；其中，所述挤出的温度为285℃；所述的冷却为侧吹风冷却，温度为20℃，相对湿度为70%，风速为0.8m/s；所述上油采用含有8wt%的含氟聚酯POY纤维用油剂的乳液；含氟聚酯POY纤维用油剂的制备：其组分按重量份计，取55份异构十三醇无规聚醚，加热到55℃，将25份聚乙二醇月桂酸双酯、15份十二烷基磷酸酯钾盐和5份全氟己基乙基甲基丙烯酸酯搅拌混合均匀，然后加入到丙二醇无规聚醚中，搅拌2个小时，即得到含氟聚酯纤维用POY油剂；所述上油的上油率为0.42%；所述卷绕的速度为3200m/min；最终制得含氟PTT聚酯POY纤维，单丝纤度为0.5dtex；断裂强度为2.5cN/dtex；断裂伸长率为100%。The POY fiber is obtained by directly extruding, cooling, oiling and winding the fluorine-containing PTT polyester melt; wherein, the extruding temperature is 285°C; the cooling is side blowing cooling, and the temperature is 20 DEG C, relative humidity is 70%, and wind speed is 0.8m/s; Described oiling adopts the emulsion that contains the oil agent for fluorine-containing polyester POY fiber of 8wt%; The preparation of oil agent for fluorine-containing polyester POY fiber: its Components in parts by weight, take 55 parts of isomeric tridecanol random polyether, heat to 55 ° C, mix 25 parts of polyethylene glycol diester laurate, 15 parts of potassium lauryl phosphate and 5 parts Perfluorohexyl ethyl methacrylate was stirred and mixed evenly, then added to propylene glycol random polyether, and stirred for 2 hours to obtain POY oil for fluorine-containing polyester fibers; the oiling rate of the oiling was 0.42 %; the winding speed is 3200m/min; the final fluorine-containing PTT polyester POY fiber is obtained, the single filament fineness is 0.5dtex; the breaking strength is 2.5cN/dtex; the elongation at break is 100%.
实施例6Example 6
一种含氟PTT聚酯的制备方法，分为酯化反应和缩聚反应两步。具体步骤为：A preparation method of fluorine-containing PTT polyester is divided into two steps of esterification reaction and polycondensation reaction. The specific steps are:
所述酯化反应：Described esterification reaction:
采用摩尔比为1.3:1的1,3丙二醇和四氟对苯二甲酸作为原料，同时加入四氟对苯二甲酸重量的0.01%的氧化镁，配成均匀浆料后进行酯化反应；酯化反应在氮气氛围中，压力控制在0.3MPa，温度控制在260℃，酯化水馏出量达到理论值的90%为酯化反应终点。1,3 propanediol and tetrafluoroterephthalic acid with a molar ratio of 1.3:1 are used as raw materials, and magnesium oxide of 0.01% of the weight of tetrafluoroterephthalic acid is added at the same time, and the esterification reaction is carried out after making a uniform slurry; The reaction is carried out in a nitrogen atmosphere, the pressure is controlled at 0.3MPa, the temperature is controlled at 260°C, and the distilled amount of esterification water reaches 90% of the theoretical value, which is the end point of the esterification reaction.
所述缩聚反应：Described polycondensation reaction:
包括缩聚反应低真空阶段和缩聚反应高真空阶段：Including low vacuum stage of polycondensation reaction and high vacuum stage of polycondensation reaction:
所述缩聚反应低真空阶段，在酯化产物中加入四氟对苯二甲酸重量的0.01%的催化剂钛酸四丁酯—醋酸镁和四氟对苯二甲酸重量的0.01%的稳定剂磷酸三苯酯，在负压的条件下开始缩聚反应，该阶段压力由常压平稳抽至绝对压力小于500Pa，温度控制在265℃，反应时间为50分钟。In the low-vacuum stage of the polycondensation reaction, 0.01% of the catalyst tetrabutyl titanate-magnesium acetate and 0.01% of the tetrafluoroterephthalic acid weight of the tetrafluoroterephthalic acid were added to the esterification product. The polycondensation reaction of phenyl ester starts under the condition of negative pressure. At this stage, the pressure is steadily pumped from normal pressure to an absolute pressure of less than 500Pa, the temperature is controlled at 265°C, and the reaction time is 50 minutes.
所述缩聚反应高真空阶段，经所述缩聚反应低真空阶段后，继续抽真空，使反应压力降至绝对压力小于100Pa，反应温度控制在270℃，反应时间4小时。缩聚反应以反应釜搅拌电机功率或在线粘度计读数为准判断反应终点。当聚合物粘度达到所需值时出料，经铸带、冷却、切粒，即得到含氟PTT聚酯切片。In the high vacuum stage of the polycondensation reaction, after the low vacuum stage of the polycondensation reaction, the vacuum is continued to reduce the reaction pressure to an absolute pressure of less than 100 Pa, the reaction temperature is controlled at 270° C., and the reaction time is 4 hours. The polycondensation reaction is based on the power of the stirring motor of the reactor or the reading of the online viscometer to judge the end point of the reaction. When the viscosity of the polymer reaches the desired value, the material is discharged, and after casting, cooling, and pelletizing, the fluorine-containing PTT polyester chips are obtained.
制备POY纤维的方法：Method for preparing POY fiber:
是由所述含氟PTT聚酯切片经螺杆熔融挤出、冷却、上油和卷绕制得POY纤维；其中，所述挤出的温度为265℃；所述的冷却为环吹风冷却，温度为25℃，相对湿度为60%，风速为0.4m/s；所述上油采用含有8wt%的含氟聚酯POY纤维用油剂的乳液；含氟聚酯POY纤维用油剂的制备：其组分按重量份计，取60份丙二醇无规聚醚，加热到45℃，将20份聚乙二醇油酸单酯、15份十二烷基磷酸酯钾盐和5份全氟辛基乙基甲基丙烯酸酯搅拌混合均匀，然后加入到丙二醇无规聚醚中，搅拌1个小时，即得到含氟聚酯纤维用POY油剂；所述上油的上油率为0.42%；所述卷绕的速度为2700m/min；最终制得含氟PTT聚酯POY纤维，单丝纤度为3.0dtex；断裂强度为1.8cN/dtex；断裂伸长率为130%。The POY fiber is obtained from the fluorine-containing PTT polyester chips through screw melt extrusion, cooling, oiling and winding; wherein, the extruding temperature is 265°C; the cooling is ring blowing cooling, the temperature The temperature is 25°C, the relative humidity is 60%, and the wind speed is 0.4m/s; the oiling adopts an emulsion containing 8wt% fluorine-containing polyester POY fiber oil; the preparation of fluorine-containing polyester POY fiber oil: Its components are calculated in parts by weight. Take 60 parts of propylene glycol random polyether, heat it to 45°C, add 20 parts of polyethylene glycol monooleate, 15 parts of potassium dodecyl phosphate and 5 parts of perfluorooctyl Ethyl methacrylate was stirred and mixed uniformly, then added to propylene glycol random polyether, and stirred for 1 hour to obtain POY oil for fluorine-containing polyester fibers; the oiling rate of the oiling was 0.42%; The winding speed is 2700m/min; the fluorine-containing PTT polyester POY fiber is finally obtained, the single filament fineness is 3.0dtex; the breaking strength is 1.8cN/dtex; the breaking elongation is 130%.
实施例7Example 7
一种含氟PTT聚酯的制备方法，分为酯化反应和缩聚反应两步。具体步骤为：A preparation method of fluorine-containing PTT polyester is divided into two steps of esterification reaction and polycondensation reaction. The specific steps are:
所述酯化反应：Described esterification reaction:
采用摩尔比为1.4:1的1,3丙二醇和四氟对苯二甲酸作为原料，同时加入四氟对苯二甲酸重量的0.05%的氧化硅，配成均匀浆料后进行酯化反应；酯化反应在氮气氛围中，压力控制在0.3MPa，温度控制在260℃，酯化水馏出量达到理论值的90%为酯化反应终点。Using 1,3 propanediol and tetrafluoroterephthalic acid with a molar ratio of 1.4:1 as raw materials, and adding 0.05% of the weight of tetrafluoroterephthalic acid silicon oxide at the same time, after making a uniform slurry, carry out esterification reaction; The reaction is carried out in a nitrogen atmosphere, the pressure is controlled at 0.3MPa, the temperature is controlled at 260°C, and the distilled amount of esterification water reaches 90% of the theoretical value, which is the end point of the esterification reaction.
所述缩聚反应：Described polycondensation reaction:
包括缩聚反应低真空阶段和缩聚反应高真空阶段：Including low vacuum stage of polycondensation reaction and high vacuum stage of polycondensation reaction:
所述缩聚反应低真空阶段，在酯化产物中加入四氟对苯二甲酸重量的0.02%的催化剂钛酸四异丙脂—醋酸镁和四氟对苯二甲酸重量的0.02%的稳定剂磷酸三苯酯，在负压的条件下开始缩聚反应，该阶段压力由常压平稳抽至绝对压力小于400Pa，温度控制在265℃，反应时间为50分钟。In the low-vacuum stage of the polycondensation reaction, add 0.02% of the catalyst tetraisopropyl titanate-magnesium acetate and 0.02% of the tetrafluoroterephthalic acid weight in the esterification product. Stabilizer phosphoric acid Triphenyl ester, the polycondensation reaction starts under the condition of negative pressure, the pressure is steadily pumped from normal pressure to the absolute pressure less than 400Pa at this stage, the temperature is controlled at 265°C, and the reaction time is 50 minutes.
所述缩聚反应高真空阶段，经所述缩聚反应低真空阶段后，继续抽真空，使反应压力降至绝对压力小于100Pa，反应温度控制在270℃，反应时间4小时。缩聚反应以反应釜搅拌电机功率或在线粘度计读数为准判断反应终点。当聚合物粘度达到所需值时出料，经铸带、冷却、切粒，即得到含氟PTT聚酯切片。In the high vacuum stage of the polycondensation reaction, after the low vacuum stage of the polycondensation reaction, the vacuum is continued to reduce the reaction pressure to an absolute pressure of less than 100 Pa, the reaction temperature is controlled at 270° C., and the reaction time is 4 hours. The polycondensation reaction is based on the power of the stirring motor of the reactor or the reading of the online viscometer to judge the end point of the reaction. When the viscosity of the polymer reaches the desired value, the material is discharged, and after casting, cooling, and pelletizing, the fluorine-containing PTT polyester chips are obtained.
制备POY纤维的方法：Method for preparing POY fiber:
是由所述含氟PTT聚酯切片经螺杆熔融挤出、冷却、上油和卷绕制得POY纤维；其中，所述挤出的温度为285℃；所述的冷却为环吹风冷却，温度为20℃，相对湿度为70%，风速为0.8m/s；所述上油采用含有8wt%的含氟聚酯POY纤维用油剂的乳液；含氟聚酯POY纤维用油剂的制备：其组分按重量份计，取50份丁醇无规聚醚，加热到40℃，将32份聚乙二醇月桂酸双酯、15份异构十三醇聚氧乙烯醚磷酸酯钾盐和3份全氟己基乙基丙烯酸酯搅拌混合均匀，然后加入到丁醇无规聚醚中，搅拌2个小时，即得到含氟聚酯纤维用POY油剂；所述上油的上油率为1.5%；所述卷绕的速度为2800m/min；最终制得含氟PTT聚酯POY纤维，单丝纤度为2.0dtex；断裂强度为2.0cN/dtex；断裂伸长率为125%。The POY fiber is obtained from the fluorine-containing PTT polyester chips through screw melt extrusion, cooling, oiling and winding; wherein, the extruding temperature is 285°C; the cooling is ring air cooling, the temperature The temperature is 20°C, the relative humidity is 70%, and the wind speed is 0.8m/s; the oiling adopts an emulsion containing 8wt% fluorine-containing polyester POY fiber oil; the preparation of fluorine-containing polyester POY fiber oil: Its components are calculated in parts by weight. Take 50 parts of butanol random polyether, heat it to 40 ° C, mix 32 parts of polyethylene glycol laurate diester, 15 parts of isomeric tridecyl polyoxyethylene ether phosphate potassium salt Stir and mix with 3 parts of perfluorohexyl ethyl acrylate, then add it into butanol random polyether, and stir for 2 hours to obtain POY oiling agent for fluorine-containing polyester fibers; the oiling rate of the oiling 1.5%; the winding speed is 2800m/min; finally fluorine-containing PTT polyester POY fiber is obtained, the single filament fineness is 2.0dtex; the breaking strength is 2.0cN/dtex; the elongation at break is 125%.
实施例8Example 8
一种含氟PTT聚酯的制备方法，分为酯化反应和缩聚反应两步。具体步骤为：A preparation method of fluorine-containing PTT polyester is divided into two steps of esterification reaction and polycondensation reaction. The specific steps are:
所述酯化反应：Described esterification reaction:
采用摩尔比为1.6:1的1,3丙二醇和四氟对苯二甲酸作为原料，同时加入四氟对苯二甲酸重量的0.04%的氧化钙，配成均匀浆料后进行酯化反应；酯化反应在氮气氛围中，压力控制在0.2MPa，温度控制在255℃，酯化水馏出量达到理论值的90%为酯化反应终点。1,3 propanediol and tetrafluoroterephthalic acid with a molar ratio of 1.6:1 are used as raw materials, and 0.04% calcium oxide of the weight of tetrafluoroterephthalic acid is added at the same time, and the esterification reaction is carried out after making a uniform slurry; The reaction is carried out in a nitrogen atmosphere, the pressure is controlled at 0.2MPa, the temperature is controlled at 255°C, and the distilled amount of esterification water reaches 90% of the theoretical value, which is the end point of the esterification reaction.
所述缩聚反应：Described polycondensation reaction:
包括缩聚反应低真空阶段和缩聚反应高真空阶段：Including low vacuum stage of polycondensation reaction and high vacuum stage of polycondensation reaction:
所述缩聚反应低真空阶段，在酯化产物中加入四氟对苯二甲酸重量的0.03%的催化剂钛酸四乙酯—醋酸镁和四氟对苯二甲酸重量的0.03%的稳定剂磷酸三甲酯，在负压的条件下开始缩聚反应，该阶段压力由常压平稳抽至绝对压力小于400Pa，温度控制在260℃，反应时间为45分钟。In the low vacuum stage of the polycondensation reaction, add 0.03% of the catalyst tetraethyl titanate-magnesium acetate and 0.03% of the tetrafluoroterephthalic acid weight in the esterification product. Methyl ester, polycondensation reaction starts under the condition of negative pressure. At this stage, the pressure is steadily pumped from normal pressure to an absolute pressure of less than 400Pa, the temperature is controlled at 260°C, and the reaction time is 45 minutes.
所述缩聚反应高真空阶段，经所述缩聚反应低真空阶段后，继续抽真空，使反应压力降至绝对压力小于80Pa，反应温度控制在270℃，反应时间3.5小时。缩聚反应以反应釜搅拌电机功率或在线粘度计读数为准判断反应终点。当聚合物粘度达到所需值时出料，经铸带、冷却、切粒，即得到含氟PTT聚酯切片。In the high vacuum stage of the polycondensation reaction, after the low vacuum stage of the polycondensation reaction, the vacuum was continued to reduce the reaction pressure to an absolute pressure of less than 80 Pa, the reaction temperature was controlled at 270° C., and the reaction time was 3.5 hours. The polycondensation reaction is based on the power of the stirring motor of the reactor or the reading of the online viscometer to judge the end point of the reaction. When the viscosity of the polymer reaches the desired value, the material is discharged, and after casting, cooling, and pelletizing, the fluorine-containing PTT polyester chips are obtained.
制备POY纤维的方法：Method for preparing POY fiber:
是由所述含氟PTT聚酯切片经螺杆熔融挤出、冷却、上油和卷绕制得POY纤维；其中，所述挤出的温度为275℃；所述的冷却为环吹风冷却，温度为22℃，相对湿度为65%，风速为0.6m/s；所述上油采用含有8wt%的含氟聚酯POY纤维用油剂的乳液；含氟聚酯POY纤维用油剂的制备：其组分按重量份计，取60份丙二醇无规聚醚，加热到60℃，将20份聚乙二醇月桂酸单酯、15份十二烷基磷酸酯钾盐和5份全氟丁基乙基丙烯酸酯搅拌混合均匀，然后加入到丙二醇无规聚醚中，搅拌1个小时，即得到含氟聚酯纤维用POY油剂；所述上油的上油率为0.96%；所述卷绕的速度为2900m/min；最终制得含氟PTT聚酯POY纤维，单丝纤度为1.5dtex；断裂强度为2.2cN/dtex；断裂伸长率为120%。The POY fiber is obtained from the fluorine-containing PTT polyester chips through screw melt extrusion, cooling, oiling and winding; wherein, the extruding temperature is 275°C; the cooling is ring air cooling, the temperature The temperature is 22°C, the relative humidity is 65%, and the wind speed is 0.6m/s; the oiling adopts the emulsion containing 8wt% oil agent for fluorine-containing polyester POY fiber; the preparation of oil agent for fluorine-containing polyester POY fiber: Its components are calculated in parts by weight. Take 60 parts of propylene glycol random polyether, heat it to 60 ° C, add 20 parts of polyethylene glycol monolaurate, 15 parts of potassium lauryl phosphate and 5 parts of perfluorobutyl Ethyl acrylate was stirred and mixed evenly, then added to propylene glycol random polyether, and stirred for 1 hour to obtain POY oil for fluorine-containing polyester fibers; the oiling rate of the oiling was 0.96%; The winding speed is 2900m/min; the fluorine-containing PTT polyester POY fiber is finally obtained, the single filament fineness is 1.5dtex; the breaking strength is 2.2cN/dtex; the breaking elongation is 120%.
实施例9Example 9
一种含氟PTT聚酯的制备方法，分为酯化反应和缩聚反应两步。具体步骤为：A preparation method of fluorine-containing PTT polyester is divided into two steps of esterification reaction and polycondensation reaction. The specific steps are:
所述酯化反应：Described esterification reaction:
采用摩尔比为1.8:1的1,3丙二醇和四氟对苯二甲酸作为原料，同时加入四氟对苯二甲酸重量的0.03%的氧化锌，配成均匀浆料后进行酯化反应；酯化反应在氮气氛围中，压力控制在0.2MPa，温度控制在250℃，酯化水馏出量达到理论值的90%为酯化反应终点。1,3 propanediol and tetrafluoroterephthalic acid with a molar ratio of 1.8:1 are used as raw materials, and 0.03% zinc oxide of the weight of tetrafluoroterephthalic acid is added at the same time, and the esterification reaction is carried out after making a uniform slurry; The reaction is carried out in a nitrogen atmosphere, the pressure is controlled at 0.2MPa, the temperature is controlled at 250°C, and the distilled amount of esterification water reaches 90% of the theoretical value, which is the end point of the esterification reaction.
所述缩聚反应：Described polycondensation reaction:
包括缩聚反应低真空阶段和缩聚反应高真空阶段：Including low vacuum stage of polycondensation reaction and high vacuum stage of polycondensation reaction:
所述缩聚反应低真空阶段，在酯化产物中加入四氟对苯二甲酸重量的0.04%的催化剂醋酸亚锡和四氟对苯二甲酸重量的0.04%的稳定剂磷酸三甲酯，在负压的条件下开始缩聚反应，该阶段压力由常压平稳抽至绝对压力小于300Pa，温度控制在270℃，反应时间为40分钟。In the low vacuum stage of the polycondensation reaction, add 0.04% of the catalyst stannous acetate of tetrafluoroterephthalic acid weight and 0.04% of the stabilizer trimethyl phosphate of tetrafluoroterephthalic acid weight in the esterification product, The polycondensation reaction starts under the condition of low pressure, and the pressure at this stage is steadily pumped from normal pressure to an absolute pressure of less than 300Pa, the temperature is controlled at 270°C, and the reaction time is 40 minutes.
所述缩聚反应高真空阶段，经所述缩聚反应低真空阶段后，继续抽真空，使反应压力降至绝对压力小于60Pa，反应温度控制在275℃，反应时间3小时。缩聚反应以反应釜搅拌电机功率或在线粘度计读数为准判断反应终点。当聚合物粘度达到所需值时出料，经铸带、冷却、切粒，即得到含氟PTT聚酯切片。In the high vacuum stage of the polycondensation reaction, after the low vacuum stage of the polycondensation reaction, the vacuum is continued to reduce the reaction pressure to an absolute pressure of less than 60 Pa, the reaction temperature is controlled at 275° C., and the reaction time is 3 hours. The polycondensation reaction is based on the power of the stirring motor of the reactor or the reading of the online viscometer to judge the end point of the reaction. When the viscosity of the polymer reaches the desired value, the material is discharged, and after casting, cooling, and pelletizing, the fluorine-containing PTT polyester chips are obtained.
制备POY纤维的方法：Method for preparing POY fiber:
是由所述含氟PTT聚酯切片经螺杆熔融挤出、冷却、上油和卷绕制得POY纤维；其中，所述挤出的温度为265℃；所述的冷却为环吹风冷却，温度为25℃，相对湿度为60%，风速为0.4m/s；所述上油采用含有8wt%的含氟聚酯POY纤维用油剂的乳液；含氟聚酯POY纤维用油剂的制备：其组分按重量份计，取50份十二醇无规聚醚，加热到50℃，将32份聚乙二醇油酸双酯、13份十二烷基磷酸酯钾盐和5份全氟丁基乙基甲基丙烯酸酯搅拌混合均匀，然后加入到丙二醇无规聚醚中，搅拌1个小时，即得到含氟聚酯纤维用POY油剂；所述上油的上油率为1.5%；所述卷绕的速度为3000m/min；最终制得含氟PTT聚酯POY纤维，单丝纤度为1.5dtex；断裂强度为2.3cN/dtex；断裂伸长率为110%。The POY fiber is obtained from the fluorine-containing PTT polyester chips through screw melt extrusion, cooling, oiling and winding; wherein, the extruding temperature is 265°C; the cooling is ring blowing cooling, the temperature The temperature is 25°C, the relative humidity is 60%, and the wind speed is 0.4m/s; the oiling adopts an emulsion containing 8wt% fluorine-containing polyester POY fiber oil; the preparation of fluorine-containing polyester POY fiber oil: Its components are calculated in parts by weight. Take 50 parts of lauryl alcohol random polyether, heat it to 50 ° C, mix 32 parts of polyethylene glycol diester, 13 parts of potassium dodecyl phosphate and 5 parts of all Fluorobutyl ethyl methacrylate was stirred and mixed evenly, then added to propylene glycol random polyether, and stirred for 1 hour to obtain POY oil for fluorine-containing polyester fibers; the oiling rate of the oiling was 1.5 %; the winding speed is 3000m/min; the final fluorine-containing PTT polyester POY fiber is obtained, the single filament fineness is 1.5dtex; the breaking strength is 2.3cN/dtex; the elongation at break is 110%.
实施例10Example 10
一种含氟PTT聚酯的制备方法，分为酯化反应和缩聚反应两步。具体步骤为：A preparation method of fluorine-containing PTT polyester is divided into two steps of esterification reaction and polycondensation reaction. The specific steps are:
所述酯化反应：Described esterification reaction:
采用摩尔比为2.0:1的1,3丙二醇和四氟对苯二甲酸作为原料，同时加入四氟对苯二甲酸重量的0.01%的氧化锰，配成均匀浆料后进行酯化反应；酯化反应在氮气氛围中，压力控制在常压，温度控制在255℃，酯化水馏出量达到理论值的90%为酯化反应终点。1,3 propanediol and tetrafluoroterephthalic acid with a molar ratio of 2.0:1 are used as raw materials, and 0.01% manganese oxide by weight of tetrafluoroterephthalic acid is added at the same time, and the esterification reaction is carried out after making a uniform slurry; The reaction is carried out in a nitrogen atmosphere, the pressure is controlled at normal pressure, the temperature is controlled at 255°C, and the esterification water distillation reaches 90% of the theoretical value, which is the end point of the esterification reaction.
所述缩聚反应：Described polycondensation reaction:
包括缩聚反应低真空阶段和缩聚反应高真空阶段：Including low vacuum stage of polycondensation reaction and high vacuum stage of polycondensation reaction:
所述缩聚反应低真空阶段，在酯化产物中加入四氟对苯二甲酸重量的0.05%的催化剂二醋酸二丁基锡和四氟对苯二甲酸重量的0.05%的稳定剂亚磷酸三甲酯，在负压的条件下开始缩聚反应，该阶段压力由常压平稳抽至绝对压力小于300Pa，温度控制在265℃，反应时间为30分钟。In the low vacuum stage of the polycondensation reaction, add 0.05% of the catalyst dibutyltin diacetate and 0.05% of the weight of tetrafluoroterephthalic acid in the esterification product. Stabilizer trimethyl phosphite, The polycondensation reaction starts under the condition of negative pressure, and the pressure in this stage is steadily pumped from normal pressure to an absolute pressure of less than 300Pa, the temperature is controlled at 265°C, and the reaction time is 30 minutes.
所述缩聚反应高真空阶段，经所述缩聚反应低真空阶段后，继续抽真空，使反应压力降至绝对压力小于50Pa，反应温度控制在275℃，反应时间3小时。缩聚反应以反应釜搅拌电机功率或在线粘度计读数为准判断反应终点。当聚合物粘度达到所需值时出料，经铸带、冷却、切粒，即得到含氟PTT聚酯切片。In the high vacuum stage of the polycondensation reaction, after the low vacuum stage of the polycondensation reaction, the vacuum is continued to reduce the reaction pressure to an absolute pressure of less than 50 Pa, the reaction temperature is controlled at 275° C., and the reaction time is 3 hours. The polycondensation reaction is based on the power of the stirring motor of the reactor or the reading of the online viscometer to judge the end point of the reaction. When the viscosity of the polymer reaches the desired value, the material is discharged, and after casting, cooling, and pelletizing, the fluorine-containing PTT polyester chips are obtained.
制备POY纤维的方法：Method for preparing POY fiber:
是由所述含氟PTT聚酯切片经螺杆熔融挤出、冷却、上油和卷绕制得POY纤维；其中，所述挤出的温度为285℃；所述的冷却为环吹风冷却，温度为20℃，相对湿度为70%，风速为0.8m/s；所述上油采用含有8wt%的含氟聚酯POY纤维用油剂的乳液；含氟聚酯POY纤维用油剂的制备：其组分按重量份计，取60份丙二醇无规聚醚，加热到45℃，将20份聚乙二醇油酸单酯、15份十二烷基磷酸酯钾盐和5份全氟辛基乙基甲基丙烯酸酯搅拌混合均匀，然后加入到丙二醇无规聚醚中，搅拌1个小时，即得到含氟聚酯纤维用POY油剂；所述上油的上油率为0.42%；所述卷绕的速度为3200m/min；最终制得含氟PTT聚酯POY纤维，单丝纤度为0.5dtex；断裂强度为2.5cN/dtex；断裂伸长率为100%。The POY fiber is obtained from the fluorine-containing PTT polyester chips through screw melt extrusion, cooling, oiling and winding; wherein, the extruding temperature is 285°C; the cooling is ring air cooling, the temperature The temperature is 20°C, the relative humidity is 70%, and the wind speed is 0.8m/s; the oiling adopts an emulsion containing 8wt% fluorine-containing polyester POY fiber oil; the preparation of fluorine-containing polyester POY fiber oil: Its components are calculated in parts by weight. Take 60 parts of propylene glycol random polyether, heat it to 45°C, add 20 parts of polyethylene glycol monooleate, 15 parts of potassium dodecyl phosphate and 5 parts of perfluorooctyl Ethyl methacrylate was stirred and mixed uniformly, then added to propylene glycol random polyether, and stirred for 1 hour to obtain POY oil for fluorine-containing polyester fibers; the oiling rate of the oiling was 0.42%; The winding speed is 3200m/min; the fluorine-containing PTT polyester POY fiber is finally obtained, the single filament fineness is 0.5dtex; the breaking strength is 2.5cN/dtex; the breaking elongation is 100%.
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