CN103469337B - Preparation method of fluorine-containing random copolyester polyester pre-oriented yarn (POY) fibers - Google Patents
Preparation method of fluorine-containing random copolyester polyester pre-oriented yarn (POY) fibers Download PDFInfo
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- CN103469337B CN103469337B CN201310447069.4A CN201310447069A CN103469337B CN 103469337 B CN103469337 B CN 103469337B CN 201310447069 A CN201310447069 A CN 201310447069A CN 103469337 B CN103469337 B CN 103469337B
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- fluorine
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- random copolyester
- acid
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 181
- 239000011737 fluorine Substances 0.000 title claims abstract description 178
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 239000000835 fiber Substances 0.000 title claims abstract description 122
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 99
- 229920000728 polyester Polymers 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 203
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 124
- 238000001816 cooling Methods 0.000 claims abstract 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 41
- 238000004804 winding Methods 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 14
- 238000001125 extrusion Methods 0.000 claims abstract description 11
- 238000006068 polycondensation reaction Methods 0.000 claims description 109
- 238000005886 esterification reaction Methods 0.000 claims description 95
- 238000006243 chemical reaction Methods 0.000 claims description 61
- 239000003921 oil Substances 0.000 claims description 58
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 45
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 41
- 229920000570 polyether Polymers 0.000 claims description 41
- -1 tetrafluoroethylene Terephthalic acid Chemical compound 0.000 claims description 41
- 230000032050 esterification Effects 0.000 claims description 39
- 239000003054 catalyst Substances 0.000 claims description 29
- 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 26
- 239000002253 acid Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000003381 stabilizer Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 15
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical group O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000839 emulsion Substances 0.000 claims description 13
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 13
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application 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
- 239000000203 mixture Substances 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 10
- 238000007664 blowing Methods 0.000 claims description 9
- 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
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 claims description 6
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 6
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 5
- 229940087291 tridecyl alcohol Drugs 0.000 claims description 5
- MUHFRORXWCGZGE-KTKRTIGZSA-N 2-hydroxyethyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCO MUHFRORXWCGZGE-KTKRTIGZSA-N 0.000 claims description 4
- 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 4
- 239000005639 Lauric acid Substances 0.000 claims description 4
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 4
- 239000008041 oiling agent Substances 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 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 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
- 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 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 229940070765 laurate Drugs 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 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 2
- 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
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims 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 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052787 antimony Inorganic materials 0.000 claims 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims 1
- 125000003438 dodecyl group Chemical group [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])* 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 229940049964 oleate Drugs 0.000 claims 1
- 230000003373 anti-fouling effect Effects 0.000 abstract description 12
- 230000003075 superhydrophobic effect Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000005871 repellent Substances 0.000 abstract description 3
- 150000002148 esters Chemical class 0.000 abstract description 2
- 239000000155 melt Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 22
- 239000000047 product Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 12
- 239000003607 modifier Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 239000000126 substance Substances 0.000 description 7
- 238000005266 casting Methods 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 238000005453 pelletization Methods 0.000 description 6
- 229940033623 potassium lauryl phosphate Drugs 0.000 description 6
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 description 5
- 150000005690 diesters Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 238000009987 spinning Methods 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
- 230000005611 electricity Effects 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 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
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 150000003384 small molecules Chemical class 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
- 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
- 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
- 238000005299 abrasion Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect 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
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000004069 differentiation 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
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000009499 grossing 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
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 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
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
本发明涉及一种含氟无规共聚酯POY纤维的制备方法，包括含氟无规共聚酯熔体的制备和含氟无规共聚酯POY纤维的制备；在含氟无规共聚酯熔体的制备工艺中采用四氟对苯二甲酸、对苯二甲酸和乙二醇作为原料制备得到含氟无规共聚酯熔体，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无规聚酯POY纤维。本发明所得的含氟无规共聚酯POY纤维单丝纤度为0.5～3.0dtex；断裂强度为1.6～2.5cN/dtex；断裂伸长率为110～150％。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 preparation method of fluorine-containing random copolyester POY fiber, comprising the preparation of fluorine-containing random copolyester melt and the preparation of fluorine-containing random copolyester POY fiber; In the preparation process of ester melt, tetrafluoroterephthalic acid, terephthalic acid and ethylene glycol are used as raw materials to prepare fluorine-containing random copolyester melt, and the melt is directly extruded or made into slices and melted by a screw Fluorine-containing random polyester POY fibers were obtained by extrusion, cooling, oiling and winding. The monofilament fineness of the fluorine-containing random copolyester POY fiber obtained in the invention is 0.5-3.0 dtex; the breaking strength is 1.6-2.5 cN/dtex; the breaking elongation is 110-150%. 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无规共聚酯POY纤维的制备方法，特别是涉及一种苯环上的氢被氟取代的含氟无规共聚酯POY纤维的制备方法。The invention relates to a preparation method of a fluorine-containing random copolyester POY fiber, in particular to a preparation method of a fluorine-containing random copolyester POY fiber in which hydrogen on a benzene ring is replaced by fluorine.
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年代就合成出了对苯二甲酸乙二醇酯(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。Polyester is currently one of the most widely used synthetic polymers. As early as the 1940s, polyethylene terephthalate (PET) was synthesized and found to have excellent properties. It is widely used in textile, packaging, medical and health, automobile, electronic appliances, safety protection, environmental protection 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 fluorine-containing polymers are mainly fluoroolefin polymers (for example: 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CN 101139434A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。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 CN 101139434A, the addition of fluorine-containing end-capping agent is adopted, and dimethyl isophthalate and butanediol are transesterified, and fluorine-containing end-capping agent N-hydroxyethyl perfluorooctylamide is added to prepare a compound containing Polyester material with low fluorine content 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.
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 polyesters 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
本发明的目的是提供一种含氟无规共聚酯POY纤维的制备方法，特别是涉及一种苯环上的氢被氟取代的含氟无规共聚酯POY纤维的制备方法。本发明含氟无规共聚酯POY纤维是是由含氟无规聚酯熔体经计量、挤出、冷却、上油和卷绕制得。本发明中所述的含氟无规共聚酯是通过对苯二甲酸、四氟对苯二甲酸与乙二醇，经过酯化反应和缩聚反应得到的含氟无规共聚酯，该含氟无规共聚酯切片可以直接纺丝、成膜。本发明中所述的含氟无规共聚酯在聚合物的主链上引入了氟原子，而且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，也可以很好的解决费时费力这类问题。The purpose of the present invention is to provide a method for preparing fluorine-containing random copolyester POY fibers, in particular to a method for preparing fluorine-containing random copolyester POY fibers in which the hydrogen on the benzene ring is replaced by fluorine. The fluorine-containing random copolyester POY fiber of the present invention is prepared from the fluorine-containing random polyester melt through metering, extruding, cooling, oiling and winding. The fluorine-containing random copolyester described in the present invention is a fluorine-containing random copolyester obtained through esterification reaction and polycondensation reaction of terephthalic acid, tetrafluoroterephthalic acid and ethylene glycol. Fluorine random copolyester chips can be directly spun and film-formed. The fluorine-containing random copolyester described in the present invention introduces fluorine atoms into the main chain of the polymer, and the hydrophobic and antifouling modification of the polyester can fundamentally solve the problem of hydrophobic and antifouling polyester. Problems such as timeliness, durability and wear resistance can also be a good solution to such problems as time-consuming and labor-intensive.
本发明提供了以下技术方案：The invention provides the following technical solutions:
一种含氟无规共聚酯POY纤维，其特征是：所述含氟无规共聚酯POY纤维是由含氟无规聚酯熔体经计量、挤出、冷却、上油和卷绕制得；所述含氟无规共聚酯是由四氟对苯二甲酸、对苯二甲酸和乙二醇共聚得到的含氟无规共聚酯；所述的四氟对苯二甲酸具有如下结构式：A fluorine-containing random copolyester POY fiber is characterized in that: the fluorine-containing random copolyester POY fiber is measured, extruded, cooled, oiled and wound from a fluorine-containing random polyester melt Prepared; the fluorine-containing random copolyester is a fluorine-containing random copolyester obtained by copolymerization of tetrafluoroterephthalic acid, terephthalic acid and ethylene glycol; the tetrafluoroterephthalic acid has The following structural formula:
如上所述的一种含氟无规共聚酯POY纤维，所述含氟无规共聚酯POY纤维的单丝纤度为0.5～3.0dtex；断裂强度为1.6～2.5cN/dtex；断裂伸长率为110～50％。A fluorine-containing random copolyester POY fiber as described above, the monofilament fineness of the fluorine-containing random copolyester POY fiber is 0.5-3.0dtex; the breaking strength is 1.6-2.5cN/dtex; the elongation at break The rate is 110-50%.
本发明还提供了一种含氟无规共聚酯POY纤维的制备方法，是将氟聚酯熔体计量、挤出、冷却、上油和卷绕制得含氟无规共聚酯POY纤维。The present invention also provides a method for preparing fluorine-containing random copolyester POY fibers, which comprises measuring, extruding, cooling, oiling and winding the fluorine-containing random copolyester POY fibers .
所述挤出的温度为285～295℃；The extrusion temperature is 285-295°C;
所述的冷却的风温为20～30℃；The air temperature of the cooling is 20-30°C;
所述上油的上油率为0.42～1.5wt％；The oiling rate of the oiling is 0.42～1.5wt%;
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℃～30℃，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-30°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 The POY oil agent for fluorine-containing polyester fibers can be obtained after 1 hour. When the oil agent is used, water is added to form an emulsion with a solid content of 8-10 wt%.
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.
所述含氟无规共聚酯是由四氟对苯二甲酸、对苯二甲酸和乙二醇共聚得到的含氟无规共聚酯；所述的四氟对苯二甲酸具有如下结构式：The fluorine-containing random copolyester is a fluorine-containing random copolyester obtained by copolymerization of tetrafluoroterephthalic acid, terephthalic acid and ethylene glycol; the tetrafluoroterephthalic acid has the following structural formula:
所述含氟无规共聚酯熔体是指熔融后的含氟无规共聚酯，所述含氟无规共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 random copolyester melt refers to the melted fluorine-containing random copolyester, and the preparation method of the fluorine-containing random copolyester is divided into two steps of esterification reaction and polycondensation reaction; the specific steps are :
所述酯化反应：Described esterification reaction:
采用对苯二甲酸和乙二醇为主要原料，四氟对苯二甲酸作为第三单体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进行，压力控制在常压～0.4MPa，温度在240～250℃，时间为2～3小时，酯化水馏出量达到理论值的90％以上为反应终点；Terephthalic acid and ethylene glycol are used as the main raw materials, tetrafluoroterephthalic acid is used as the third monomer to form a uniform slurry, and then the esterification reaction is carried out; the esterification reaction is carried out under pressure in a nitrogen atmosphere, and the pressure is controlled at normal temperature. The pressure is ~0.4MPa, the temperature is 240-250°C, the time is 2-3 hours, and the distilled amount of esterification water reaches more than 90% of the theoretical value, which is the end point of the 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，在所述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，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1KPa以下，温度控制在250～270℃，反应时间为40～60分钟；In the low-vacuum stage of the polycondensation reaction, a catalyst and a stabilizer are added to the esterification product, and the polycondensation reaction starts under negative pressure conditions, and the pressure at this stage is steadily pumped from normal pressure to The absolute pressure is below 1KPa, the temperature is controlled at 250-270°C, and the reaction time is 40-60 minutes;
所述缩聚反应高真空阶段，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270～280℃，反应时间2～3小时，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, continue vacuuming to reduce the reaction pressure to an absolute pressure of less than 100Pa, control the reaction temperature at 270-280°C, and the reaction time is 2-3 hours. The power of the stirring motor of the reactor or the reading of the online viscometer is Accurately judge the end point of the reaction.
作为优选的技术方案：As a preferred technical solution:
如上所述的一种氟聚酯POY纤维的制备方法，所述氟聚酯熔体是由聚合直接获得或由氟聚酯切片经螺杆熔融得到。According to the above-mentioned preparation method of fluoropolyester POY fiber, the fluoropolyester melt is directly obtained by polymerization or obtained by melting fluoropolyester chips through a screw.
如上所述的一种含氟无规共聚酯POY纤维的制备方法，所述的原料单体为对苯二甲酸(PTA)、四氟对苯二甲酸(FPTA)、乙二醇(EG)。其摩尔比为：PTA：FPTA＝1:0.02～1；(PTA+FPTA)：EG＝1:1.2～2。A kind of preparation method of fluorine-containing random copolyester POY fiber as above, described raw material monomer is terephthalic acid (PTA), tetrafluoroterephthalic acid (FPTA), ethylene glycol (EG) . Its molar ratio is: PTA:FPTA=1:0.02～1; (PTA+FPTA):EG=1:1.2～2.
如上所述的一种含氟无规共聚酯POY纤维的制备方法，所述的催化剂选自三氧化二锑、乙二醇锑和醋酸锑中的一种，催化剂用量为所述四氟对苯二甲酸和对苯二甲酸总重量的0.01％～0.03％。A method for preparing a fluorine-containing random copolyester POY fiber as described above, the catalyst is selected from one of antimony trioxide, antimony ethylene glycol and antimony acetate, and the amount of the catalyst is 0.01% to 0.03% of the total weight of phthalic acid and terephthalic acid.
如上所述的一种含氟无规共聚酯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和对苯二甲酸总重量的0.01％～0.03％。A kind of preparation method of fluorine-containing random copolyester POY fiber as mentioned above, described stabilizer is selected from a kind of in triphenyl phosphate, trimethyl phosphate and trimethyl phosphite, and the dosage of stabilizer is 0.01%-0.03% of the total weight of the tetrafluoroterephthalic acid and terephthalic acid.
如上所述的一种含氟无规共聚酯POY纤维的制备方法，当四氟对苯二甲酸与对苯二甲酸摩尔比为0.5～1:1时，所述酯化反应还加入氧化镁、氧化硅、氧化钙、氧化锌和氧化锰中的一种，作为抑制剂，加入量为所述四氟对苯二甲酸和对苯二甲酸总重量的0.01％～0.05％。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。A method for preparing a fluorine-containing random copolyester POY fiber as described above, when the molar ratio of tetrafluoroterephthalic acid to terephthalic acid is 0.5 to 1:1, magnesium oxide is also added to the esterification reaction , one of silicon oxide, calcium oxide, zinc oxide and manganese oxide, as an inhibitor, added in an amount of 0.01% to 0.05% of the total weight of tetrafluoroterephthalic acid and terephthalic acid. Due to the presence of fluorine atoms on the benzene ring of the dibasic carboxylic acid used, the electronegativity of the fluorine atom is large, and the conjugation effect of the fluorine atom in the esterification reaction stage makes the acidity of the dibasic carboxylic acid stronger, resulting in The increase in the activity of the carboxyl group makes the reaction speed faster, and the increase in the reaction speed is easy to cause side reactions. These side reaction products have a greater impact on the subsequent polycondensation reaction, especially the generation of end-capped products of olefins and aldehydes, which restricts the production of products. The increase of molecular weight; From the experimental results, if no inhibitor is added, the molecular weight of the synthesized polyester is low, which cannot meet the needs of spinning and film formation; the addition of inhibitor is used to control the speed of the esterification reaction stage, reducing the The side reaction increases the molecular weight of the product to meet 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, it has a strong attraction to the electron pairs of oxygen ions, which can weaken the O—H bond and facilitate the reaction dissociation; 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.
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 amount of water distilled out actually produced in the esterification reaching 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.
本发明所得的含氟无规共聚酯POY纤维的单丝纤度为0.5-3.0dtex；断裂强度为1.6～1.9cN/dtex；断裂伸长率为110～150％。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 fluorine-containing random copolyester POY fiber obtained by the invention is 0.5-3.0dtex; the breaking strength is 1.6-1.9cN/dtex; the breaking elongation is 110-150%. 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、所得含氟无规共聚酯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 fluorine-containing random copolyester POY fiber contains fluorine atoms. Due to the strong electronegativity of fluorine, the high C-F bond energy and the shielding protection effect on the carbon chain, the final copolyester POY fiber has good Excellent 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、所得含氟无规共聚酯POY纤维具有一定的结构稳定性和可加工性。2. The obtained fluorine-containing random copolyester POY fiber has certain structural stability and processability.
3、所得含氟无规共聚酯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 fluorine-containing random copolyester POY fiber has hydrophobic and anti-fouling properties by introducing fluorine atoms.
4、所得含氟无规共聚酯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 resulting fluorine-containing random copolyester 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 description
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.
一种含氟无规共聚酯POY纤维，其特征是：所述含氟无规共聚酯POY纤维是由含氟无规聚酯熔体经计量、挤出、冷却、上油和卷绕制得；所述含氟无规共聚酯是由四氟对苯二甲酸、对苯二甲酸和乙二醇共聚得到的含氟无规共聚酯；所述的四氟对苯二甲酸具有如下结构式：A fluorine-containing random copolyester POY fiber is characterized in that: the fluorine-containing random copolyester POY fiber is measured, extruded, cooled, oiled and wound from a fluorine-containing random polyester melt Prepared; the fluorine-containing random copolyester is a fluorine-containing random copolyester obtained by copolymerization of tetrafluoroterephthalic acid, terephthalic acid and ethylene glycol; the tetrafluoroterephthalic acid has The following structural formula:
如上所述的一种含氟无规共聚酯POY纤维，所述含氟无规共聚酯POY纤维的单丝纤度为0.5～3.0dtex；断裂强度为1.6～2.5cN/dtex；断裂伸长率为110～50％。A fluorine-containing random copolyester POY fiber as described above, the monofilament fineness of the fluorine-containing random copolyester POY fiber is 0.5-3.0dtex; the breaking strength is 1.6-2.5cN/dtex; the elongation at break The rate is 110-50%.
实施例1Example 1
一种含氟无规共聚酯的制备方法，分为酯化反应和缩聚反应两步。具体步骤为：A preparation method of fluorine-containing random copolyester is divided into two steps of esterification reaction and polycondensation reaction. The specific steps are:
所述酯化反应：Described esterification reaction:
采用对苯二甲酸(PTA)、乙二醇(EG)为主要原料，含氟改性剂四氟对苯二甲酸(FPTA)作为第三单体配成均匀浆料后进行酯化反应。原料中对苯二甲酸(PTA)、四氟对苯二甲酸(FPTA)、乙二醇(EG)摩尔比为：PTA:FPTA＝1:0.02；(PTA+FPTA):EG＝1:1.2。酯化反应中无需外加催化剂，氮气氛围中加压，压力控制在0.4MPa下进行，温度控制在250℃，酯化水馏出量达到理论值的90％以上为反应终点。Terephthalic acid (PTA) and ethylene glycol (EG) are used as main raw materials, and fluorine-containing modifier tetrafluoroterephthalic acid (FPTA) is used as a third monomer to form a homogeneous slurry for esterification. The molar ratios of terephthalic acid (PTA), tetrafluoroterephthalic acid (FPTA), and ethylene glycol (EG) in the raw materials are: PTA:FPTA=1:0.02; (PTA+FPTA):EG=1:1.2. In the esterification reaction, no external catalyst is needed, pressurized in a nitrogen atmosphere, the pressure is controlled at 0.4MPa, the temperature is controlled at 250°C, and the distilled amount of esterification water reaches more than 90% of the theoretical value as the reaction end point.
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，在酯化产物中加入所用二元酸重量的0.01％的催化剂三氧化二锑和所用二元酸重量的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1KPa，温度控制在255℃，反应时间为60分钟。In the low-vacuum stage of the polycondensation reaction, add 0.01% of the catalyst antimony trioxide and 0.01% of the dibasic acid weight used in the esterification product to the stabilizer triphenyl phosphate. At this stage, the pressure was steadily pumped from normal pressure to an absolute pressure of less than 1KPa, the temperature was controlled at 255°C, and the reaction time was 60 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 100 Pa, the reaction temperature is controlled at 270° 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:
是由所述含氟无规共聚酯熔体直接挤出、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30℃，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；最终制得含氟无规共聚酯POY纤维，单丝纤度为3.0dtex；断裂强度为1.6cN/dtex；断裂伸长率为150％。The POY fiber is obtained by directly extruding, cooling, oiling and winding the fluorine-containing random copolyester melt; wherein, the extruding temperature is 285°C; the cooling is side blowing cooling, The temperature is 30°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; 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 60 ° C, mix 20 parts of polyethylene glycol monolaurate, 15 parts of potassium lauryl phosphate and 5 parts of perfluoro Butyl 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 0.42%; The above-mentioned winding speed is 2700m/min; the fluorine-containing random copolyester POY fiber is finally obtained, the single filament fineness is 3.0dtex; the breaking strength is 1.6cN/dtex; the breaking elongation is 150%.
实施例2Example 2
一种含氟无规共聚酯的制备方法，分为酯化反应和缩聚反应两步。具体步骤为：A preparation method of fluorine-containing random copolyester is divided into two steps of esterification reaction and polycondensation reaction. The specific steps are:
所述酯化反应：Described esterification reaction:
采用对苯二甲酸(PTA)、乙二醇(EG)为主要原料，含氟改性剂四氟对苯二甲酸(FPTA)作为第三单体配成均匀浆料后进行酯化反应。原料中对苯二甲酸(PTA)、四氟对苯二甲酸(FPTA)、乙二醇(EG)摩尔比为：PTA:FPTA＝1:0.06；(PTA+FPTA):EG＝1:1.4。酯化反应中无需外加催化剂，氮气氛围中加压，压力控制在0.3MPa下进行，温度控制在245℃，酯化水馏出量达到理论值的90％以上为反应终点。Terephthalic acid (PTA) and ethylene glycol (EG) are used as main raw materials, and fluorine-containing modifier tetrafluoroterephthalic acid (FPTA) is used as a third monomer to form a homogeneous slurry for esterification. The molar ratios of terephthalic acid (PTA), tetrafluoroterephthalic acid (FPTA), and ethylene glycol (EG) in the raw materials are: PTA:FPTA=1:0.06; (PTA+FPTA):EG=1:1.4. In the esterification reaction, no external catalyst is needed, pressurized in a nitrogen atmosphere, the pressure is controlled at 0.3MPa, the temperature is controlled at 245°C, and the distilled amount of esterification water reaches more than 90% of the theoretical value as the reaction end point.
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，在酯化产物中加入所用二元酸重量的0.02％的催化剂乙二醇锑和所用二元酸重量的0.02％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800Pa，温度控制在250℃，反应时间为50分钟。In the low vacuum stage of the polycondensation reaction, 0.02% of the catalyst ethylene glycol antimony and 0.02% of the weight of the dibasic acid used are added to the esterification product, and the stabilizer trimethyl phosphate is added under negative pressure conditions. At this stage, the pressure was steadily pumped from normal pressure to an absolute pressure of less than 800Pa, the temperature was controlled at 250°C, and the reaction time was 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80Pa，反应温度控制在275℃，反应时间2.5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 is continued to reduce the reaction pressure to an absolute pressure of less than 80 Pa, the reaction temperature is controlled at 275° C., and the reaction time is 2.5 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:
是由所述含氟无规共聚酯熔体直接挤出、冷却、上油和卷绕制得POY纤维；其中，所述挤出的温度为295℃；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；最终制得含氟无规共聚酯POY纤维，单丝纤度为2.0dtex；断裂强度为1.8cN/dtex；断裂伸长率为140％。The POY fiber is obtained by directly extruding, cooling, oiling and winding the fluorine-containing random copolyester melt; wherein, the extruding temperature is 295°C; the cooling is side blowing cooling, The temperature is 20°C, the relative humidity is 70%, and the wind speed is 0.8m/s; the oiling adopts an emulsion containing 9wt% fluorine-containing polyester POY fiber oil; preparation of fluorine-containing polyester POY fiber oil : Its components are calculated in parts by weight. Take 50 parts of butanol random polyether, heat to 40 ° C, and mix 32 parts of polyethylene glycol laurate diester, 15 parts of isomeric tridecyl alcohol polyoxyethylene ether potassium phosphate 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 fiber; the oiled oil The rate is 1.5%; the speed of the winding is 2800m/min; the final fluorine-containing random copolyester POY fiber is obtained, and the monofilament fineness is 2.0dtex; the breaking strength is 1.8cN/dtex; the elongation at break is 140 %.
实施例3Example 3
一种含氟无规共聚酯的制备方法，分为酯化反应和缩聚反应两步。具体步骤为：A preparation method of fluorine-containing random copolyester is divided into two steps of esterification reaction and polycondensation reaction. The specific steps are:
所述酯化反应：Described esterification reaction:
采用对苯二甲酸(PTA)、乙二醇(EG)为主要原料，含氟改性剂四氟对苯二甲酸(FPTA)作为第三单体配成均匀浆料后进行酯化反应。原料中对苯二甲酸(PTA)、四氟对苯二甲酸(FPTA)、乙二醇(EG)摩尔比为：PTA:FPTA＝1:0.1；(PTA+FPTA):EG＝1:1.6。酯化反应中无需外加催化剂，氮气氛围中加压，压力控制在0.2MPa下进行，温度控制在240℃，酯化水馏出量达到理论值的90％以上为反应终点。Terephthalic acid (PTA) and ethylene glycol (EG) are used as main raw materials, and fluorine-containing modifier tetrafluoroterephthalic acid (FPTA) is used as a third monomer to form a homogeneous slurry for esterification. The molar ratios of terephthalic acid (PTA), tetrafluoroterephthalic acid (FPTA), and ethylene glycol (EG) in the raw materials are: PTA:FPTA=1:0.1; (PTA+FPTA):EG=1:1.6. No external catalyst is needed in the esterification reaction, pressurization is carried out in a nitrogen atmosphere, the pressure is controlled at 0.2 MPa, the temperature is controlled at 240 ° C, and the distilled amount of esterification water reaches more than 90% of the theoretical value as the reaction end point.
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，在酯化产物中加入所用二元酸重量的0.03％的催化剂醋酸锑和所用二元酸重量的0.03％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600Pa，温度控制在260℃，反应时间为40分钟。In the low vacuum stage of the polycondensation reaction, 0.03% of the catalyst antimony acetate and 0.03% of the weight of the dibasic acid used were added to the esterification product, and the stabilizer trimethyl phosphite was added under negative pressure conditions. Start the polycondensation reaction, the pressure at this stage is steadily pumped from normal pressure to an absolute pressure of less than 600Pa, the temperature is controlled at 260°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2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 2 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:
是由所述含氟无规共聚酯熔体直接挤出、冷却、上油和卷绕制得POY纤维；其中，所述挤出的温度为290℃；所述的冷却为侧吹风冷却，温度为25℃，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；最终制得含氟无规共聚酯POY纤维，单丝纤度为1.5dtex；断裂强度为2.0cN/dtex；断裂伸长率为135％。The POY fiber is obtained by directly extruding, cooling, oiling and winding the fluorine-containing random copolyester melt; wherein, the extruding temperature is 290°C; the cooling is side blowing cooling, The temperature is 25°C, the relative humidity is 65%, and the wind speed is 0.6m/s; the oiling uses an emulsion containing 10wt% oil for fluorine-containing polyester POY fibers; preparation of oil for fluorine-containing polyester POY fibers : Its components are calculated by weight, get 58 parts of lauric acid atactic polyether, heat to 60 ℃, with 30 parts of polyethylene glycol monooleic acid ester, 10 parts of potassium salt of tetradecyl alcohol phosphate and 2 parts Perfluorooctyl ethyl acrylate 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 0.96% The winding speed is 2900m/min; the fluorine-containing random copolyester POY fiber is finally obtained, the single filament fineness is 1.5dtex; the breaking strength is 2.0cN/dtex; the breaking elongation is 135%.
实施例4Example 4
一种含氟无规共聚酯的制备方法，分为酯化反应和缩聚反应两步。具体步骤为：A preparation method of fluorine-containing random copolyester is divided into two steps of esterification reaction and polycondensation reaction. The specific steps are:
所述酯化反应：Described esterification reaction:
采用对苯二甲酸(PTA)、乙二醇(EG)为主要原料，含氟改性剂四氟对苯二甲酸(FPTA)作为第三单体配成均匀浆料后进行酯化反应。原料中对苯二甲酸(PTA)、四氟对苯二甲酸(FPTA)、乙二醇(EG)摩尔比为：PTA:FPTA＝1:0.2；(PTA+FPTA):EG＝1:1.8。酯化反应中无需外加催化剂，氮气氛围中加压，压力控制在0.2MPa下进行，温度控制在245℃，酯化水馏出量达到理论值的90％以上为反应终点。Using terephthalic acid (PTA) and ethylene glycol (EG) as the main raw materials, and the fluorine-containing modifier tetrafluoroterephthalic acid (FPTA) as the third monomer to form a uniform slurry for esterification. The molar ratios of terephthalic acid (PTA), tetrafluoroterephthalic acid (FPTA), and ethylene glycol (EG) in the raw materials are: PTA:FPTA=1:0.2; (PTA+FPTA):EG=1:1.8. In the esterification reaction, no external catalyst is needed, pressurized in a nitrogen atmosphere, the pressure is controlled at 0.2MPa, the temperature is controlled at 245°C, and the distilled amount of esterification water reaches more than 90% of the theoretical value as the reaction end point.
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，在酯化产物中加入所用二元酸重量的0.03％的催化剂三氧化二锑和所用二元酸重量的0.03％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500Pa，温度控制在260℃，反应时间为40分钟。In the low vacuum stage of the polycondensation reaction, add 0.03% of the catalyst antimony trioxide and 0.03% of the dibasic acid weight used in the esterification product to the stabilizer trimethyl phosphite of the used dibasic acid weight. The polycondensation reaction starts under the same conditions, and the pressure at this stage is steadily pumped from normal pressure to an absolute pressure of less than 500Pa, the temperature is controlled at 260°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50Pa，反应温度控制在280℃，反应时间2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 280° C., and the reaction time is 2 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:
是由所述含氟无规共聚酯熔体直接挤出、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30℃，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；最终制得含氟无规共聚酯POY纤维，单丝纤度为1.0dtex；断裂强度为2.2cN/dtex；断裂伸长率为125％。The POY fiber is obtained by directly extruding, cooling, oiling and winding the fluorine-containing random copolyester melt; wherein, the extruding temperature is 285°C; the cooling is side blowing cooling, The temperature is 30°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; preparation of fluorine-containing polyester POY fiber oil : Its components are calculated by weight, take 50 parts of lauryl alcohol random polyether, heat to 50 ℃, mix 32 parts of polyethylene glycol diester, 13 parts of dodecyl phosphate potassium salt and 5 parts Perfluorobutyl 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; the fluorine-containing random copolyester POY fiber is finally obtained, the single filament fineness is 1.0dtex; the breaking strength is 2.2cN/dtex; the breaking elongation is 125%.
实施例5Example 5
一种含氟无规共聚酯的制备方法，分为酯化反应和缩聚反应两步。具体步骤为：A preparation method of fluorine-containing random copolyester is divided into two steps of esterification reaction and polycondensation reaction. The specific steps are:
所述酯化反应：Described esterification reaction:
采用对苯二甲酸(PTA)、乙二醇(EG)为主要原料，含氟改性剂四氟对苯二甲酸(FPTA)作为第三单体配成均匀浆料后进行酯化反应。原料中对苯二甲酸(PTA)、四氟对苯二甲酸(FPTA)、乙二醇(EG)摩尔比为：PTA:FPTA＝1:0.3；(PTA+FPTA):EG＝1:1.8。酯化反应中无需外加催化剂，氮气氛围中加压，压力控制在常压下进行，温度控制在250℃，酯化水馏出量达到理论值的90％以上为反应终点。Terephthalic acid (PTA) and ethylene glycol (EG) are used as main raw materials, and fluorine-containing modifier tetrafluoroterephthalic acid (FPTA) is used as a third monomer to form a homogeneous slurry for esterification. The molar ratios of terephthalic acid (PTA), tetrafluoroterephthalic acid (FPTA), and ethylene glycol (EG) in the raw materials are: PTA:FPTA=1:0.3; (PTA+FPTA):EG=1:1.8. In the esterification reaction, no external catalyst is needed, pressurized in a nitrogen atmosphere, the pressure is controlled at normal pressure, the temperature is controlled at 250°C, and the distilled amount of esterification water reaches more than 90% of the theoretical value as the reaction end point.
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，在酯化产物中加入所用二元酸重量的0.03％的催化剂三氧化二锑和所用二元酸重量的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500Pa，温度控制在265℃，反应时间为45分钟。In the low-vacuum stage of the polycondensation reaction, add 0.03% of the catalyst antimony trioxide and 0.03% of the dibasic acid weight used in the esterification product to the stabilizer trimethyl phosphate. At this stage, the pressure was steadily pumped from normal pressure to an absolute pressure of less than 500Pa, the temperature was controlled at 265°C, and the reaction time was 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30Pa，反应温度控制在275℃，反应时间2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 30 Pa, the reaction temperature is controlled at 275° C., and the reaction time is 2 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:
是由所述含氟无规共聚酯熔体直接挤出、冷却、上油和卷绕制得POY纤维；其中，所述挤出的温度为295℃；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；最终制得含氟无规共聚酯POY纤维，单丝纤度为0.5dtex；断裂强度为2.5cN/dtex；断裂伸长率为110％。The POY fiber is obtained by directly extruding, cooling, oiling and winding the fluorine-containing random copolyester melt; wherein, the extruding temperature is 295°C; the cooling is side blowing cooling, The temperature is 20°C, the relative humidity is 70%, and the wind speed is 0.8m/s; the oiling uses an emulsion containing 10wt% oil for fluorine-containing polyester POY fibers; preparation of oil for fluorine-containing polyester POY fibers : Its components are calculated in parts by weight. Get 55 parts of isomeric tridecanol random polyether, heat to 55 ℃, mix 25 parts of polyethylene glycol lauric acid diesters, 15 parts of potassium lauryl phosphate and 5 parts of perfluorohexyl ethyl methacrylate were stirred and mixed evenly, then added to propylene glycol random polyether, and stirred for 2 hours to obtain POY oil for fluorine-containing polyester fiber; the oiling rate of the oiling is 0.42%; the winding speed is 3200m/min; the fluorine-containing random copolyester POY fiber is finally obtained, and the single filament fineness is 0.5dtex; the breaking strength is 2.5cN/dtex; the elongation at break is 110% .
实施例6Example 6
一种含氟无规共聚酯的制备方法，分为酯化反应和缩聚反应两步。具体步骤为：A preparation method of fluorine-containing random copolyester is divided into two steps of esterification reaction and polycondensation reaction. The specific steps are:
所述酯化反应：Described esterification reaction:
采用对苯二甲酸(PTA)、乙二醇(EG)为主要原料，含氟改性剂四氟对苯二甲酸(FPTA)作为第三单体配成均匀浆料后进行酯化反应。原料中对苯二甲酸(PTA)、四氟对苯二甲酸(FPTA)、乙二醇(EG)摩尔比为：PTA:FPTA＝1:0.5；(PTA+FPTA)：EG＝1:2。酯化反应中无需外加催化剂，氮气氛围中加压，压力控制在常压下进行，温度控制在240℃，酯化水馏出量达到理论值的90％以上为反应终点。Terephthalic acid (PTA) and ethylene glycol (EG) are used as main raw materials, and fluorine-containing modifier tetrafluoroterephthalic acid (FPTA) is used as a third monomer to form a homogeneous slurry for esterification. The molar ratio of terephthalic acid (PTA), tetrafluoroterephthalic acid (FPTA), and ethylene glycol (EG) in the raw materials is: PTA:FPTA=1:0.5; (PTA+FPTA):EG=1:2. In the esterification reaction, no external catalyst is needed, pressurized in a nitrogen atmosphere, the pressure is controlled at normal pressure, the temperature is controlled at 240°C, and the distilled amount of esterification water reaches more than 90% of the theoretical value as the reaction end point.
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，在酯化产物中加入所用二元酸重量的0.03％的催化剂乙二醇锑和所用二元酸重量的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300Pa，温度控制在260℃，反应时间为40分钟。In the low vacuum stage of the polycondensation reaction, 0.03% of the catalyst ethylene glycol antimony and 0.03% of the weight of the dibasic acid used are added to the esterification product, and the stabilizer trimethyl phosphate is added under negative pressure conditions. At this stage, the pressure was steadily pumped from normal pressure to an absolute pressure of less than 300Pa, the temperature was controlled at 260°C, and the reaction time was 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30Pa，反应温度控制在275℃，反应时间2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，即得到含氟无规共聚酯切片。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 30 Pa, the reaction temperature is controlled at 275° C., and the reaction time is 2 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 required value, the material is discharged, and after casting, cooling and pelletizing, the fluorine-containing random copolyester chips are obtained.
制备POY纤维的方法：Method for preparing POY fiber:
是由所述含氟无规共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30℃，相对湿度为60％，风速为0.4m/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；最终制得含氟无规共聚酯POY纤维，单丝纤度为3.0dtex；断裂强度为1.6cN/dtex；断裂伸长率为150％。The POY fiber is obtained from the fluorine-containing random copolyester chips through screw melt extrusion, cooling, oiling and winding; wherein, the extruding temperature is 285°C; the cooling is ring air cooling , the temperature is 30°C, the relative humidity is 60%, and the wind speed is 0.4m/s; the oiling adopts the emulsion containing 9wt% oil for fluorine-containing polyester POY fiber; the oil for oil for fluorine-containing polyester POY fiber Preparation: The 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 lauryl phosphate and 5 parts of all Fluorooctyl 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 0.42 %; the winding speed is 2700m/min; the fluorine-containing random copolyester POY fiber is finally obtained, the single filament fineness is 3.0dtex; the breaking strength is 1.6cN/dtex; the breaking elongation is 150%.
实施例7Example 7
一种含氟无规共聚酯的制备方法，分为酯化反应和缩聚反应两步。具体步骤为：A preparation method of fluorine-containing random copolyester is divided into two steps of esterification reaction and polycondensation reaction. The specific steps are:
所述酯化反应：Described esterification reaction:
采用对苯二甲酸(PTA)、乙二醇(EG)为主要原料，含氟改性剂四氟对苯二甲酸(FPTA)作为第三单体配成均匀浆料，同时加入所用二元酸总重量的0.01％的氧化镁，进行酯化反应。原料中对苯二甲酸(PTA)、四氟对苯二甲酸(FPTA)、乙二醇(EG)摩尔比为：PTA:FPTA＝1:0.5；(PTA+FPTA):EG＝1:1.2。酯化反应中无需外加催化剂，氮气氛围中加压，压力控制在0.4MPa下进行，温度控制在250℃，酯化水馏出量达到理论值的90％以上为反应终点。Use terephthalic acid (PTA) and ethylene glycol (EG) as the main raw materials, and the fluorine-containing modifier tetrafluoroterephthalic acid (FPTA) as the third monomer to make a uniform slurry, and add the dibasic acid used at the same time 0.01% of the total weight of magnesium oxide is used for esterification. The molar ratios of terephthalic acid (PTA), tetrafluoroterephthalic acid (FPTA), and ethylene glycol (EG) in the raw materials are: PTA:FPTA=1:0.5; (PTA+FPTA):EG=1:1.2. In the esterification reaction, no external catalyst is needed, pressurized in a nitrogen atmosphere, the pressure is controlled at 0.4MPa, the temperature is controlled at 250°C, and the distilled amount of esterification water reaches more than 90% of the theoretical value as the reaction end point.
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，在酯化产物中加入所用二元酸重量的0.01％的催化剂三氧化二锑和所用二元酸重量的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1KPa，温度控制在255℃，反应时间为60分钟。In the low-vacuum stage of the polycondensation reaction, add 0.01% of the catalyst antimony trioxide and 0.01% of the dibasic acid weight used in the esterification product to the stabilizer triphenyl phosphate. At this stage, the pressure was steadily pumped from normal pressure to an absolute pressure of less than 1KPa, the temperature was controlled at 255°C, and the reaction time was 60 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，即得到含氟无规共聚酯切片。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 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 required value, the material is discharged, and after casting, cooling and pelletizing, the fluorine-containing random copolyester chips are obtained.
制备POY纤维的方法：Method for preparing POY fiber:
是由所述含氟无规共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295℃；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；最终制得含氟无规共聚酯POY纤维，单丝纤度为2.0dtex；断裂强度为1.8cN/dtex；断裂伸长率为140％。The POY fiber is obtained from the fluorine-containing random copolyester chips through screw melt extrusion, cooling, oiling and winding; wherein, the extruding temperature is 295°C; the cooling is ring air cooling , the temperature is 20°C, the relative humidity is 70%, and the wind speed is 0.8m/s; the oiling adopts the emulsion containing 10wt% oil for fluorine-containing polyester POY fiber; the oil for oil for fluorine-containing polyester POY fiber Preparation: The 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 tridecanol polyoxyethylene ether phosphate Potassium salt and 3 parts of perfluorohexyl ethyl acrylate were stirred and mixed uniformly, then added to butanol random polyether, and stirred for 2 hours to obtain POY oil for fluorine-containing polyester fiber; the oiled The oil rate is 1.5%; the speed of the winding is 2800m/min; the final fluorine-containing random copolyester POY fiber is obtained, and the single filament fineness is 2.0dtex; the breaking strength is 1.8cN/dtex; the elongation at break is 140%.
实施例8Example 8
一种含氟无规共聚酯的制备方法，分为酯化反应和缩聚反应两步。具体步骤为：A preparation method of fluorine-containing random copolyester is divided into two steps of esterification reaction and polycondensation reaction. The specific steps are:
所述酯化反应：Described esterification reaction:
采用对苯二甲酸(PTA)、乙二醇(EG)为主要原料，含氟改性剂四氟对苯二甲酸(FPTA)作为第三单体配成均匀浆料，同时加入所用二元酸总重量的0.02％的氧化硅，进行酯化反应。原料中对苯二甲酸(PTA)、四氟对苯二甲酸(FPTA)、乙二醇(EG)摩尔比为：PTA:FPTA＝1:0.6；(PTA+FPTA):EG＝1:1.4。酯化反应中无需外加催化剂，氮气氛围中加压，压力控制在0.3MPa下进行，温度控制在245℃，酯化水馏出量达到理论值的90％以上为反应终点。Use terephthalic acid (PTA) and ethylene glycol (EG) as the main raw materials, and the fluorine-containing modifier tetrafluoroterephthalic acid (FPTA) as the third monomer to make a uniform slurry, and add the dibasic acid used at the same time 0.02% of the total weight of silicon oxide for esterification. The molar ratios of terephthalic acid (PTA), tetrafluoroterephthalic acid (FPTA), and ethylene glycol (EG) in the raw materials are: PTA:FPTA=1:0.6; (PTA+FPTA):EG=1:1.4. In the esterification reaction, no external catalyst is needed, pressurized in a nitrogen atmosphere, the pressure is controlled at 0.3MPa, the temperature is controlled at 245°C, and the distilled amount of esterification water reaches more than 90% of the theoretical value as the reaction end point.
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，在酯化产物中加入所用二元酸重量的0.02％的催化剂乙二醇锑和所用二元酸重量的0.02％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800Pa，温度控制在250℃，反应时间为50分钟。In the low vacuum stage of the polycondensation reaction, 0.02% of the catalyst ethylene glycol antimony and 0.02% of the weight of the dibasic acid used are added to the esterification product, and the stabilizer trimethyl phosphate is added under negative pressure conditions. At this stage, the pressure was steadily pumped from normal pressure to an absolute pressure of less than 800Pa, the temperature was controlled at 250°C, and the reaction time was 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80Pa，反应温度控制在275℃，反应时间2.5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，即得到含氟无规共聚酯切片。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 80 Pa, the reaction temperature is controlled at 275° C., and the reaction time is 2.5 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 required value, the material is discharged, and after casting, cooling and pelletizing, the fluorine-containing random copolyester chips are obtained.
制备POY纤维的方法：Method for preparing POY fiber:
是由所述含氟无规共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290℃；所述的冷却为环吹风冷却，温度为25℃，相对湿度为65％，风速为0.6m/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；最终制得含氟无规共聚酯POY纤维，单丝纤度为1.5dtex；断裂强度为2.0cN/dtex；断裂伸长率为135％。The POY fiber is obtained from the fluorine-containing random copolyester chips through screw melt extrusion, cooling, oiling and winding; wherein, the extrusion temperature is 290°C; the cooling is ring air cooling , the temperature is 25°C, the relative humidity is 65%, and the wind speed is 0.6m/s; the oiling adopts the emulsion containing 9wt% oil for fluorine-containing polyester POY fibers; the oil for oil for fluorine-containing polyester POY fibers Preparation: The components are calculated in parts by weight. Take 60 parts of propylene glycol random polyether, heat it to 60°C, mix 20 parts of polyethylene glycol monolaurate, 15 parts of potassium lauryl phosphate and 5 parts of all Fluorobutyl 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 random copolyester POY fiber is finally obtained, the single filament fineness is 1.5dtex; the breaking strength is 2.0cN/dtex; the breaking elongation is 135%.
实施例9Example 9
一种含氟无规共聚酯的制备方法，分为酯化反应和缩聚反应两步。具体步骤为：A preparation method of fluorine-containing random copolyester is divided into two steps of esterification reaction and polycondensation reaction. The specific steps are:
所述酯化反应：Described esterification reaction:
采用对苯二甲酸(PTA)、乙二醇(EG)为主要原料，含氟改性剂四氟对苯二甲酸(FPTA)作为第三单体配成均匀浆料，同时加入所用二元酸总重量的0.03％的氧化钙，进行酯化反应。原料中对苯二甲酸(PTA)、四氟对苯二甲酸(FPTA)、乙二醇(EG)摩尔比为：PTA:FPTA＝1:0.8；(PTA+FPTA):EG＝1:1.6。酯化反应中无需外加催化剂，氮气氛围中加压，压力控制在0.2MPa下进行，温度控制在240℃，酯化水馏出量达到理论值的90％以上为反应终点。Use terephthalic acid (PTA) and ethylene glycol (EG) as the main raw materials, and the fluorine-containing modifier tetrafluoroterephthalic acid (FPTA) as the third monomer to make a uniform slurry, and add the dibasic acid used at the same time 0.03% of the total weight of calcium oxide for esterification. The molar ratios of terephthalic acid (PTA), tetrafluoroterephthalic acid (FPTA), and ethylene glycol (EG) in the raw materials are: PTA:FPTA=1:0.8; (PTA+FPTA):EG=1:1.6. No external catalyst is needed in the esterification reaction, pressurization is carried out in a nitrogen atmosphere, the pressure is controlled at 0.2 MPa, the temperature is controlled at 240 ° C, and the distilled amount of esterification water reaches more than 90% of the theoretical value as the reaction end point.
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，在酯化产物中加入所用二元酸重量的0.03％的催化剂醋酸锑和所用二元酸重量的0.03％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600Pa，温度控制在260℃，反应时间为40分钟。In the low vacuum stage of the polycondensation reaction, 0.03% of the catalyst antimony acetate and 0.03% of the weight of the dibasic acid used were added to the esterification product, and the stabilizer trimethyl phosphite was added under negative pressure conditions. Start the polycondensation reaction, the pressure at this stage is steadily pumped from normal pressure to an absolute pressure of less than 600Pa, the temperature is controlled at 260°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2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，即得到含氟无规共聚酯切片。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 2 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 required value, the material is discharged, and after casting, cooling and pelletizing, the fluorine-containing random copolyester chips are obtained.
制备POY纤维的方法：Method for preparing POY fiber:
是由所述含氟无规共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30℃，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；最终制得含氟无规共聚酯POY纤维，单丝纤度为1.5dtex；断裂强度为2.2cN/dtex；断裂伸长率为125％。The POY fiber is obtained from the fluorine-containing random copolyester chips through screw melt extrusion, cooling, oiling and winding; wherein, the extruding temperature is 285°C; the cooling is ring air cooling , the temperature is 30°C, the relative humidity is 60%, and the wind speed is 0.4m/s; the oiling adopts the emulsion containing 8wt% oil for fluorine-containing polyester POY fiber; the oil for oil for fluorine-containing polyester POY fiber Preparation: The components are calculated in parts by weight. Take 50 parts of lauryl alcohol random polyether, heat it to 50 ° C, and mix 32 parts of polyethylene glycol diester, 13 parts of potassium dodecyl phosphate and 5 parts One part of perfluorobutyl 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 The winding speed is 1.5%; the winding speed is 3000m/min; the fluorine-containing random copolyester POY fiber is finally obtained, and the single filament fineness is 1.5dtex; the breaking strength is 2.2cN/dtex; the elongation at break is 125% .
实施例10Example 10
一种含氟无规共聚酯的制备方法，分为酯化反应和缩聚反应两步。具体步骤为：A preparation method of fluorine-containing random copolyester is divided into two steps of esterification reaction and polycondensation reaction. The specific steps are:
所述酯化反应：Described esterification reaction:
采用对苯二甲酸(PTA)、乙二醇(EG)为主要原料，含氟改性剂四氟对苯二甲酸(FPTA)作为第三单体配成均匀浆料，同时加入所用二元酸总重量的0.04％的氧化锌，进行酯化反应。原料中对苯二甲酸(PTA)、四氟对苯二甲酸(FPTA)、乙二醇(EG)摩尔比为：PTA:FPTA＝1:1；(PTA+FPTA):EG＝1:1.8。酯化反应中无需外加催化剂，氮气氛围中加压，压力控制在0.2MPa下进行，温度控制在245℃，酯化水馏出量达到理论值的90％以上为反应终点。Use terephthalic acid (PTA) and ethylene glycol (EG) as the main raw materials, and the fluorine-containing modifier tetrafluoroterephthalic acid (FPTA) as the third monomer to make a uniform slurry, and add the dibasic acid used at the same time 0.04% of the total weight of zinc oxide for esterification. The molar ratios of terephthalic acid (PTA), tetrafluoroterephthalic acid (FPTA), and ethylene glycol (EG) in the raw materials are: PTA:FPTA=1:1; (PTA+FPTA):EG=1:1.8. In the esterification reaction, no external catalyst is needed, pressurized in a nitrogen atmosphere, the pressure is controlled at 0.2 MPa, the temperature is controlled at 245 ° C, and the distilled amount of esterification water reaches more than 90% of the theoretical value as the reaction end point.
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，在酯化产物中加入所用二元酸重量的0.03％的催化剂三氧化二锑和所用二元酸重量的0.03％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500Pa，温度控制在260℃，反应时间为40分钟。In the low vacuum stage of the polycondensation reaction, add 0.03% of the catalyst antimony trioxide and 0.03% of the dibasic acid weight used in the esterification product to the stabilizer trimethyl phosphite of the used dibasic acid weight. The polycondensation reaction starts under the same conditions, and the pressure at this stage is steadily pumped from normal pressure to an absolute pressure of less than 500Pa, the temperature is controlled at 260°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50Pa，反应温度控制在280℃，反应时间2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，即得到含氟无规共聚酯切片。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 280° C., and the reaction time is 2 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 required value, the material is discharged, and after casting, cooling and pelletizing, the fluorine-containing random copolyester chips are obtained.
制备POY纤维的方法：Method for preparing POY fiber:
是由所述含氟无规共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295℃；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；最终制得含氟无规共聚酯POY纤维，单丝纤度为0.5dtex；断裂强度为2.5cN/dtex；断裂伸长率为110％。The POY fiber is obtained from the fluorine-containing random copolyester chips through screw melt extrusion, cooling, oiling and winding; wherein, the extruding temperature is 295°C; the cooling is ring air cooling , the temperature is 20°C, the relative humidity is 70%, and the wind speed is 0.8m/s; the oiling adopts the emulsion containing 10wt% oil for fluorine-containing polyester POY fibers; the oil for oil for fluorine-containing polyester POY fibers Preparation: The components are calculated in parts by weight. Take 60 parts of propylene glycol random polyether, heat it to 45°C, mix 20 parts of polyethylene glycol monooleate, 15 parts of potassium lauryl phosphate and 5 parts of all Fluorooctyl 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 fiber; the oiling rate of the oiling was 0.42 %; the winding speed is 3200m/min; the fluorine-containing random copolyester POY fiber is finally obtained, the single filament fineness is 0.5dtex; the breaking strength is 2.5cN/dtex; the breaking elongation is 110%.
实施例11Example 11
一种含氟无规共聚酯的制备方法，分为酯化反应和缩聚反应两步。具体步骤为：A preparation method of fluorine-containing random copolyester is divided into two steps of esterification reaction and polycondensation reaction. The specific steps are:
所述酯化反应：Described esterification reaction:
采用对苯二甲酸(PTA)、乙二醇(EG)为主要原料，含氟改性剂四氟对苯二甲酸(FPTA)作为第三单体配成均匀浆料，同时加入所用二元酸总重量的0.05％的氧化锰，进行酯化反应。原料中对苯二甲酸(PTA)、四氟对苯二甲酸(FPTA)、乙二醇(EG)摩尔比为：PTA:FPTA＝1:0.8；(PTA+FPTA):EG＝1:2。酯化反应中无需外加催化剂，氮气氛围中加压，压力控制在常压下进行，温度控制在240℃，酯化水馏出量达到理论值的90％以上为反应终点。Use terephthalic acid (PTA) and ethylene glycol (EG) as the main raw materials, and the fluorine-containing modifier tetrafluoroterephthalic acid (FPTA) as the third monomer to make a uniform slurry, and add the dibasic acid used at the same time 0.05% of the total weight of manganese oxide for esterification. The molar ratios of terephthalic acid (PTA), tetrafluoroterephthalic acid (FPTA), and ethylene glycol (EG) in the raw materials are: PTA:FPTA=1:0.8; (PTA+FPTA):EG=1:2. In the esterification reaction, no external catalyst is needed, pressurized in a nitrogen atmosphere, the pressure is controlled at normal pressure, the temperature is controlled at 240°C, and the distilled amount of esterification water reaches more than 90% of the theoretical value as the reaction end point.
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，在酯化产物中加入所用二元酸重量的0.03％的催化剂乙二醇锑和所用二元酸重量的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300Pa，温度控制在260℃，反应时间为40分钟。In the low vacuum stage of the polycondensation reaction, 0.03% of the catalyst ethylene glycol antimony and 0.03% of the weight of the dibasic acid used are added to the esterification product, and the stabilizer trimethyl phosphate is added under negative pressure conditions. At this stage, the pressure was steadily pumped from normal pressure to an absolute pressure of less than 300Pa, the temperature was controlled at 260°C, and the reaction time was 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30Pa，反应温度控制在275℃，反应时间2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，即得到含氟无规共聚酯切片。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 30 Pa, the reaction temperature is controlled at 275° C., and the reaction time is 2 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 required value, the material is discharged, and after casting, cooling and pelletizing, the fluorine-containing random copolyester chips are obtained.
制备POY纤维的方法：Method for preparing POY fiber:
是由所述含氟无规共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30℃，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；最终制得含氟无规共聚酯POY纤维，单丝纤度为1.5dtex；断裂强度为2.2cN/dtex；断裂伸长率为125％。The POY fiber is obtained from the fluorine-containing random copolyester chips through screw melt extrusion, cooling, oiling and winding; wherein, the extruding temperature is 285°C; the cooling is ring air cooling , the temperature is 30°C, the relative humidity is 60%, and the wind speed is 0.4m/s; the oiling adopts the emulsion containing 8wt% oil for fluorine-containing polyester POY fiber; the oil for oil for fluorine-containing polyester POY fiber Preparation: The components are calculated in parts by weight. Take 50 parts of lauryl alcohol random polyether, heat it to 50 ° C, and mix 32 parts of polyethylene glycol diester, 13 parts of potassium dodecyl phosphate and 5 parts One part of perfluorobutyl 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 The winding speed is 1.5%; the winding speed is 3000m/min; the fluorine-containing random copolyester POY fiber is finally obtained, and the single filament fineness is 1.5dtex; the breaking strength is 2.2cN/dtex; the elongation at break is 125% .
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