CN103469359A - Fluorine-containing PTT-PET skin-core composite fiber and method for preparing same - Google Patents
Fluorine-containing PTT-PET skin-core composite fiber and method for preparing same Download PDFInfo
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- CN103469359A CN103469359A CN2013104472011A CN201310447201A CN103469359A CN 103469359 A CN103469359 A CN 103469359A CN 2013104472011 A CN2013104472011 A CN 2013104472011A CN 201310447201 A CN201310447201 A CN 201310447201A CN 103469359 A CN103469359 A CN 103469359A
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 106
- 239000011737 fluorine Substances 0.000 title claims abstract description 99
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000000835 fiber Substances 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title abstract description 11
- 238000005886 esterification reaction Methods 0.000 claims abstract description 68
- 238000002360 preparation method Methods 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 37
- 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 31
- 238000009987 spinning Methods 0.000 claims abstract description 21
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 10
- 239000003112 inhibitor Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 230000032050 esterification Effects 0.000 claims description 67
- 238000006068 polycondensation reaction Methods 0.000 claims description 64
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 230000001054 cortical effect Effects 0.000 claims description 16
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- 239000011162 core material Substances 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011654 magnesium acetate Substances 0.000 claims description 9
- 229940069446 magnesium acetate Drugs 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 238000004513 sizing Methods 0.000 claims description 7
- 238000004804 winding Methods 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 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
- 150000002148 esters Chemical class 0.000 claims description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 5
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 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
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 125000001449 isopropyl group Chemical class [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 abstract description 12
- 230000002209 hydrophobic effect Effects 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000012643 polycondensation polymerization Methods 0.000 abstract 1
- 238000010186 staining Methods 0.000 abstract 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 41
- 229920000728 polyester Polymers 0.000 description 40
- 229920000139 polyethylene terephthalate Polymers 0.000 description 40
- 239000005020 polyethylene terephthalate Substances 0.000 description 40
- 239000000047 product Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 8
- -1 polyethylene terephthalate Polymers 0.000 description 7
- 150000001991 dicarboxylic acids Chemical class 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 230000002940 repellent Effects 0.000 description 6
- 239000005871 repellent Substances 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000005453 pelletization Methods 0.000 description 5
- 239000002689 soil Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 239000004811 fluoropolymer Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 238000009941 weaving Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004812 Fluorinated ethylene propylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 229960005082 etohexadiol Drugs 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- LTHCSWBWNVGEFE-UHFFFAOYSA-N octanamide Chemical compound CCCCCCCC(N)=O LTHCSWBWNVGEFE-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920009441 perflouroethylene propylene Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Multicomponent Fibers (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a fluorine-containing PTT-PET skin-core composite fiber and a method for preparing the fluorine-containing PTT-PET skin-core composite fiber. The method comprises the preparation of fluorine-containing skin material PTT and the preparation of skin-core composite fiber. Tetrafluoroterephthalic acid and 1, 3- propylene glycol are adopted as raw materials, inhibitor is added to the raw materials and esterification reaction and condensation polymerization are carried out under a proper condition to obtain the fluorine-containing PTT. Then, the fluorine-containing PTT serves as the skin, PET serves as the core and a proper composite spinning technology is adopted to prepare the skin-core composite fiber. The obtained fluorine-containing PTT has good heat stability and processibility and the hydrophobic performance and the oleophobic performance of the fluorine-containing PTT are improved due to the introduction of fluorine atoms. The fiber prepared through composite spinning has good mechanical property for preparing the PET and the PTT and good staining resisting performance, greatly saves cost and has huge prospects in manufacturing of waterproof clothes, staining-resisting work clothes and work clothes in some special industries.
Description
Technical field
The present invention relates to a kind of fluorine-containing PTT-PET core-skin composite fiber and preparation method thereof, comprise the preparation of the fluorine-containing PTT of cortical material and the preparation of core-skin composite fiber.Particularly relate to and a kind ofly take the polytetrafluoro propylene glycol ester terephthalate as the fluorine-containing PTT material of cortex, core-skin composite fiber that the PET of take is core material and preparation method thereof.
Background technology
Along with the development and progress of technology, the continuous lifting that people require, the fiber of homogenous material can not well meet people's demand, and various composite fibres just arise at the historic moment.They have homogenous material fiber the performance that can not simultaneously possess, have the advantage of multiple fiber concurrently, better performance can be provided, wherein, core-skin composite fiber is exactly a kind of good composite fibre.This fiber not only can have the partial properties that Cortical fiber possesses, the partial properties that also there is the sandwich layer fiber, reasonably the performance combination just can obtain the core-skin composite fiber of function admirable, and preparation technology is simple, can reduce the consumption of cortical material simultaneously, cost-saving.
Polyester is one of the most widely used synthetic high polymer of the current mankind; just synthesized ethylene glycol terephthalate (PET) forties as far back as twentieth century; and find that it has excellent performance, and be widely used in the fields such as weaving, packing, health care, automobile, electronic apparatus, security protection, environmental protection.Polytrimethylene terephthalate (PTT) is a kind of new polyester macromolecular material that has development prospect of new research and development after polyethylene terephthalate (PET) and mutual-phenenyl two acid bromide two alcohol ester (PBT), within 1998, by the U.S., is chosen as one of six large petrochemical industry new products.With PET, PBT, compare, PTT has better elasticity, DIMENSIONAL STABILITY and dyeability etc.There is the multiple good characteristics such as uvioresistant, anti-internal stress, low water absorbable, low static and good biological degradability, reusable edible simultaneously, therefore be widely used in the fields such as carpet industry, dress materials, engineering plastics.Along with social progress, the raising of living standards of the people, need more and more higher to differential, the functionalization of polyester fiber.Therefore also become particularly important of the modification of polyester, the polyester modification purpose, except the conventional polyester performance is optimized, is mainly to give new polyester differential functional characteristic by modified method.Such as: antistatic, fire-retardant, moisture absorbing and sweat releasing, antifouling deodorization etc.At present, the main new varieties of polyester have: antistatic polyester, high-strength wearable polyester, imitative cotton ultra-soft polyester, super-hydrophobicity polyester, anti-soil polyester etc.At present, by introduce fluorine atom in polymer, thereby improve the surface property of material, as hydro-oleophobicity and soil resistance etc., and give polyester material various functions.Because fluoropolymer has low-surface-energy, low-friction coefficient and non-adhesiveness usually, the dust dirt such as is difficult to adhere at the characteristic, so the anti-soil ABRASION RESISTANCE of fluoropolymer is good.And current fluoropolymer be take the fluoroolefin base polymer as main (such as polytetrafluoroethylene (PTFE), Kynoar, fluorinated ethylene propylene copolymer, ethylene-tetrafluoroethylene copolymer etc.); The research of fluorochemical urethane, fluorochemical polyether, fluorine-containing polyester etc. relatively lags behind.Many scholars are studied the fluorochemical modified poly ester, and have obtained certain achievement.The mode of fluorochemical modified poly ester is mainly by adding fluorine-containing end-capping reagent at present, or adds the fluorochemicals such as Fluorinated dihydric alcohol, fluorine-containing binary acid to carry out modified poly ester as the 3rd monomer.Adopt adding of fluorine-containing end-capping reagent in Chinese patent CN101139434A, dimethyl isophthalate and butanediol adopt ester-interchange method, add fluorine-containing end-capping reagent N-ethoxy perfluor caprylamide, have prepared the low and polyester material that the stain resistant performance is good of fluorinated volume.Hu Juan (Hu Juan. the MOLECULE DESIGN of fluorine-containing polyester and photoresist waveguide material and performance study [D]. Master's thesis, Jilin: Jilin University, 2007.) utilize the principle of MOLECULE DESIGN, by adding the mode of Fluorinated dihydric alcohol copolymerization, paraphthaloyl chloride, hexafluoro bisphenol-a and fluorine-containing ethohexadiol ternary polymerization have been synthesized to the polyester of novel high fluorinated volume.This polyester has excellent performance and is applied to optical waveguide material.Yet the polyester that these are contained to fluorine element is applied to, in weaving and packaging material, certain limitation is arranged, subject matter is that the molecular weight of polyesters that contains fluorine element of prior art is low, can not meet the requirement of spinning and film forming; Prior art is mainly to give its water proof anti-soil function by the fluorine-containing rear Collator Mode of fabric at present, and the problem such as that the shortcoming of this class methods maximum is to be difficult to solve is ageing, durability and ABRASION RESISTANCE, and waste time and energy.
Therefore, develop fluorine-containing polyester sheath core compound fibre for super-hydrophobic, the hydrophobic and oil repellent of weaving and packaging material, the modification of antifouling property, will there is important theory significance and using value.
Summary of the invention
The purpose of this invention is to provide a kind of fluorine-containing PTT-PET core-skin composite fiber and preparation method thereof, comprise the preparation of the fluorine-containing PTT of cortical material and the preparation of core-skin composite fiber.Wherein fluorine-containing PTT refers to the polytetrafluoro propylene glycol ester terephthalate.Fluorine-containing PTT of the present invention has introduced fluorine atom on the main chain of polymer, and the fluorine-containing PTT section of preparing can be directly used in spinning, can give fluorine-containing ptt fiber permanent hydrophobic and oil repellent performance, solve the problem that the modification of conventional P TT fiber hydrophobic and oil repellent is wasted time and energy.Simultaneously, adopt composite spinning method to prepare and take fluorine-containing PTT as the core-skin composite fiber that cortical material, PET are core material, not only given core-skin composite fiber good mechanical property and hydrophobic and oil repellent performance, also provide cost savings greatly.
A kind of fluorine-containing PTT-PET core-skin composite fiber of the present invention, cortical material is fluorine-containing PTT, core material is PET; Described fluorine-containing PTT is the polytetrafluoro propylene glycol ester terephthalate, and its general structure is
N=70～200 wherein.
A kind of fluorine-containing PTT-PET core-skin composite fiber as above, the ratio of the cortex of described fluorine-containing PTT-PET core-skin composite fiber and the sectional area of sandwich layer is 2～5: 5.
As above require 1 described a kind of fluorine-containing PTT-PET core-skin composite fiber, the filament number of described fluorine-containing PTT-PET core-skin composite fiber is 1～15dtex.
The present invention also provides a kind of preparation method of fluorine-containing PTT-PET core-skin composite fiber, comprises the preparation method of fluorine-containing PTT and the preparation method of core-skin composite fiber, and concrete steps are:
1. the preparation method of fluorine-containing PTT
Be divided into esterification and polycondensation reaction two steps; Concrete steps are:
Described esterification:
Adopt tetrafluoro terephthalic acid (TPA) and 1,3-PD as raw material, add inhibitor, carry out esterification after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and pressure is controlled at normal pressure～0.3MPa, and temperature is at 250～260 ℃, and what esterification water quantity of distillate reached theoretical value is the esterification terminal more than 90%;
Described inhibitor is a kind of in magnesia, silica, calcium oxide, zinc oxide and manganese oxide; There is fluorine atom on phenyl ring due to dicarboxylic acids used, the electronegativity of fluorine atom is large, conjugation at esterification stage fluorine atom makes the acidity of dicarboxylic acids strengthen, cause the activity of carboxyl in dicarboxylic acids to increase simultaneously, make reaction speed accelerate, and the reaction speed increase easily makes side reaction produce, these side reaction products have larger impact to follow-up polycondensation reaction, particularly generate the end-blocking product of alkene and aldehyde, restricted the increase of molecular weight of product; From experimental result, if do not add inhibitor, synthetic molecular weight of polyesters is on the low side, can not meet the demand of spinning and film forming; Adding for controlling the speed in esterification stage of inhibitor, reduced side reaction, improved the molecular weight of product, makes and meet spinning requirement.
Usually, it in the polyester esterification process, is the hydrogen ion that ionizes out by the dicarboxylic acids used catalyst as esterification, carry out self-catalyzed reaction, temperature by regulating esterification, pressure and micromolecularly eject the speed of controlling its esterification, however the prerequisite of carrying out esterification is just can carry out esterification under certain reaction temperature and pressure.In the situation that temperature is too low or pressure is inadequate, esterification can not carry out or speed extremely slow, thereby affect follow-up technique.If the little molecule in esterification is failed timely discharge and is easily caused unnecessary side reaction.In building-up process, conjugation due to fluorine, at esterification stage fluorine atom, make the acidity of dicarboxylic acids strengthen, cause the activity of carboxyl in dicarboxylic acids to increase simultaneously, make reaction speed accelerate, side reaction increases, be difficult to control, and then affect the growth of molecular weight of product, thus add inhibitor, by selecting metal oxide used to regulate.Described metal oxide can dissociate by following two kinds of modes:
Here M is metal ion, if the electronegativity of M is quite large, the duplet of oxonium ion is had to stronger attraction, so just can make O-H key weaken, and is conducive to reaction from solution; On the contrary, if the electronegativity of M is little, so just will generate the alkali center.M-O-H is similar with amphoteric compound, and when having alkaline matter to exist, reaction will be undertaken by the mode of acid dissociation; And, when acidic materials exist, by the mode of alkali formula ionization, undertaken.M-O-and the M of back reaction from acid dissociation mode and alkali formula ionization mode
+visible, M
+as acid centre, its intensity only has direct relation with the electronegativity of metal ion, and M-O
-in the O ion relevant with the negative charge density on oxygen as the intensity at alkali center, negative charge density is larger, intensity is also larger.Negative charge density on visible oxonium ion and metal ion electronegativity have close relationship, and the metal ion electronegativity is less, and negative charge density is just larger.So, the acid and alkalescence of metal oxide has just all connected with the electronegativity of metal ion, and the oxide that the electronegativity of metal ion is large is mainly acid, and what electronegativity was little is alkalescence.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig;
The described polycondensation reaction low vacuum stage, add catalyst and stabilizing agent in esterification products, under the condition of negative pressure, start polycondensation reaction, this staged pressure steadily is evacuated to below absolute pressure 500Pa by normal pressure, temperature is controlled at 260～270 ℃, and the reaction time is 30～50 minutes;
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continue to vacuumize, and makes reaction pressure be down to absolute pressure and be less than 100Pa, and reaction temperature is controlled at 260～275 ℃, 3～4 hours reaction time.Polycondensation reaction is with reactor stirring motor power or the in-line viscometer reading judgement reaction end that is as the criterion.
2. the preparation method of fluorine-containing PTT-PET core-skin composite fiber
Using described fluorine-containing PTT as cortical material, PET, as core material, carries out the core-sheath spinning, and spinning temperature is 275-290 ℃, and winding speed is controlled at 2700～3200m/min.
As preferred technical scheme:
The preparation method of a kind of fluorine-containing PTT-PET core-skin composite fiber as above, the mol ratio of described 1,3-PD and tetrafluoro terephthalic acid (TPA) is 1.3～2.0: 1.
The preparation method of a kind of fluorine-containing PTT-PET core-skin composite fiber as above, described catalyst is selected from a kind of in butyl titanate-magnesium acetate, metatitanic acid four isopropyl esters-magnesium acetate, tetraethyl titanate-magnesium acetate, stannous acetate, dibutyltin diacetate, and catalyst amount is 0.01%～0.05% of described tetrafluoro terephthalic acid (TPA) weight.
The preparation method of a kind of fluorine-containing PTT-PET core-skin composite fiber as above, described stabilizing agent is selected from a kind of in triphenyl phosphate, trimethyl phosphate and Trimethyl phosphite, and stabilizing agent dosage is 0.01%～0.05% of described tetrafluoro terephthalic acid (TPA) weight.
The preparation method of a kind of fluorine-containing PTT-PET core-skin composite fiber as above, the addition of described inhibitor is 0.01%～0.05% of described tetrafluoro terephthalic acid (TPA) weight.
Esterification of the present invention is in the stage, reaction end actual water quantity of distillate produced in esterification reach theoretical value 90% with on grasp.The quantity of distillate that theoretical value is gained water while pressing the chemical equation complete reaction.Due to esterification this as reversible reaction, moreover raw material has residually in conveyance conduit, and, along with the carrying out of reaction, the viscosity of system increases, the shipwreck that can cause esterification to produce is therefrom to discharge.
In polycondensation reaction high vacuum stage of Fig of the present invention, the numerical value that reaction end reaches setting by reactor beater motor power and in-line viscometer calculation value is grasped.The setting numerical value of its reactor beater motor power of different devices and in-line viscometer calculation value is not necessarily identical, and setting determining of numerical value can obtain by the analysis to polyester slice.
The fluorine-containing PTT of gained of the present invention is due to the introducing of fluorine atom, improved the hydrophobic and oil repellent performance of PTT material, so the fluorine-containing PTT of take in the present invention is cortex, the core-skin composite fiber that PET is sandwich layer not only has good mechanical property, the dirty performance of good permanent oil resistant is also arranged, and cost reduces greatly, make it at waterproof garment, in the Work Clothes manufacture of the Work Clothes born dirty and some special industry, huge prospect is arranged.
Beneficial effect:
1, the PTT contain fluorine atoms made; strong electronegativity due to fluorine; high C-F bond energy and make the copolyesters synthesized except the performance of the traditional polyester of further lifting to the shielding protection effect of carbochain; the surface that has also reduced polyester material can; make material that permanent hydrophobic and oil repellent be arranged, the oil rub resistance performance.
2, can control the speed of esterification in fluorine-containing PTT esterification process by inhibiting, reduce the generation of side reaction.
3, the fluorine-containing PTT section of gained can direct fabrics.
4, the fluorine-containing PTT of gained has good heat endurance and machinability.
5, adopting fluorine-containing PTT is that cortical material, PET are that the core-skin composite fiber that core material makes has good mechanical property and the dirty performance of permanent oil resistant, and compare fiber prepared by the fluorine-containing PTT of independent use, cost reduces greatly, thereby better using value is arranged.
The specific embodiment
Below in conjunction with the specific embodiment, further set forth the present invention.Should be understood that these embodiment only are not used in and limit the scope of the invention for the present invention is described.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
A kind of fluorine-containing PTT-PET core-skin composite fiber of the present invention, cortical material is fluorine-containing PTT, core material is PET; Described fluorine-containing PTT is the polytetrafluoro propylene glycol ester terephthalate, and its general structure is
N=70～200 wherein.
A kind of fluorine-containing PTT-PET core-skin composite fiber as above, the ratio of the cortex of described fluorine-containing PTT-PET core-skin composite fiber and the sectional area of sandwich layer is 2～5: 5.
As above require 1 described a kind of fluorine-containing PTT-PET core-skin composite fiber, the filament number of described fluorine-containing PTT-PET core-skin composite fiber is 1～15dtex.
Embodiment 1
1. the preparation method of fluorine-containing PTT polyester, be divided into esterification and polycondensation reaction two steps.Concrete steps are:
Described esterification:
Adopt 1,3 propylene glycol that mol ratio is 1.3: 1 and tetrafluoro terephthalic acid (TPA) as raw material, add 0.01% magnesia of tetrafluoro terephthalic acid (TPA) weight simultaneously, carry out esterification after being made into uniform sizing material; Esterification is in nitrogen atmosphere, and pressure is controlled at 0.3MPa, and temperature is controlled at 260 ℃, and it is the esterification terminal that esterification water quantity of distillate reaches 90% of theoretical value.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, 0.01% the stabilizing agent triphenyl phosphate that adds 0.01% catalyst metatitanic acid four butyl esters of tetrafluoro terephthalic acid (TPA) weight-magnesium acetate and tetrafluoro terephthalic acid (TPA) weight in esterification products, start polycondensation reaction under the condition of negative pressure, this staged pressure steadily is evacuated to absolute pressure by normal pressure and is less than 500Pa, temperature is controlled at 265 ℃, and the reaction time is 50 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continue to vacuumize, and makes reaction pressure be down to absolute pressure and be less than 100Pa, and reaction temperature is controlled at 270 ℃, 4 hours reaction time.Polycondensation reaction is with reactor stirring motor power or the in-line viscometer reading judgement reaction end that is as the criterion.Discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, obtain fluorine-containing PTT polyester slice.
2. the preparation of core-skin composite fiber: using described fluorine-containing PTT as cortical material, PET is as core material, the ratio that carries out the cross-sectional area of core-sheath spinning cortex and sandwich layer is 2:5, spinning temperature is 275 ℃, winding speed is controlled at 2700m/min, and the filament number of the fluorine-containing PTT-PET core-skin composite fiber of gained is 1dtex.
Embodiment 2
1. the preparation method of fluorine-containing PTT polyester, be divided into esterification and polycondensation reaction two steps.Concrete steps are:
Described esterification:
Adopt 1,3 propylene glycol that mol ratio is 1.4: 1 and tetrafluoro terephthalic acid (TPA) as raw material, add 0.03% silica of tetrafluoro terephthalic acid (TPA) weight simultaneously, carry out esterification after being made into uniform sizing material; Esterification is in nitrogen atmosphere, and pressure is controlled at 0.3MPa, and temperature is controlled at 260 ℃, and it is the esterification terminal that esterification water quantity of distillate reaches 90% of theoretical value.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, 0.02% the stabilizing agent triphenyl phosphate that adds 0.02% catalyst metatitanic acid four isopropyl esters of tetrafluoro terephthalic acid (TPA) weight-magnesium acetate and tetrafluoro terephthalic acid (TPA) weight in esterification products, start polycondensation reaction under the condition of negative pressure, this staged pressure steadily is evacuated to absolute pressure by normal pressure and is less than 400Pa, temperature is controlled at 265 ℃, and the reaction time is 50 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continue to vacuumize, and makes reaction pressure be down to absolute pressure and be less than 100Pa, and reaction temperature is controlled at 270 ℃, 4 hours reaction time.Polycondensation reaction is with reactor stirring motor power or the in-line viscometer reading judgement reaction end that is as the criterion.Discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, obtain fluorine-containing PTT polyester slice.
2. the preparation of core-skin composite fiber: using described fluorine-containing PTT as cortical material, PET is as core material, carry out the core-sheath spinning, the ratio of the cross-sectional area of cortex and sandwich layer is 4: 5, spinning temperature is 290 ℃, winding speed is controlled at 3200m/min, and the filament number of the fluorine-containing PTT-PET core-skin composite fiber of gained is 15dtex.
Embodiment 3
1. the preparation method of fluorine-containing PTT polyester, be divided into esterification and polycondensation reaction two steps.Concrete steps are:
Described esterification:
Adopt 1,3 propylene glycol that mol ratio is 1.6: 1 and tetrafluoro terephthalic acid (TPA) as raw material, add 0.05% calcium oxide of tetrafluoro terephthalic acid (TPA) weight simultaneously, carry out esterification after being made into uniform sizing material; Esterification is in nitrogen atmosphere, and pressure is controlled at 0.2MPa, and temperature is controlled at 255 ℃, and it is the esterification terminal that esterification water quantity of distillate reaches 90% of theoretical value.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, 0.03% the stabilizing agent trimethyl phosphate that adds catalyst metatitanic acid tetra-ethyl ester-magnesium acetate of 0.03% of tetrafluoro terephthalic acid (TPA) weight and tetrafluoro terephthalic acid (TPA) weight in esterification products, start polycondensation reaction under the condition of negative pressure, this staged pressure steadily is evacuated to absolute pressure by normal pressure and is less than 400Pa, temperature is controlled at 260 ℃, and the reaction time is 45 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continue to vacuumize, and makes reaction pressure be down to absolute pressure and be less than 80Pa, and reaction temperature is controlled at 270 ℃, 3.5 hours reaction time.Polycondensation reaction is with reactor stirring motor power or the in-line viscometer reading judgement reaction end that is as the criterion.Discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, obtain fluorine-containing PTT polyester slice.
2. the preparation of core-skin composite fiber: using described fluorine-containing PTT as cortical material, PET is as core material, carry out the core-sheath spinning, the ratio of the cross-sectional area of cortex and sandwich layer is 3: 5, spinning temperature is 278 ℃, winding speed is controlled at 2900m/min, and the filament number of the fluorine-containing PTT-PET core-skin composite fiber of gained is 8dtex.
Embodiment 4
1. the preparation method of fluorine-containing PTT polyester, be divided into esterification and polycondensation reaction two steps.Concrete steps are:
Described esterification:
Adopt 1,3 propylene glycol that mol ratio is 1.8: 1 and tetrafluoro terephthalic acid (TPA) as raw material, add 0.03% zinc oxide of tetrafluoro terephthalic acid (TPA) weight simultaneously, carry out esterification after being made into uniform sizing material; Esterification is in nitrogen atmosphere, and pressure is controlled at 0.2MPa, and temperature is controlled at 250 ℃, and it is the esterification terminal that esterification water quantity of distillate reaches 90% of theoretical value.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, 0.04% the stabilizing agent trimethyl phosphate that adds the inferior tin of 0.04% catalyst acetic acid of tetrafluoro terephthalic acid (TPA) weight and tetrafluoro terephthalic acid (TPA) weight in esterification products, start polycondensation reaction under the condition of negative pressure, this staged pressure steadily is evacuated to absolute pressure by normal pressure and is less than 300Pa, temperature is controlled at 270 ℃, and the reaction time is 40 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continue to vacuumize, and makes reaction pressure be down to absolute pressure and be less than 60Pa, and reaction temperature is controlled at 275 ℃, 3 hours reaction time.Polycondensation reaction is with reactor stirring motor power or the in-line viscometer reading judgement reaction end that is as the criterion.Discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, obtain fluorine-containing PTT polyester slice.
2. the preparation of core-skin composite fiber: using described fluorine-containing PTT as cortical material, PET is as core material, carry out the core-sheath spinning, the ratio of the cross-sectional area of cortex and sandwich layer is 5: 5, spinning temperature is 280 ℃, winding speed is controlled at 2800m/min, and the filament number of the fluorine-containing PTT-PET core-skin composite fiber of gained is 5dtex.
Embodiment 5
1. the preparation method of fluorine-containing PTT polyester, be divided into esterification and polycondensation reaction two steps.Concrete steps are:
Described esterification:
Adopt 1,3 propylene glycol that mol ratio is 2.0: 1 and tetrafluoro terephthalic acid (TPA) as raw material, add 0.04% manganese oxide of tetrafluoro terephthalic acid (TPA) weight simultaneously, carry out esterification after being made into uniform sizing material; Esterification is in nitrogen atmosphere, and pressure is controlled at normal pressure, and temperature is controlled at 255 ℃, and it is the esterification terminal that esterification water quantity of distillate reaches 90% of theoretical value.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, 0.05% the stabilizing agent Trimethyl phosphite that adds 0.05% catalyst dibutyltin diacetate of tetrafluoro terephthalic acid (TPA) weight and tetrafluoro terephthalic acid (TPA) weight in esterification products, start polycondensation reaction under the condition of negative pressure, this staged pressure steadily is evacuated to absolute pressure by normal pressure and is less than 300Pa, temperature is controlled at 265 ℃, and the reaction time is 30 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continue to vacuumize, and makes reaction pressure be down to absolute pressure and be less than 50Pa, and reaction temperature is controlled at 275 ℃, 3 hours reaction time.Polycondensation reaction is with reactor stirring motor power or the in-line viscometer reading judgement reaction end that is as the criterion.Discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, obtain fluorine-containing PTT polyester slice.
2. the preparation of core-skin composite fiber: using described fluorine-containing PTT as cortical material, PET is as core material, carry out the core-sheath spinning, the ratio of the cross-sectional area of cortex and sandwich layer is 1: 2, spinning temperature is 285 ℃, winding speed is controlled at 3100m/min, and the filament number of the fluorine-containing PTT-PET core-skin composite fiber of gained is 13dtex.
Claims (8)
1. a fluorine-containing PTT-PET core-skin composite fiber, it is characterized in that: the cortical material of described fluorine-containing PTT-PET core-skin composite fiber is fluorine-containing PTT, core material is PET; Described fluorine-containing PTT is the polytetrafluoro propylene glycol ester terephthalate, and its general structure is
N=70～200 wherein.
2. a kind of fluorine-containing PTT-PET core-skin composite fiber according to claim 1, is characterized in that, the ratio of the cortex of described fluorine-containing PTT-PET core-skin composite fiber and the sectional area of sandwich layer is 2～5: 5.
3. a kind of fluorine-containing PTT-PET core-skin composite fiber according to claim 1, is characterized in that, the filament number of described fluorine-containing PTT-PET core-skin composite fiber is 1～15dtex.
4. the preparation method of a kind of fluorine-containing PTT-PET core-skin composite fiber as claimed in claim 1, is characterized in that, comprises the preparation method of fluorine-containing PTT and the preparation method of core-skin composite fiber, and concrete steps are:
1) preparation method of described fluorine-containing PTT is divided into esterification and polycondensation reaction two steps;
Described esterification:
Adopt tetrafluoro terephthalic acid (TPA) and 1,3-PD as raw material, add inhibitor, carry out esterification after being made into uniform sizing material, obtain esterification products; Esterification is pressurizeed in nitrogen atmosphere, and pressure is controlled at normal pressure～0.3MPa, and temperature is at 250～260 ℃, and what esterification water quantity of distillate reached theoretical value is the esterification terminal more than 90%;
Described inhibitor is a kind of in magnesia, silica, calcium oxide, zinc oxide and manganese oxide;
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, add catalyst and stabilizing agent in esterification products, under the condition of negative pressure, start polycondensation reaction, this staged pressure steadily is evacuated to below absolute pressure 500Pa by normal pressure, temperature is controlled at 260～270 ℃, and the reaction time is 30～50 minutes;
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continue to vacuumize, and makes reaction pressure be down to absolute pressure and be less than 100Pa, and reaction temperature is controlled at 260～275 ℃, 3～4 hours reaction time;
Make fluorine-containing PTT;
2) preparation method of described core-skin composite fiber is: using described fluorine-containing PTT as cortical material, PET, as core material, carries out the core-sheath spinning, and spinning temperature is 275-290 ℃, and winding speed is controlled at 2700～3200m/min.
5. the preparation method of a kind of fluorine-containing PTT-PET core-skin composite fiber according to claim 4, is characterized in that, the addition of described inhibitor is 0.01%～0.05% of described tetrafluoro terephthalic acid (TPA) weight.
6. the preparation method of a kind of fluorine-containing PTT-PET core-skin composite fiber according to claim 4, is characterized in that, the mol ratio of described 1,3-PD and tetrafluoro terephthalic acid (TPA) is 1.3～2.0: 1.
7. the preparation method of a kind of fluorine-containing PTT-PET core-skin composite fiber according to claim 4, it is characterized in that, described catalyst is selected from a kind of in butyl titanate-magnesium acetate, metatitanic acid four isopropyl esters-magnesium acetate, tetraethyl titanate-magnesium acetate, stannous acetate, dibutyltin diacetate, and catalyst amount is 0.01%～0.05% of described tetrafluoro terephthalic acid (TPA) weight.
8. the preparation method of a kind of fluorine-containing PTT-PET core-skin composite fiber according to claim 4, it is characterized in that, described stabilizing agent is selected from a kind of in triphenyl phosphate, trimethyl phosphate and Trimethyl phosphite, and stabilizing agent dosage is 0.01%～0.05% of described tetrafluoro terephthalic acid (TPA) weight.
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| JPH02167337A (en) * | 1988-09-22 | 1990-06-27 | Toray Ind Inc | Fluorine-containing polyester |
| CN1171408A (en) * | 1997-06-11 | 1998-01-28 | 中国科学院上海有机化学研究所 | Process for synthesizing fluoric aromatic polyester |
| WO2002036659A2 (en) * | 2000-11-03 | 2002-05-10 | Corning Incorporated | Highly-halogenated low optical loss polyester |
| CN1702094A (en) * | 2004-05-28 | 2005-11-30 | 株式会社日本触媒 | Transparent resin material |
| CN101613465A (en) * | 2009-07-21 | 2009-12-30 | 武汉理工大学 | A kind of Weather-proof self-cleaning transparent material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02167337A (en) * | 1988-09-22 | 1990-06-27 | Toray Ind Inc | Fluorine-containing polyester |
| CN1171408A (en) * | 1997-06-11 | 1998-01-28 | 中国科学院上海有机化学研究所 | Process for synthesizing fluoric aromatic polyester |
| WO2002036659A2 (en) * | 2000-11-03 | 2002-05-10 | Corning Incorporated | Highly-halogenated low optical loss polyester |
| CN1702094A (en) * | 2004-05-28 | 2005-11-30 | 株式会社日本触媒 | Transparent resin material |
| CN101613465A (en) * | 2009-07-21 | 2009-12-30 | 武汉理工大学 | A kind of Weather-proof self-cleaning transparent material and preparation method thereof |
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Application publication date: 20131225 Assignee: Beijing Zhiling Technology Co.,Ltd. Assignor: Beijing Zhongzhi Environmental Protection Technology Co.,Ltd. Contract record no.: X2024980005061 Denomination of invention: A preparation method for fluorine-containing PTT-PET skin core composite fibers Granted publication date: 20160127 License type: Common License Record date: 20240429 |
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Application publication date: 20131225 Assignee: Beijing Yiding Yiyi Management Consulting Co.,Ltd. Assignor: Beijing Zhongzhi Environmental Protection Technology Co.,Ltd. Contract record no.: X2024980010031 Denomination of invention: Preparation method of fluorinated PTT-PET skin core composite fiber Granted publication date: 20160127 License type: Common License Record date: 20240717 |