CN103526335A - Fluorine-containing PBT (polybutylene terephthalate)-PBT sheath-core composite fiber and preparation method thereof - Google Patents
Fluorine-containing PBT (polybutylene terephthalate)-PBT sheath-core composite fiber and preparation method thereof Download PDFInfo
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 107
- 239000011737 fluorine Substances 0.000 title claims abstract description 100
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000000835 fiber Substances 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- -1 polybutylene terephthalate Polymers 0.000 title claims description 10
- 229920001707 polybutylene terephthalate Polymers 0.000 title description 83
- 238000005886 esterification reaction Methods 0.000 claims abstract description 68
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 65
- 239000000463 material Substances 0.000 claims abstract description 35
- 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 9
- 230000032050 esterification Effects 0.000 claims description 67
- 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 28
- 239000002253 acid Substances 0.000 claims description 16
- 230000001054 cortical effect Effects 0.000 claims description 16
- 239000011162 core material Substances 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 14
- 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 10
- 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
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 5
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 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 group [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
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 claims description 2
- 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 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 abstract 2
- 229920000728 polyester Polymers 0.000 description 40
- 239000000047 product Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 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
- 239000004952 Polyamide Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 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
- 239000005022 packaging material Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000036632 reaction speed Effects 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
- 230000008901 benefit Effects 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 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
- 229920006351 engineering plastic Polymers 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920006324 polyoxymethylene Polymers 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
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009941 weaving Methods 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
- 0 Cc(c(*)c(c(C#CC)c1C)[N+](C(*)(*)*)[O-])c1[N+](*)[O-] Chemical compound Cc(c(*)c(c(C#CC)c1C)[N+](C(*)(*)*)[O-])c1[N+](*)[O-] 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
- 239000004727 Noryl Substances 0.000 description 1
- 229920001207 Noryl Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- 229920004933 Terylene® Polymers 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
- 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004891 communication Methods 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
- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000010292 electrical insulation Methods 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
- 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
- 238000000465 moulding Methods 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
- 229920000139 polyethylene terephthalate 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
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Multicomponent Fibers (AREA)
Abstract
The invention relates to a fluorine-containing PBT-PBT sheath-core composite fiber and a preparation method thereof. The preparation method comprises preparation of a sheath layer material of fluorine-containing PBT and preparation of a sheath-core composite fiber. According to the fluorine-containing PBT, tetrafluoroterephthalic acid and 1,4-butanediol serve as raw materials, an inhibitor is added, and an esterification reaction and a polycondensation reaction are conducted under appropriate conditions to obtain the fluorine-containing PBT. Then the fluorine-containing PBT is used as a sheath, PBT is used as a core, and an appropriate composite spinning technology is used for preparing the sheath-core composite fiber. According to the fluorine-containing PBT-PBT sheath-core composite fiber, the obtained fluorine-containing PBT has the good heat stability and processibility, and hydrophobic and oleophobic properties of the fluorine-containing PBT-PBT sheath-core composite fiber are improved through introduction of fluorine atoms. The fiber prepared through composite spinning has good mechanical properties of the PBT as well as the good stain resistance, and meanwhile, the cost is greatly saved, so that the fiber has great prospects in manufacturing of water-proof clothes, stain-resistant work clothes and work clothes of certain particular industries.
Description
Technical field
The present invention relates to a kind of fluorine-containing PBT-PBT core-skin composite fiber and preparation method thereof, comprise the preparation of the fluorine-containing PBT of cortical material and the preparation of core-skin composite fiber.Particularly relate to and a kind ofly take polytetrafluoro mutual-phenenyl two acid bromide two alcohol ester as the fluorine-containing PBT material of cortex, core-skin composite fiber that the PBT 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 has not been well positioned to 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 also with sandwich layer fiber, reasonably 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; as far back as twentieth century, just synthesized ethylene glycol terephthalate (PET) forties; 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.Polybutylene terephthalate (PBT) (PBT) is a kind of crystallinity line style saturated polyester, has that high temperature resistant, moisture-proof, electrical insulation capability are good, a feature such as oil resistant, resistance to chemical attack, moulding are fast.Its some application examples in industry demonstrate the superiority that it can not be substituted in some aspects, now it has become the fifth-largest general engineering plastic after polyamide (PA), Merlon (PC), polyformaldehyde (POM) and Noryl (MPPO), is widely used in auto industry, electronic apparatus industry, food medicine equipment, packaging material, environmental project, communication apparatus, Sport & Casual apparatus etc.Along with the research of PBT structure and performance is deepened constantly, not only develop different stage, dissimilar engineering plastics, as HI high impact, heat-resisting, fire-retardant etc., and its application aspect synthetic fiber is more and more paid attention to.PBT fibrous elasticity is superior, soft, and dyeing is convenient, has terylene, polyamide fibre, spandex three's advantage concurrently.Along with social progress, the raising of living standards of the people, needs more and more higher to differential, the functionalization of polyester fiber.Therefore also become particularly important of the modification of polyester, polyester modification object, except 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 conventionally, 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 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 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.In Chinese patent CN101139434A, adopt adding of fluorine-containing end-capping reagent, 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 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 there is certain limitation in weaving and packaging material, 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, the fluorine-containing polyester sheath core compound fibre of development of new for weave and super-hydrophobic, the hydrophobic and oil repellent of packaging material, the modification of antifouling property will have important theory significance and using value.At waterproof garment, in the Work Clothes manufacture of the Work Clothes bearing dirty and some special industry, there is huge prospect.
Summary of the invention
The object of this invention is to provide a kind of fluorine-containing PBT-PBT core-skin composite fiber and preparation method thereof, comprise the preparation of the fluorine-containing PBT of cortical material and the preparation of core-skin composite fiber.Wherein fluorine-containing PBT refers to polytetrafluoro mutual-phenenyl two acid bromide two alcohol ester.Fluorine-containing PBT of the present invention has introduced fluorine atom on the main chain of polymer, and the fluorine-containing PBT section of preparing can be directly used in spinning, can give fluorine-containing PBT fiber permanent hydrophobic and oil repellent performance, solve the problem that the modification of conventional P BT fiber hydrophobic and oil repellent is wasted time and energy.Meanwhile, adopt composite spinning method to prepare and take fluorine-containing PBT as the core-skin composite fiber that cortical material, PBT are core material, not only given core-skin composite fiber good hydrophobic and oil repellent performance, also provide cost savings greatly.
A kind of fluorine-containing PBT-PBT core-skin composite fiber of the present invention, cortical material is fluorine-containing PBT, core material is PBT; Described fluorine-containing PBT is polytetrafluoro mutual-phenenyl two acid bromide two alcohol ester, and its general structure is
N=70～150 wherein.
A kind of fluorine-containing PBT-PBT core-skin composite fiber as above, the ratio of the cortex of described fluorine-containing PBT-PBT core-skin composite fiber and the sectional area of sandwich layer is 2～5:5.
A kind of fluorine-containing PBT-PBT core-skin composite fiber as above, the filament number of described fluorine-containing PBT-PBT core-skin composite fiber is 1～15dtex.
The present invention also provides a kind of preparation method of fluorine-containing PBT-PBT core-skin composite fiber, comprises the preparation method of fluorine-containing PBT and the preparation method of core-skin composite fiber, and concrete steps are:
1. the preparation method of fluorine-containing PBT
Be divided into esterification and polycondensation reaction two steps; Concrete steps are:
Described esterification:
Adopt tetrafluoro terephthalic acid (TPA) and BDO 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 to be less than under absolute pressure 1KPa and carries out, and temperature is at 160～220 ℃, and the time is 2～3 hours, and what esterification water quantity of distillate reached theoretical value more than 90% is esterification terminal;
Described inhibitor is a kind of in magnesia, silica, calcium oxide, zinc oxide and manganese oxide; On phenyl ring due to dicarboxylic acids used, there is fluorine atom, the electronegativity of fluorine atom is large, conjugation at esterification stage fluorine atom strengthens the acidity of dicarboxylic acids, cause the activity of carboxyl in dicarboxylic acids to increase simultaneously, reaction speed is accelerated, and reaction speed increase easily makes side reaction produce, these side reaction products have larger impact to follow-up polycondensation reaction, the end-blocking product that particularly generates alkene and aldehyde, has 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, has reduced side reaction, has improved the molecular weight of product, makes to meet spinning requirement.
Conventionally, in polyester esterification process, be that the hydrogen ion that ionizes out by dicarboxylic acids used is as the catalyst of esterification, carry out self-catalyzed reaction, by regulating the temperature, pressure of esterification and micromolecularly ejecting the speed of controlling its esterification, yet the prerequisite of carrying out esterification is under certain reaction temperature and pressure, just can carry out esterification.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, the acidity of dicarboxylic acids is strengthened, cause the activity of carboxyl in dicarboxylic acids to increase simultaneously, reaction speed is accelerated, 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 react dissociation; On the contrary, if the electronegativity of M is little, so just will generate alkali center.M-O-H is similar with amphoteric compound, and when having alkaline matter to exist, reaction will be undertaken by the mode of acid dissociation; And when acidic materials exist, by the mode of alkali formula ionization, undertaken.The M-O of back reaction from acid dissociation mode and alkali formula ionization mode
-and M
+visible, M
+as acid centre, its intensity only has direct relation with the electronegativity of metal ion, and M-O
-in 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 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 large oxide of electronegativity of metal ion 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;
In the described polycondensation reaction low vacuum stage, add catalyst and stabilizing agent in esterification products, under the condition of negative pressure, starts polycondensation reaction, and described negative pressure refers to below absolute pressure 500Pa, and temperature is controlled at 260～270 ℃, and the reaction time is 40～60 minutes;
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature is controlled at 270～275 ℃, 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 PBT-PBT core-skin composite fiber
Using described fluorine-containing PBT as cortical material, PBT, as core material, carries out core-sheath spinning, and spinning temperature is 270-280 ℃, and winding speed is controlled at 2700～3200m/min.
As preferred technical scheme:
The preparation method of a kind of fluorine-containing PBT-PBT core-skin composite fiber as above, the mol ratio of described butanediol and tetrafluoro terephthalic acid (TPA) is 1.4～2.0:1.
The preparation method of a kind of fluorine-containing PBT-PBT core-skin composite fiber as above, described catalyst is selected from a kind of in butyl titanate, metatitanic acid four isopropyl esters, tetraethyl titanate, 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 PBT-PBT 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 PBT-PBT 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 producing in esterification reach theoretical value 90% with on grasp.Theoretical value is the quantity of distillate of gained water while pressing 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, and can cause shipwreck that esterification produces 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 PBT of gained of the present invention is due to the introducing of fluorine atom, improved the hydrophobic and oil repellent performance of PBT material, so the fluorine-containing PBT of take in the present invention is cortex, PBT is that the core-skin composite fiber of sandwich layer not only has good mechanical property, also there is the dirty performance of good permanent oil resistant, and cost reduces greatly, make it at waterproof garment, in the Work Clothes manufacture of the Work Clothes bearing dirty and some special industry, there is huge prospect.
Beneficial effect:
1, the PBT contain fluorine atoms making; strong electronegativity due to fluorine; high C-F bond energy and make the copolyesters synthesizing 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 have permanent hydrophobic and oil repellent, oil rub resistance performance.
2, in fluorine-containing PBT esterification process, by inhibiting, can control the speed of esterification, reduce the generation of side reaction.
3, the fluorine-containing PBT section of gained can direct fabrics.
4, the fluorine-containing PBT of gained has good heat endurance and machinability.
5, adopting fluorine-containing PBT is that cortical material, PBT 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 PBT of independent use, cost reduces greatly, thereby has better using value.
The specific embodiment
Below in conjunction with the specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of 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 PBT-PBT core-skin composite fiber of the present invention, cortical material is fluorine-containing PBT, core material is PBT; Described fluorine-containing PBT is polytetrafluoro mutual-phenenyl two acid bromide two alcohol ester, and its general structure is
N=70～150 wherein.
A kind of fluorine-containing PBT-PBT core-skin composite fiber as above, the ratio of the cortex of described fluorine-containing PBT-PBT core-skin composite fiber and the sectional area of sandwich layer is 2～5:5.
A kind of fluorine-containing PBT-PBT core-skin composite fiber as above, the filament number of described fluorine-containing PBT-PBT core-skin composite fiber is 1～15dtex.
Embodiment 1
1. the preparation method of fluorine-containing PBT polyester, is divided into esterification and polycondensation reaction two steps.Concrete steps are:
Described esterification:
Adopt BDO that mol ratio is 1.4:1 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 below 1KPa, and temperature is controlled at 220 ℃, and it is 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 and tetrafluoro terephthalic acid (TPA) weight in esterification products, under the condition of negative pressure, start polycondensation reaction, described negative pressure refers to that absolute pressure is less than 500Pa, temperature is controlled at 265 ℃, and the reaction time is 60 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is 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, obtains fluorine-containing PBT polyester slice.
2. the preparation of core-skin composite fiber: using described fluorine-containing PBT as cortical material, PBT is as core material, carry out core-sheath spinning, the ratio of the cross-sectional area of cortex and sandwich layer is 2:5, spinning temperature is 270 ℃, winding speed is controlled at 2700m/min, and the filament number of the fluorine-containing PBT-PBT core-skin composite fiber of gained is 1dtex.
Embodiment 2
1. the preparation method of fluorine-containing PBT polyester, is divided into esterification and polycondensation reaction two steps.Concrete steps are:
Described esterification:
Adopt BDO that mol ratio is 1.6:1 and tetrafluoro terephthalic acid (TPA) as raw material, add 0.02% 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 below 900Pa, and temperature is controlled at 200 ℃, and it is 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 and tetrafluoro terephthalic acid (TPA) weight in esterification products, under the condition of negative pressure, start polycondensation reaction, described negative pressure refers to that absolute pressure is less than 400Pa, temperature is controlled at 260 ℃, and the reaction time is 60 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 80Pa, 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, obtains fluorine-containing PBT polyester slice.
2. the preparation of core-skin composite fiber: using described fluorine-containing PBT as cortical material, PBT is as core material, carry out core-sheath spinning, the ratio of the cross-sectional area of cortex and sandwich layer is 4:5, spinning temperature is 274 ℃, winding speed is controlled at 3200m/min, and the filament number of the fluorine-containing PBT-PBT core-skin composite fiber of gained is 15dtex.
Embodiment 3
1. the preparation method of fluorine-containing PBT polyester, is divided into esterification and polycondensation reaction two steps.Concrete steps are:
Described esterification:
Adopt BDO that mol ratio is 1.8:1 and tetrafluoro terephthalic acid (TPA) as raw material, add 0.03% 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 below 800Pa, and temperature is controlled at 180 ℃, and it is 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 0.03% catalyst metatitanic acid tetra-ethyl ester of tetrafluoro terephthalic acid (TPA) weight and tetrafluoro terephthalic acid (TPA) weight in esterification products, under the condition of negative pressure, start polycondensation reaction, described negative pressure refers to that absolute pressure is less than 300Pa, 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, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 60Pa, and reaction temperature is controlled at 275 ℃, 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, obtains fluorine-containing PBT polyester slice.
2. the preparation of core-skin composite fiber: using described fluorine-containing PBT as cortical material, PBT is as core material, carry out core-sheath spinning, the ratio of the cross-sectional area of cortex and sandwich layer is 3:5, spinning temperature is 279 ℃, winding speed is controlled at 2900m/min, and the filament number of the fluorine-containing PBT-PBT core-skin composite fiber of gained is 10dtex.
Embodiment 4
1. the preparation method of fluorine-containing PBT polyester, is divided into esterification and polycondensation reaction two steps.Concrete steps are:
Described esterification:
Adopt BDO that mol ratio is 1.9:1 and tetrafluoro terephthalic acid (TPA) as raw material, add 0.04% 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 below 700Pa, and temperature is controlled at 170 ℃, and it is 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 sub-tin of 0.04% catalyst acetic acid of tetrafluoro terephthalic acid (TPA) weight and tetrafluoro terephthalic acid (TPA) weight in esterification products, under the condition of negative pressure, start polycondensation reaction, described negative pressure refers to that absolute pressure 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, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is 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, obtains fluorine-containing PBT polyester slice.
2. the preparation of core-skin composite fiber: using described fluorine-containing PBT as cortical material, PBT is as core material, carry out core-sheath spinning, the ratio of the cross-sectional area of cortex and sandwich layer is 5:5, spinning temperature is 275 ℃, winding speed is controlled at 2800m/min, and the filament number of the fluorine-containing PBT-PBT core-skin composite fiber of gained is 5dtex.
Embodiment 5
1. the preparation method of fluorine-containing PBT polyester, is divided into esterification and polycondensation reaction two steps.Concrete steps are:
Described esterification:
Adopt BDO that mol ratio is 2.0:1 and tetrafluoro terephthalic acid (TPA) as raw material, add 0.05% 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 below 600Pa, and temperature is controlled at 160 ℃, and it is 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, under the condition of negative pressure, start polycondensation reaction, described negative pressure refers to that absolute pressure is less than 300Pa, temperature is controlled at 265 ℃, and the reaction time is 40 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is 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, obtains fluorine-containing PBT polyester slice.
2. the preparation of core-skin composite fiber: using described fluorine-containing PBT as cortical material, PBT is as core material, carry out core-sheath spinning, the ratio of the cross-sectional area of cortex and sandwich layer is 1:2, spinning temperature is 280 ℃, winding speed is controlled at 3100m/min, and the filament number of the fluorine-containing PBT-PBT core-skin composite fiber of gained is 3dtex.
Claims (8)
1. a fluorine-containing PBT-PBT core-skin composite fiber, is characterized in that: the cortical material of described fluorine-containing PBT-PBT core-skin composite fiber is fluorine-containing PBT, and core material is PBT; Described fluorine-containing PBT is polytetrafluoro mutual-phenenyl two acid bromide two alcohol ester, and its general structure is
N=70～150 wherein.
2. a kind of fluorine-containing PBT-PBT core-skin composite fiber according to claim 1, is characterized in that, the ratio of the cortex of described fluorine-containing PBT-PBT core-skin composite fiber and the sectional area of sandwich layer is 2～5:5.
3. a kind of fluorine-containing PBT-PBT core-skin composite fiber according to claim 1, is characterized in that, the filament number of described fluorine-containing PBT-PBT core-skin composite fiber is 1～15dtex.
4. the preparation method of a kind of fluorine-containing PBT-PBT core-skin composite fiber as claimed in claim 1, is characterized in that, comprises the preparation method of fluorine-containing PBT and the preparation method of core-skin composite fiber, and concrete steps are:
1) preparation method of described fluorine-containing PBT is divided into esterification and polycondensation reaction two steps;
Described esterification:
Adopt tetrafluoro terephthalic acid (TPA) and BDO as raw material, add inhibitor, carry out esterification after being made into uniform sizing material, obtain esterification products; Esterification is in nitrogen atmosphere, and pressure is controlled at and is less than absolute pressure 1KPa, and temperature is at 160～220 ℃, and the time is 2～3 hours, and what esterification water quantity of distillate reached theoretical value more than 90% is esterification terminal;
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:
In the described polycondensation reaction low vacuum stage, add catalyst and stabilizing agent in esterification products, under the condition of negative pressure, starts polycondensation reaction, and described negative pressure refers to below absolute pressure 500Pa, and temperature is controlled at 260～270 ℃, and the reaction time is 40～60 minutes;
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature is controlled at 270～275 ℃, 3～4 hours reaction time;
Make fluorine-containing PBT;
2) preparation method of described core-skin composite fiber is: using described fluorine-containing PBT as cortical material, PBT, as core material, carries out core-sheath spinning, and spinning temperature is 270-280 ℃, and winding speed is controlled at 2700～3200m/min.
5. the preparation method of a kind of fluorine-containing PBT-PBT 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 PBT-PBT core-skin composite fiber according to claim 4, is characterized in that, the mol ratio of described BDO and tetrafluoro terephthalic acid (TPA) is 1.4～2.0:1.
7. the preparation method of a kind of fluorine-containing PBT-PBT core-skin composite fiber according to claim 4, it is characterized in that, described catalyst is selected from a kind of in butyl titanate, metatitanic acid four isopropyl esters, tetraethyl titanate, 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 PBT-PBT 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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