CN103469356A - Fluorine-containing PET-PET sheath-core composite fibers and preparation method thereof - Google Patents
Fluorine-containing PET-PET sheath-core composite fibers and preparation method thereof Download PDFInfo
- Publication number
- CN103469356A CN103469356A CN2013104454738A CN201310445473A CN103469356A CN 103469356 A CN103469356 A CN 103469356A CN 2013104454738 A CN2013104454738 A CN 2013104454738A CN 201310445473 A CN201310445473 A CN 201310445473A CN 103469356 A CN103469356 A CN 103469356A
- Authority
- CN
- China
- Prior art keywords
- pet
- fluorine
- core
- preparation
- composite fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to fluorine-containing PET-PET sheath-core composite fibers and a preparation method thereof. The preparation method comprises preparation of fluorine-containing PET as a sheath material and preparation of the fluorine-containing PET-PET sheath-core composite fibers. 2,5-difluoroterephthalic acid or tetrafluoroterephthalic acid and glycol as raw materials are added with an inhibitor and the mixture undergoes an esterification reaction and the esterification product undergoes a polycondensation reaction to produce fluorine-containing PET under appropriate conditions. The fluorine-containing PET as the sheath and PET as the core are processed into the fluorine-containing PET-PET sheath-core composite fibers by an appropriate composite spinning technology. The fluorine-containing PET-PET sheath-core composite fibers have good heat stability and machinability. Through use of fluorine atoms, hydrophobic and oleophobic performances are improved. The fluorine-containing PET-PET sheath-core composite fibers have good mechanical properties of PET and good antifouling properties, greatly reduce a cost and have a wide application prospect in manufacture of waterproof and antifouling working clothes and special industry working clothes.
Description
Technical field
The present invention relates to a kind of fluorine-containing PET-PET core-skin composite fiber and preparation method thereof, comprise the preparation of the fluorine-containing PET of cortical material and the preparation of core-skin composite fiber.Particularly relate to a kind of take gather the difluoro ethylene glycol terephthalate or the polytetrafluoro ethylene glycol terephthalate is the fluorine-containing PET 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 (PET) is one of the most widely used synthetic high polymer of the current mankind; just synthesized PET the 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.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 PET-PET core-skin composite fiber for super-hydrophobic, the hydrophobic and oil repellent of weaving and packaging material, the modification of antifouling property, will there is important theory significance and using value.
Summary of the invention
The purpose of this invention is to provide a kind of fluorine-containing PET-PET core-skin composite fiber and preparation method thereof, comprise the preparation of the fluorine-containing PET of cortical material and the preparation of core-skin composite fiber.Wherein fluorine-containing PET refers to poly-difluoro ethylene glycol terephthalate or polytetrafluoro ethylene glycol terephthalate.Fluorine-containing PET of the present invention has introduced fluorine atom on the main chain of polymer, and the fluorine-containing PET section of preparing can be directly used in spinning, can give fluorine-containing PET fiber permanent hydrophobic and oil repellent performance, solve the problem that the modification of conventional P ET fiber hydrophobic and oil repellent is wasted time and energy.Simultaneously, adopt composite spinning method to prepare and take fluorine-containing PET as the core-skin composite fiber that cortical material, PET are core material, not only given the hydrophobic and oil repellent performance that fluorine-containing PET fiber is good, also provide cost savings greatly.
A kind of fluorine-containing PET-PET core-skin composite fiber of the present invention, cortical material is fluorine-containing PET, core material is PET; Described fluorine-containing PET is polytetrafluoro ethylene glycol terephthalate or poly-difluoro ethylene glycol terephthalate, and its general structure is
Or
N=80～200 wherein.
A kind of fluorine-containing PET-PET core-skin composite fiber as above, the ratio of the cortex of described fluorine-containing PET-PET core-skin composite fiber and the sectional area of sandwich layer is 2～5:5.
A kind of fluorine-containing PET-PET core-skin composite fiber as above, the filament number of described fluorine-containing PET-PET core-skin composite fiber is 1～15dtex.
The present invention also provides a kind of preparation method of fluorine-containing PET-PET core-skin composite fiber, comprises the preparation method of fluorine-containing PET and the preparation method of core-skin composite fiber, and concrete steps are:
1. the preparation method of fluorine-containing PET
Be divided into esterification and polycondensation reaction two steps; Concrete steps are:
Described esterification:
Adopt fluorine-containing terephthalic acid (TPA) and ethylene glycol 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～0.4MPa, and temperature is at 230～250 ℃, and what esterification water quantity of distillate reached theoretical value is the esterification terminal more than 90%;
Described fluorine-containing terephthalic acid (TPA) is tetrafluoro terephthalic acid (TPA) or 2,5-difluoro terephthalic acid (TPA);
Described inhibitor is a kind of in magnesia, silica, calcium oxide, zinc oxide and manganese oxide; There is fluorine atom on phenyl ring due to dicarboxylic acids used, the electronegativity of fluorine atom is large, conjugation at esterification stage fluorine atom makes the acidity of dicarboxylic acids strengthen, cause the activity of carboxyl in dicarboxylic acids to increase simultaneously, make reaction speed accelerate, and the reaction speed increase easily makes side reaction produce, these side reaction products have larger impact to follow-up polycondensation reaction, particularly generate the end-blocking product of alkene and aldehyde, restricted the increase of molecular weight of product; From experimental result, if do not add inhibitor, synthetic molecular weight of polyesters is on the low side, can not meet the demand of spinning and film forming; Adding for controlling the speed in esterification stage of inhibitor, reduced side reaction, improved the molecular weight of product, makes and meet spinning requirement.
Usually, it in the polyester esterification process, is the hydrogen ion that ionizes out by the dicarboxylic acids used catalyst as esterification, carry out self-catalyzed reaction, temperature by regulating esterification, pressure and micromolecularly eject the speed of controlling its esterification, however the prerequisite of carrying out esterification is just can carry out esterification under certain reaction temperature and pressure.In the situation that temperature is too low or pressure is inadequate, esterification can not carry out or speed extremely slow, thereby affect follow-up technique.If the little molecule in esterification is failed timely discharge and is easily caused unnecessary side reaction.In building-up process, conjugation due to fluorine, at esterification stage fluorine atom, make the acidity of dicarboxylic acids strengthen, cause the activity of carboxyl in dicarboxylic acids to increase simultaneously, make reaction speed accelerate, side reaction increases, be difficult to control, and then affect the growth of molecular weight of product, thus add inhibitor, by selecting metal oxide used to regulate.Described metal oxide can dissociate by following two kinds of modes:
Here M is metal ion, if the electronegativity of M is quite large, the duplet of oxonium ion is had to stronger attraction, so just can make O-H key weaken, and is conducive to reaction from solution; On the contrary, if the electronegativity of M is little, so just will generate the alkali center.M-O-H is similar with amphoteric compound, and when having alkaline matter to exist, reaction will be undertaken by the mode of acid dissociation; And, when acidic materials exist, by the mode of alkali formula ionization, undertaken.The M-O of back reaction from acid dissociation mode and alkali formula ionization mode
-and M
+visible, M
+as acid centre, its intensity only has direct relation with the electronegativity of metal ion, and M-O
-in the O ion relevant with the negative charge density on oxygen as the intensity at alkali center, negative charge density is larger, intensity is also larger.Negative charge density on visible oxonium ion and metal ion electronegativity have close relationship, and the metal ion electronegativity is less, and negative charge density is just larger.So, the acid and alkalescence of metal oxide has just all connected with the electronegativity of metal ion, and the oxide that the electronegativity of metal ion is large is mainly acid, and what electronegativity was little is alkalescence.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig;
The described polycondensation reaction low vacuum stage, add catalyst and stabilizing agent in esterification products, under the condition of negative pressure, start polycondensation reaction, this staged pressure steadily is evacuated to below absolute pressure 1KPa by normal pressure, temperature is controlled at 250～270 ℃, and the reaction time is 40～60 minutes;
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continue to vacuumize, and makes reaction pressure be down to absolute pressure and be less than 100Pa, and reaction temperature is controlled at 270～285 ℃, 1～2 hour 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 PET-PET core-skin composite fiber
Using described fluorine-containing PET as cortical material, PET, as core material, carries out the core-sheath spinning, and spinning temperature is
275-290 ℃, winding speed is controlled at 2700～3200m/min.
As preferred technical scheme:
The preparation method of a kind of fluorine-containing PET-PET core-skin composite fiber as above, the mol ratio of described ethylene glycol and fluorine-containing terephthalic acid (TPA) is 1.2～2.0:1.
The preparation method of a kind of fluorine-containing PET-PET core-skin composite fiber as above, described catalyst is selected from a kind of in antimonous oxide, antimony glycol and antimony acetate, and catalyst amount is 0.01%～0.05% of described fluorine-containing terephthalic acid (TPA) weight.
The preparation method of a kind of fluorine-containing PET-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 fluorine-containing terephthalic acid (TPA) weight.
The preparation method of a kind of fluorine-containing PET-PET core-skin composite fiber as above, the addition of described inhibitor is 0.01%～0.05% of described fluorine-containing 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 PET of gained of the present invention is due to the introducing of fluorine atom, improved the hydrophobic and oil repellent performance of PET material, so the fluorine-containing PET 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 PET contain fluorine atoms made; strong electronegativity due to fluorine; high C-F bond energy and make the copolyesters synthesized except the performance of further lifting conventional P ET to the shielding protection effect of carbochain; the surface that has also reduced the PET material can; make fluorine-containing PET material permanent hydrophobic and oil repellent be arranged, the oil rub resistance performance.
2, can control the speed of esterification in fluorine-containing PET esterification process by inhibiting, reduce the generation of side reaction.
3, the fluorine-containing PET section of gained can direct fabrics.
4, the fluorine-containing PET of gained has good heat endurance and machinability.
5, adopting fluorine-containing PET 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 PET 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 PET-PET core-skin composite fiber of the present invention, cortical material is fluorine-containing PET, core material is PET; Described fluorine-containing PET is polytetrafluoro ethylene glycol terephthalate or poly-difluoro ethylene glycol terephthalate, and its general structure is
Or
N=80～200 wherein.
A kind of fluorine-containing PET-PET core-skin composite fiber as above, the ratio of the cortex of described fluorine-containing PET-PET core-skin composite fiber and the sectional area of sandwich layer is 2～5:5.
A kind of fluorine-containing PET-PET core-skin composite fiber as above, the filament number of described fluorine-containing PET-PET core-skin composite fiber is 1～15dtex.
Embodiment 1
1, the preparation of fluorine-containing PET: be divided into esterification and polycondensation reaction two steps, concrete steps are:
Described esterification:
Adopt ethylene glycol that mol ratio is 1.2:1 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 0.4MPa, 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, 0.01% the stabilizing agent triphenyl phosphate that adds 0.01% the catalytic antimony trioxide 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 1KPa, temperature is controlled at 255 ℃, and the reaction time is 60 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 ℃, 2 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 polyester slice.
2, the preparation of core-skin composite fiber: using described fluorine-containing PET 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 2:5, spinning temperature is 275 ℃, winding speed is controlled at 2700m/min, and the filament number of the fluorine-containing PET-PET core-skin composite fiber of gained is 1dtex.
Embodiment 2
1, the preparation of fluorine-containing PET: be divided into esterification and polycondensation reaction two steps, concrete steps are:
Described esterification:
Adopt ethylene glycol that mol ratio is 1.4:1 and 2,5-difluoro terephthalic acid (TPA) as raw material, add 0.03% silica of 2,5-difluoro terephthalic acid (TPA) weight simultaneously, carry out esterification after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and pressure is controlled at 0.3MPa, and temperature is controlled at 245 ℃, 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, add 2 in esterification products, 0.02% catalyst glycol antimony and 2 of 5-difluoro terephthalic acid (TPA) weight, 0.02% stabilizing agent trimethyl phosphate of 5-difluoro terephthalic acid (TPA) weight, 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 800Pa, and temperature is controlled at 250 ℃, 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 80Pa, and reaction temperature is controlled at 275 ℃, 2 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 polyester slice.
2, the preparation of core-skin composite fiber: using described fluorine-containing PET 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 PET-PET core-skin composite fiber of gained is 15dtex.
Embodiment 3
1, the preparation of fluorine-containing PET: be divided into esterification and polycondensation reaction two steps, concrete steps are:
Described esterification:
Adopt ethylene 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 pressurizeed in nitrogen atmosphere, and pressure is controlled at 0.2MPa, and temperature is controlled at 240 ℃, 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 phosphite that adds 0.03% catalyst acetic acid antimony 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 600Pa, temperature is controlled at 260 ℃, 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 60Pa, and reaction temperature is controlled at 280 ℃, 1.5 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 polyester slice.
2, the preparation of core-skin composite fiber: using described fluorine-containing PET 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 PET-PET core-skin composite fiber of gained is 10dtex.
Embodiment 4
1, the preparation of fluorine-containing PET: be divided into esterification and polycondensation reaction two steps, concrete steps are:
Described esterification:
Adopt ethylene 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 pressurizeed in nitrogen atmosphere, and pressure is controlled at 0.2MPa, and temperature is controlled at 235 ℃, 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 0.04% the catalytic antimony trioxide 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 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 50Pa, and reaction temperature is controlled at 280 ℃, 1 hour 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 polyester slice.
2, the preparation of core-skin composite fiber: using described fluorine-containing PET 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 284 ℃, winding speed is controlled at 2950m/min, and the filament number of the fluorine-containing PET-PET core-skin composite fiber of gained is 3dtex.
Embodiment 5
1, the preparation of fluorine-containing PET: be divided into esterification and polycondensation reaction two steps, concrete steps are:
Described esterification:
Adopt ethylene glycol that mol ratio is 2.0:1 and 2,5-difluoro terephthalic acid (TPA) as raw material, add 0.04% manganese oxide of 2,5-difluoro terephthalic acid (TPA) weight simultaneously, carry out esterification after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and pressure is controlled at normal pressure, and temperature is controlled at 230 ℃, 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, add 2 in esterification products, 0.05% the catalytic antimony trioxide and 2 of 5-difluoro terephthalic acid (TPA) weight, 0.05% stabilizing agent triphenyl phosphate of 5-difluoro terephthalic acid (TPA) weight, 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, and 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 50Pa, and reaction temperature is controlled at 285 ℃, 1 hour 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 polyester slice.
2, the preparation of core-skin composite fiber: using described fluorine-containing PET 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 288 ℃, winding speed is controlled at 3100m/min, and the filament number of the fluorine-containing PET-PET core-skin composite fiber of gained is 8dtex.
Claims (8)
1. a fluorine-containing PET-PET core-skin composite fiber, it is characterized in that: the cortical material of described fluorine-containing PET-PET core-skin composite fiber is fluorine-containing PET, core material is PET; Described fluorine-containing PET is polytetrafluoro ethylene glycol terephthalate or poly-difluoro ethylene glycol terephthalate, and its general structure is
Or
N=80～200 wherein.
2. a kind of fluorine-containing PET-PET core-skin composite fiber according to claim 1, is characterized in that, the ratio of the cortex of described fluorine-containing PET-PET core-skin composite fiber and the sectional area of sandwich layer is 2～5:5.
3. a kind of fluorine-containing PET-PET core-skin composite fiber according to claim 1, is characterized in that, the filament number of described fluorine-containing PET-PET core-skin composite fiber is 1～15dtex.
4. the preparation method of a kind of fluorine-containing PET-PET core-skin composite fiber as claimed in claim 1, is characterized in that, comprises the preparation method of fluorine-containing PET and the preparation method of core-skin composite fiber, and concrete steps are:
1) preparation method of described fluorine-containing PET is divided into esterification and polycondensation reaction two steps;
Described esterification:
Adopt fluorine-containing terephthalic acid (TPA) and ethylene glycol 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～0.4MPa, and temperature is at 230～250 ℃, and what esterification water quantity of distillate reached theoretical value is the esterification terminal more than 90%;
Described fluorine-containing terephthalic acid (TPA) is tetrafluoro terephthalic acid (TPA) or 2,5-difluoro terephthalic acid (TPA);
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 described esterification products, under the condition of negative pressure, start polycondensation reaction, this staged pressure steadily is evacuated to below absolute pressure 1KPa by normal pressure, temperature is controlled at 250～270 ℃, and the reaction time is 40～60 minutes;
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continue to vacuumize, and makes reaction pressure be down to absolute pressure and be less than 100Pa, and reaction temperature is controlled at 270～285 ℃, 1～2 hour reaction time;
Make fluorine-containing PET;
2) preparation method of described core-skin composite fiber is: using described fluorine-containing PET 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 PET-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 fluorine-containing terephthalic acid (TPA) weight.
6. the preparation method of a kind of fluorine-containing PET-PET core-skin composite fiber according to claim 4, is characterized in that, the mol ratio of described ethylene glycol and fluorine-containing terephthalic acid (TPA) is 1.2～2.0:1.
7. the preparation method of a kind of fluorine-containing PET-PET core-skin composite fiber according to claim 4, it is characterized in that, described catalyst is selected from a kind of in antimonous oxide, antimony glycol and antimony acetate, and catalyst amount is 0.01%～0.05% of described fluorine-containing terephthalic acid (TPA) weight.
8. the preparation method of a kind of fluorine-containing PET-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 fluorine-containing terephthalic acid (TPA) weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310445473.8A CN103469356B (en) | 2013-09-26 | 2013-09-26 | A kind of preparation method of fluorine-containing PET-PET core-skin composite fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310445473.8A CN103469356B (en) | 2013-09-26 | 2013-09-26 | A kind of preparation method of fluorine-containing PET-PET core-skin composite fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103469356A true CN103469356A (en) | 2013-12-25 |
| CN103469356B CN103469356B (en) | 2016-01-27 |
Family
ID=49794389
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310445473.8A Active CN103469356B (en) | 2013-09-26 | 2013-09-26 | A kind of preparation method of fluorine-containing PET-PET core-skin composite fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103469356B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109234844A (en) * | 2018-08-30 | 2019-01-18 | 江苏国望高科纤维有限公司 | A kind of hydrophobic polyester fiber and preparation method thereof |
| CN114457459A (en) * | 2022-03-02 | 2022-05-10 | 邵阳深镁科技时尚有限公司 | High-strength light wig fiber and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20050209480A1 (en) * | 2002-10-18 | 2005-09-22 | Sony Chemicals Corp. | Perfluoropolyether ester compound, lubricant and magnetic recording medium |
| EP1600797A1 (en) * | 2004-05-28 | 2005-11-30 | Nippon Shokubai Co., Ltd. | 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 |
-
2013
- 2013-09-26 CN CN201310445473.8A patent/CN103469356B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20050209480A1 (en) * | 2002-10-18 | 2005-09-22 | Sony Chemicals Corp. | Perfluoropolyether ester compound, lubricant and magnetic recording medium |
| EP1600797A1 (en) * | 2004-05-28 | 2005-11-30 | Nippon Shokubai Co., Ltd. | 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109234844A (en) * | 2018-08-30 | 2019-01-18 | 江苏国望高科纤维有限公司 | A kind of hydrophobic polyester fiber and preparation method thereof |
| CN109234844B (en) * | 2018-08-30 | 2024-03-15 | 江苏国望高科纤维有限公司 | Hydrophobic polyester fiber and preparation method thereof |
| CN114457459A (en) * | 2022-03-02 | 2022-05-10 | 邵阳深镁科技时尚有限公司 | High-strength light wig fiber and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103469356B (en) | 2016-01-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103469335B (en) | Wear-resisting industrial yarn of a kind of fluorine polyester high-strength and preparation method thereof | |
| CN103524723B (en) | A kind of fluorine polyester and preparation method thereof | |
| CN103524722B (en) | A kind of fluorine-containing PBT atactic polyester and preparation method thereof | |
| CN103469360B (en) | A kind of preparation method of fluorine-containing PBT-PET core-skin composite fiber | |
| CN103510184B (en) | Fluorine-containing PET-PBT (polyethylene terephthalate- polybutylene terephthalate) copolyester DTY (draw texturing yarn) fiber and preparation method thereof | |
| CN103469344B (en) | Fluorine-containing PTT-PBT copolyester POY fiber and preparation method thereof | |
| CN103469339B (en) | A kind of preparation method of fluorine polyester DTY fiber | |
| CN103526335B (en) | A kind of preparation method of fluorine-containing PBT-PBT core-skin composite fiber | |
| CN103469340B (en) | Fluorine-containing PBT random co-polyester DTY fiber and method for preparing same | |
| CN103469355B (en) | A kind of preparation method of fluorine-containing PET-PET blended fiber | |
| CN103469348B (en) | Fluorine-containing PBT polyester DTY fiber and preparation method thereof | |
| CN103469356B (en) | A kind of preparation method of fluorine-containing PET-PET core-skin composite fiber | |
| CN103469358B (en) | A kind of preparation method of fluorine-containing PTT-PTT core-skin composite fiber | |
| CN103469338B (en) | A kind of preparation method of fluorine polyester POY fiber | |
| CN103588964B (en) | A kind of preparation method of fluorine-containing atactic polyester | |
| CN103469336B (en) | A kind of preparation method of fluorine-containing PTT polyester POY fiber | |
| CN103467718B (en) | A kind of fluorine-containing PET-PTT copolyesters and preparation method thereof | |
| CN103469334B (en) | A kind of preparation method of fluorine-containing PBT polyester POY fiber | |
| CN103469361B (en) | A kind of preparation method of fluorine-containing PBT-PET blended fiber | |
| CN103467722B (en) | A kind of fluorine-containing PTT-PBT copolyesters and preparation method thereof | |
| CN103467720B (en) | Fluorine-containing poly(ethylene terephthalate) (PET)-poly(butylene terephthalate) (PBT) copolyester and preparation method thereof | |
| CN103469337A (en) | Fluorine-containing random copolyester polyester pre-oriented yarn (POY) fibers and preparation method thereof | |
| CN103469359B (en) | A kind of preparation method of fluorine-containing PTT-PET core-skin composite fiber | |
| CN103467719B (en) | A kind of preparation method of fluorine-containing PTT atactic polyester | |
| CN103467721B (en) | A kind of preparation method of fluorine-containing PTT polyester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210531 Address after: No. 58, Yingbin Avenue, Xiadu community, Pingnan County, Guigang City, Guangxi Zhuang Autonomous Region, 537300 Patentee after: Li Weizhi Address before: 215228 industrial concentration area, Shengze Town, Wujiang City, Suzhou City, Jiangsu Province Patentee before: JIANGSU LIXIN CHEMICAL FIBER TECHNOLOGY Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220601 Address after: No. 16-9, Xinjing Road, development zone, Nantong City, Jiangsu Province, 226000 Patentee after: Jiangsu Yinghao New Material Technology Co.,Ltd. Address before: No. 58, Yingbin Avenue, Xiadu community, Pingnan County, Guigang City, Guangxi Zhuang Autonomous Region, 537300 Patentee before: Li Weizhi |