CN103469338A - Fluorinated polyester polyester pre-oriented yarn (POY) fibers and preparation method thereof - Google Patents
Fluorinated polyester polyester pre-oriented yarn (POY) fibers and preparation method thereof Download PDFInfo
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Abstract
The invention relates to fluorinated polyester polyester pre-oriented yarn (POY) fibers and a preparation method thereof. The preparation method comprises fluorinated polyester melt preparation and fluorinated polyester POY fiber preparation, and concretely comprises the following steps of 1, adding an inhibitor into fluorine-containing terephthalic acid and glycol as raw materials, and preparing the mixture into fluorinated polyester melt, and 2, carrying out direct extrusion on the fluorinated polyester melt or carrying out slicing and screw melt extrusion on the slices, and carrying cooling, oil coating and winding to obtain the fluorinated polyester POY fibers. The novel fluorinated polyester POY fibers have monofilament fineness of 0.5-3.0dtex, fiber breaking strength of 1.6-2.5cN/dtex and breaking elongation of 110-150%. Through use of fluorine atoms, super-hydrophobic, hydrophobic, oleophobic and antifouling performances of the polyester POY fibers are improved. The fluorinated polyester POY fibers 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 polyester POY fiber and preparation method thereof, particularly relate to fluorine polyester POY fiber that a kind of benzene ring hydrogen replaced by fluorine and preparation method thereof.
Background technology
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.Pre-oriented yarn POY, refer to unstretched but can directly carry out the precursor of stretcher strain processing, requires the POY silk can long storage time, and have certain structural stability and machinability.The POY silk generally not there will be repiece difficulty, finished silk lousiness, low strength and the uniform situation of stained clot-h in process.It is high around volume speed that its technique has spinning, and the sub-hardness of winding reel is high, weight large, the advantage of cheap transportation; And in spinning process, shelf stability is good, suitable DTY processing.
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.Wang Zhong has just waited (Wang Zhonggang, Li Wenjuan, by the industry that continues. there is fluorine-containing polyester of low-surface-energy and preparation method thereof [P]: China, CN101139434A, 2008.) 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 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, the fluorine-containing polyester fiber of development of new, for super-hydrophobic, the hydrophobic and oil repellent of weaving and 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 born dirty and some special industry, huge prospect is arranged.
Summary of the invention
The invention provides a kind of fluorine polyester POY fiber and preparation method thereof, fluorine polyester POY fiber that particularly provides a kind of benzene ring hydrogen to be replaced by fluorine and preparation method thereof.A kind of fluorine polyester POY fiber of the present invention adopts fluorine-containing Direct-spinning of PET Fiber, and described fluorine-containing polyester has been introduced fluorine atom on the main chain of polymer, can well solve this class problem that wastes time and energy.Fluorine-containing polyester described in the present invention is terephthalic acid (TPA) and the ethylene glycol by contain fluorine atoms on phenyl ring, the novel fluorine polyester obtained through over-churning and polycondensation.By copolymerization method, polyester is carried out to hydrophobic antifouling modification, can fundamentally solve the problems such as ageing, the durability of hydrophobic antifouling polyester and ABRASION RESISTANCE.
The invention provides following technical scheme:
A kind of fluorine polyester POY fiber, be by the fluorine polyester fondant directly extrude or make section through screw rod melt extrude, cooling, oil and coiling makes; Described fluorine polyester refers to the polyethylene terephthalate that the benzene ring hydrogen is replaced by fluorine, and its general structure is
Or
N=80～200 wherein.
A kind of fluorine polyester POY fiber as above, the filament number of described fluorine polyester POY fiber is 0.5～3.0dtex; Fracture strength is 1.6～2.5cN/dtex; Elongation at break is 110～50%.
The present invention also provides a kind of preparation method of fluorine polyester POY fiber, be by the fluorine polyester fondant measure, extrude, cooling, oil and coiling makes fluorine polyester POY fiber.
The described temperature of extruding is 285～295 ℃;
Described cooling wind-warm syndrome is 20～30 ℃;
The described oil applying rate oiled is 0.42～1.5wt%;
The speed of described coiling is 2700～3200m/min;
Described lateral blowing or the ring quenching of being cooled to, temperature is 20 ℃～30 ℃, and relative humidity is 65% ± 5%, and wind speed is 0.4～0.8m/s;
The described finish oiled is fluorine-containing polyester POY fiber finish, its component by weight:
Component A: atactic polyether, 50～60 parts;
B component: cithrol, 20～32 parts;
Component C: phosphate kalium salt, 10～15 parts;
Component D: perfluoroalkyl acrylate, 2～5 parts;
The finish preparation method:
By atactic polyether, be heated to 40～60 ℃, cithrol, phosphate kalium salt and perfluoroalkyl acrylate are uniformly mixed, then join in atactic polyether, stir 1～2 hour, obtain fluorine-containing polyester fiber POY finish, finish adds water while using and is made into the emulsion that solid content is 8～10wt%.
Described fluorine-containing polyester POY fiber is with in finish, and component A atactic polyether is smooth agent: this material is a kind of in propylene glycol atactic polyether, butanols atactic polyether, laurate atactic polyether, lauryl alcohol atactic polyether and isomerous tridecanol atactic polyether.The good heat resistance of atactic polyether, be fuming few, and coking is few, and flowing temperature is low, good stability, and coefficient of friction is low, and anti-shear ability is strong, and viscosity coefficient is low, can form the highly stable lubricant film with large absorption affinity and bearing capacity in polyester fibre surface.
Described fluorine-containing polyester POY fiber is with in finish, and the B component cithrol is emulsifying agent: this material is a kind of in polyethylene glycol lauric acid monoester, polyethylene glycol laurate dibasic acid esters, polyethylene glycol oleic acid monoester and polyethylene glycol Glycol Oleic Acid Ester.Oil film that cithrol becomes has the performances such as good surface tension, interfacial tension, penetrability, dispersiveness and emulsibility, its form finish can reduce between silk and silk, thread and metal between quiet/kinetic force of friction, for fluorine-containing polyester fiber provides certain antistatic behaviour, improve convergence.
Described fluorine-containing polyester POY fiber is with in finish, and component C phosphate kalium salt is antistatic additive: this material is a kind of in 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, isomerous tridecanol polyoxyethylene ether phosphate kalium salt and ten tetracosanol phosphate kalium salts.In spinning process, easily produce a large amount of static, the generation that the flatness by fiber surface reduces static content is inadequate, also needs to add the antistatic additive of superior performance.Phosphate kalium salt is a kind of good antistatic additive, it is a kind of anion surfactant, consists of hydrophobic grouping energy and polyester fibre surface combination hydrophobic group and hydrophilic radical, the hydrophilic radical phosphate group upwards, can form the continuous moisture film of " interfacial agent-water ".Can effectively fall low-fiber coefficient of friction, increase the dielectric constant between friction piece, prevent that static from occurring.
Described fluorine-containing polyester POY fiber is with in finish, and component D perfluoroalkyl acrylate is additive: this material is a kind of in perfluoro butyl ethyl propylene acid esters, perfluoro hexyl ethyl propylene acid esters, perfluoro capryl ethyl propylene acid esters, perfluoro butyl ethyl-methyl acrylate, perfluoro hexyl ethyl-methyl acrylate and perfluoro capryl ethyl-methyl acrylate.Its effect is the surface tension that suitably reduces finish, makes it be easy to form uniform continuous oil film.Fluorinated acrylate has lower surface energy, and appropriate interpolation can be lowered the surface tension of finish, makes the wettability of finish and penetrability greatly increase, and is easy to the wetting of fiber and sprawls, and forms uniform oil film.
Described fluorine polyester fondant refers to the fluorine polyester after melting, and the preparation method of described fluorine polyester is 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 the fluorine polyester 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 the building-up process of fluorine polyester, conjugation due to fluorine, at esterification stage fluorine atom, make the acidity of dicarboxylic acids strengthen, cause the activity of carboxyl in dicarboxylic acids to increase simultaneously, make reaction speed accelerate, side reaction increases, be difficult to control, and then affect the growth of molecular weight of product, thus add inhibitor, by selecting metal oxide used to regulate.Described metal oxide can dissociate by following two kinds of modes:
Here M is metal ion, if the electronegativity of M is quite large, the duplet of oxonium ion is had to stronger attraction, so just can make O-H key weaken, and is conducive to reaction from solution; On the contrary, if the electronegativity of M is little, so just will generate the alkali center.M-O-H is similar with amphoteric compound, and when having alkaline matter to exist, reaction will be undertaken by the mode of acid dissociation; And, when acidic materials exist, by the mode of alkali formula ionization, undertaken.M-O-and the M+ of back reaction from acid dissociation mode and alkali formula ionization mode, M+ is as acid centre, its intensity only has direct relation with the electronegativity of metal ion, O ion in M-O-is relevant with the negative charge density on oxygen as the intensity at alkali center, negative charge density is larger, and 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.
As preferred technical scheme:
The preparation method of a kind of fluorine polyester POY 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 polyester POY 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 polyester POY 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 polyester POY fiber as above, described fluorine polyester fondant is directly obtained or obtained through the screw rod melting by the fluorine polyester slice by polymerization.
The preparation method of a kind of fluorine polyester POY 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 filament number of the novel fluorine polyester POY fiber of gained of the present invention is 0.5-3.0dtex; Fracture strength is 1.6～1.9cN/dtex; Elongation at break is 110～150%.Due to the introducing of fluorine atom, improved super-hydrophobic, hydrophobic and oil repellent, the antifouling aspect performance of polyester material, 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 novel fluorine polyester of gained POY fiber contain fluorine atoms; strong electronegativity due to fluorine; high C-F bond energy and to make the copolyesters POY fiber finally made have to the shielding protection effect of carbochain well heat-resisting, ageing-resistant, resistance to chemical attack and low electric capacity; low combustible; the performances such as low-refraction also have some special electric property, as low-k simultaneously; the advantages such as high-insulativity, expanded range of application.
2, the novel fluorine polyester of gained POY fiber has certain structural stability and machinability.
3, the novel fluorine polyester of gained POY fiber is introduced fluorine atom by employing, thereby has hydrophobic antifouling characteristic.
4, the novel fluorine polyester of gained POY fiber is by adopting modification by copolymerization, fundamentally solved the problems such as ageing, the durability of hydrophobic antifouling polyester and ABRASION RESISTANCE.
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 polyester POY fiber, be by the fluorine polyester fondant extrude, cooling, oil and coiling makes; Described fluorine polyester refers to the polyethylene terephthalate that the benzene ring hydrogen is replaced by fluorine, and its general structure is
Or
N=80～200 wherein.
A kind of fluorine polyester POY fiber as above, the filament number of described fluorine polyester POY fiber is 0.5～3.0dtex; Fracture strength is 1.6～2.5cN/dtex; Elongation at break is 110～150%.
Embodiment 1
A kind of preparation method of fluorine polyester, 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.
The method for preparing the POY fiber:
Be by described fluorine polyester fondant directly extrude, cooling, oil and coiling makes the POY fiber; Wherein, the described temperature of extruding is 285 ℃; Described to be cooled to lateral blowing cooling, and temperature is 30 ℃, and relative humidity is 60%, and wind speed is 0.4m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 8wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 60 parts of propylene glycol atactic polyethers, be heated to 60 ℃, 20 parts of polyethylene glycol lauric acid monoesters, 15 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluoro butyl ethyl propylene acid esters are uniformly mixed, then join in the propylene glycol atactic polyether, stir 1 hour, obtain fluorine-containing polyester fiber POY finish; The described oil applying rate oiled is 0.42%; The speed of described coiling is 2700m/min; Finally make fluorine polyester POY fiber, filament number is 3.0dtex; Fracture strength is 1.6cN/dtex; Elongation at break is 150%.
Embodiment 2
A kind of preparation method of fluorine polyester, 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 0.02% 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.
The method for preparing the POY fiber:
Be by described fluorine polyester fondant directly extrude, cooling, oil and coiling makes the POY fiber; Wherein, the described temperature of extruding is 295 ℃; Described to be cooled to lateral blowing cooling, and temperature is 20 ℃, and relative humidity is 70%, and wind speed is 0.8m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 9wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 50 parts of butanols atactic polyethers, be heated to 40 ℃, 32 parts of polyethylene glycol laurate dibasic acid esters, 15 parts of isomerous tridecanol polyoxyethylene ether phosphate kalium salts and 3 parts of perfluoro hexyl ethyl propylene acid esters are uniformly mixed, then join in the butanols atactic polyether, stir 2 hours, obtain fluorine-containing polyester fiber POY finish; The described oil applying rate oiled is 1.5%; The speed of described coiling is 2800m/min; Finally make fluorine polyester POY fiber, filament number is 2.0dtex; Fracture strength is 1.8cN/dtex; Elongation at break is 140%.
Embodiment 3
A kind of preparation method of fluorine polyester, 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 0.03% 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.
The method for preparing the POY fiber:
Be by described fluorine polyester fondant directly extrude, cooling, oil and coiling makes the POY fiber; Wherein, the described temperature of extruding is 290 ℃; Described to be cooled to lateral blowing cooling, and temperature is 25 ℃, and relative humidity is 65%, and wind speed is 0.6m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 10wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 58 parts of laurate atactic polyethers, be heated to 60 ℃, 30 parts of polyethylene glycol oleic acid monoesters, 10 part of ten tetracosanol phosphate kalium salt and 2 parts of perfluoro capryl ethyl propylene acid esters are uniformly mixed, then join in the propylene glycol atactic polyether, stir 1 hour, obtain fluorine-containing polyester fiber POY finish; The described oil applying rate oiled is 0.96%; The speed of described coiling is 2900m/min; Finally make fluorine polyester POY fiber, filament number is 1.5dtex; Fracture strength is 2.0cN/dtex; Elongation at break is 135%.
Embodiment 4
A kind of preparation method of fluorine polyester, 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 0.04% 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.
The method for preparing the POY fiber:
Be by described fluorine polyester fondant directly extrude, cooling, oil and coiling makes the POY fiber; Wherein, the described temperature of extruding is 285 ℃; Described to be cooled to lateral blowing cooling, and temperature is 30 ℃, and relative humidity is 60%, and wind speed is 0.4m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 8wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 50 parts of lauryl alcohol atactic polyethers, be heated to 50 ℃, 32 parts of polyethylene glycol Glycol Oleic Acid Ester, 13 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluoro butyl ethyl-methyl acrylate are uniformly mixed, then join in the propylene glycol atactic polyether, stir 1 hour, obtain fluorine-containing polyester fiber POY finish; The described oil applying rate oiled is 1.5%; The speed of described coiling is 3000m/min; Finally make fluorine polyester POY fiber, filament number is 1.0dtex; Fracture strength is 2.2cN/dtex; Elongation at break is 125%.
Embodiment 5
A kind of preparation method of fluorine polyester, 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 0.05% 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.
The method for preparing the POY fiber:
Be by described fluorine polyester fondant directly extrude, cooling, oil and coiling makes the POY fiber; Wherein, the described temperature of extruding is 295 ℃; Described to be cooled to lateral blowing cooling, and temperature is 20 ℃, and relative humidity is 70%, and wind speed is 0.8m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 10wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 55 parts of isomerous tridecanol atactic polyethers, be heated to 55 ℃, 25 parts of polyethylene glycol laurate dibasic acid esters, 15 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluoro hexyl ethyl-methyl acrylate are uniformly mixed, then join in the propylene glycol atactic polyether, stir 2 hours, obtain fluorine-containing polyester fiber POY finish; The described oil applying rate oiled is 0.42%; The speed of described coiling is 3200m/min; Finally make fluorine polyester POY fiber, filament number is 0.5dtex; Fracture strength is 2.5cN/dtex; Elongation at break is 110%.
Embodiment 6
A kind of preparation method of fluorine polyester, 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 0.005% 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 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.
The method for preparing the POY fiber:
Be by described fluorine polyester slice through screw rod melt extrude, cooling, oil and coiling makes the POY fiber; Wherein, the described temperature of extruding is 285 ℃; The described ring quenching that is cooled to, temperature is 30 ℃, and relative humidity is 60%, and wind speed is 0.4m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 9wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 60 parts of propylene glycol atactic polyethers, be heated to 45 ℃, 20 parts of polyethylene glycol oleic acid monoesters, 15 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluoro capryl ethyl-methyl acrylate are uniformly mixed, then join in the propylene glycol atactic polyether, stir 1 hour, obtain fluorine-containing polyester fiber POY finish; The described oil applying rate oiled is 0.42%; The speed of described coiling is 2700m/min; Finally make fluorine polyester POY fiber, filament number is 3.0dtex; Fracture strength is 1.6cN/dtex; Elongation at break is 150%.
Embodiment 7
A kind of preparation method of fluorine polyester, 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 0.006% 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 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 ℃, 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.
The method for preparing the POY fiber:
Be by described fluorine polyester slice through screw rod melt extrude, cooling, oil and coiling makes the POY fiber; Wherein, the described temperature of extruding is 295 ℃; The described ring quenching that is cooled to, temperature is 20 ℃, and relative humidity is 70%, and wind speed is 0.8m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 10wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 50 parts of butanols atactic polyethers, be heated to 40 ℃, 32 parts of polyethylene glycol laurate dibasic acid esters, 15 parts of isomerous tridecanol polyoxyethylene ether phosphate kalium salts and 3 parts of perfluoro hexyl ethyl propylene acid esters are uniformly mixed, then join in the butanols atactic polyether, stir 2 hours, obtain fluorine-containing polyester fiber POY finish; The described oil applying rate oiled is 1.5%; The speed of described coiling is 2800m/min; Finally make fluorine polyester POY fiber, filament number is 2.0dtex; Fracture strength is 1.8cN/dtex; Elongation at break is 140%.
Embodiment 8
A kind of preparation method of fluorine polyester, 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 0.006% 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 275 ℃, 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.
The method for preparing the POY fiber:
Be by described fluorine polyester slice through screw rod melt extrude, cooling, oil and coiling makes the POY fiber; Wherein, the described temperature of extruding is 290 ℃; The described ring quenching that is cooled to, temperature is 25 ℃, and relative humidity is 65%, and wind speed is 0.6m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 9wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 60 parts of propylene glycol atactic polyethers, be heated to 60 ℃, 20 parts of polyethylene glycol lauric acid monoesters, 15 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluoro butyl ethyl propylene acid esters are uniformly mixed, then join in the propylene glycol atactic polyether, stir 1 hour, obtain fluorine-containing polyester fiber POY finish; The described oil applying rate oiled is 0.96%; The speed of described coiling is 2900m/min; Finally make fluorine polyester POY fiber, filament number is 1.5dtex; Fracture strength is 2.0cN/dtex; Elongation at break is 135%.
Embodiment 9
A kind of preparation method of fluorine polyester, 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 0.008% 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.
The method for preparing the POY fiber:
Be by described fluorine polyester slice through screw rod melt extrude, cooling, oil and coiling makes the POY fiber; Wherein, the described temperature of extruding is 285 ℃; The described ring quenching that is cooled to, temperature is 30 ℃, and relative humidity is 60%, and wind speed is 0.4m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 8wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 50 parts of lauryl alcohol atactic polyethers, be heated to 50 ℃, 32 parts of polyethylene glycol Glycol Oleic Acid Ester, 13 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluoro butyl ethyl-methyl acrylate are uniformly mixed, then join in the propylene glycol atactic polyether, stir 1 hour, obtain fluorine-containing polyester fiber POY finish; The described oil applying rate oiled is 1.5%; The speed of described coiling is 3000m/min; Finally make fluorine polyester POY fiber, filament number is 1.5dtex; Fracture strength is 2.2cN/dtex; Elongation at break is 125%.
Embodiment 10
A kind of preparation method of fluorine polyester, 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 0.01% 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.
The method for preparing the POY fiber:
Be by described fluorine polyester slice through screw rod melt extrude, cooling, oil and coiling makes the POY fiber; Wherein, the described temperature of extruding is 295 ℃; The described ring quenching that is cooled to, temperature is 20 ℃, and relative humidity is 70%, and wind speed is 0.8m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 10wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 60 parts of propylene glycol atactic polyethers, be heated to 45 ℃, 20 parts of polyethylene glycol oleic acid monoesters, 15 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluoro capryl ethyl-methyl acrylate are uniformly mixed, then join in the propylene glycol atactic polyether, stir 1 hour, obtain fluorine-containing polyester fiber POY finish; The described oil applying rate oiled is 0.42%; The speed of described coiling is 3200m/min; Finally make fluorine polyester POY fiber, filament number is 0.5dtex; Fracture strength is 2.5cN/dtex; Elongation at break is 110%.
Claims (10)
1. a fluorine polyester POY fiber is characterized in that: described fluorine polyester POY fiber be by the fluorine polyester fondant through measuring, extrude, cooling, oil and coiling makes; Described fluorine polyester refers to the polyethylene terephthalate that the benzene ring hydrogen is replaced by fluorine, and its general structure is
Or
N=80～200 wherein.
2. a kind of fluorine polyester POY fiber according to claim 1, is characterized in that, the filament number of described fluorine polyester POY fiber is 0.5～3.0dtex; Fracture strength is 1.6～2.5cN/dtex; Elongation at break is 110～150%.
3. the preparation method of a kind of fluorine polyester POY fiber as claimed in claim 1 is characterized in that: by the fluorine polyester fondant through measuring, extrude, cooling, the step that oils and reel, make fluorine polyester POY fiber;
The described temperature of extruding is 285～295 ℃;
Described cooling temperature is 20～30 ℃;
The described oil applying rate oiled is 0.42～1.5wt%;
The speed of described coiling is 2700～3200m/min;
The described finish oiled is fluorine-containing polyester POY fiber finish, its component by weight:
Atactic polyether, 50～60 parts;
Cithrol, 20～32 parts;
Phosphate kalium salt, 10～15 parts;
Perfluoroalkyl acrylate, 2～5 parts;
The preparation method of finish:
By atactic polyether, be heated to 40～60 ℃, cithrol, phosphate kalium salt and perfluoroalkyl acrylate are uniformly mixed, then join in atactic polyether, stir 1～2 hour, obtain fluorine-containing polyester POY fiber finish, finish adds water while using and is made into the emulsion that solid content is 8～10wt%;
Described fluorine polyester fondant refers to the fluorine polyester after melting, and the preparation method of described fluorine polyester is 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, 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 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.
4. the preparation method of a kind of fluorine polyester POY fiber according to claim 3, is characterized in that, described lateral blowing or the ring quenching of being cooled to, and temperature is 20 ℃～30 ℃, and relative humidity is 65% ± 5%, and wind speed is 0.4～0.8m/s.
5. the preparation method of a kind of fluorine polyester POY fiber according to claim 3, is characterized in that, the mol ratio of described ethylene glycol and fluorine-containing terephthalic acid (TPA) is 1.2～2.0:1.
6. the preparation method of a kind of fluorine polyester POY fiber according to claim 3, 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.
7. the preparation method of a kind of fluorine polyester POY fiber according to claim 3, 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.
8. the preparation method of a kind of fluorine polyester POY fiber according to claim 3, is characterized in that, the addition of described inhibitor is 0.01%～0.05% of described fluorine-containing terephthalic acid (TPA) weight.
9. the preparation method of a kind of fluorine polyester POY fiber according to claim 3, is characterized in that, described fluorine polyester fondant is directly obtained or obtained through the screw rod melting by the fluorine polyester slice by polymerization.
10. the preparation method of a kind of fluorine polyester POY fiber according to claim 3, it is characterized in that, described atactic polyether is a kind of in propylene glycol atactic polyether, butanols atactic polyether, laurate atactic polyether, lauryl alcohol atactic polyether and isomerous tridecanol atactic polyether; Described cithrol is a kind of in polyethylene glycol lauric acid monoester, polyethylene glycol laurate dibasic acid esters, polyethylene glycol oleic acid monoester and polyethylene glycol Glycol Oleic Acid Ester; Described phosphate kalium salt is a kind of in 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, isomerous tridecanol polyoxyethylene ether phosphate kalium salt and ten tetracosanol phosphate kalium salts; Described perfluoroalkyl acrylate is a kind of in perfluoro butyl ethyl propylene acid esters, perfluoro hexyl ethyl propylene acid esters, perfluoro capryl ethyl propylene acid esters, perfluoro butyl ethyl-methyl acrylate, perfluoro hexyl ethyl-methyl acrylate and perfluoro capryl ethyl-methyl acrylate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104448278A (en) * | 2014-12-12 | 2015-03-25 | 东华大学 | Antifouling, flame-retardant and anti-droplet polyester and preparation method thereof |
| CN109853072A (en) * | 2018-11-22 | 2019-06-07 | 常州灵达特种纤维有限公司 | A kind of preparation method of modification by copolymerization anti-pollution terylene bulk filament |
| CN113355767A (en) * | 2021-07-10 | 2021-09-07 | 杭州恒吉新材料科技有限公司 | High-wear-resistance POY polyester yarn and preparation method thereof |
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| CN113355767A (en) * | 2021-07-10 | 2021-09-07 | 杭州恒吉新材料科技有限公司 | High-wear-resistance POY polyester yarn and preparation method thereof |
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