CN103469350A - Fluorinated polyester fully drawn yarn (FDY) fibers and preparation method thereof - Google Patents
Fluorinated polyester fully drawn yarn (FDY) fibers and preparation method thereof Download PDFInfo
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Abstract
The invention relates to fluorinated polyester fully drawn yarn (FDY) fibers and a preparation method thereof. The preparation method comprises fluorinated polyester melt preparation and fluorinated polyester FDY 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 then screw melt extrusion on the slices, and carrying cooling, oil coating, drawing and winding to obtain the fluorinated polyester FDY fibers. The novel fluorinated polyester FDY fibers have fiber breaking strength of 3-5cN/dex and breaking elongation of 18-45%. Through use of fluorine atoms, super-hydrophobic, hydrophobic, oleophobic and antifouling performances of the polyester FDY fibers are improved. The fluorinated polyester FDY 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 FDY fiber and preparation method thereof, particularly relate to fluorine polyester FDY 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.Introduce stretching action in spinning process, can obtain the undrawn yarn with high-orientation and crystalline medium degree, be called fullly drawn yarn (FDY), i.e. FDY.FDY is mainly as the warp thread of water jet looms fabric, and the conventional fullly drawn yarn (FDY) that terylene and polyamide fibre are arranged, all belong to chemical-fibres filaments.The smooth softness of FDY fabric feel, be often used in and weave silk-like fabric, at clothes and family, has been widely used aspect spinning.
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, ethene～TFE 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.(the Q Z Zhu such as Qingzeng Zhu, C C Han.Synthesis and crystalization behaviors of highly fluorinated aromatic polyesters[J] .Polymer2007 (48): 3624～3631.) by adding the mode modified poly ester of fluorine-containing binary acid copolymerization, 2,3,4,5～ptfe phthalate modification polyethylene glycol phthalate, the crystal property of polyester improves.
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 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 invention provides a kind of fluorine polyester FDY fiber and preparation method thereof, fluorine polyester FDY fiber that particularly provides a kind of benzene ring hydrogen to be replaced by fluorine and preparation method thereof.A kind of fluorine polyester FDY fiber of the present invention adopts fluorine-containing Direct-spinning of PET Fiber, described fluorine-containing polyester is to introduce fluorine atom on the main chain of polymer, the novel fluorine polyester that terephthalic acid (TPA) by contain fluorine atoms on phenyl ring and ethylene glycol obtain 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, also can well solve this class problem that wastes time and energy.
The invention provides following technical scheme:
A kind of fluorine polyester FDY fiber, be by the fluorine polyester fondant directly extrude or make section through screw rod melt extrude, cooling, oil, stretch 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 FDY fiber as above, the fracture strength 3～5cN/dex of described fluorine polyester FDY fiber; Elongation at break is 18～45%.
The present invention also provides a kind of preparation method of fluorine polyester FDY fiber, be by the fluorine polyester fondant measure, extrude, cooling, oil, stretch and coiling makes fluorine polyester FDY fiber.
The described temperature of extruding is 275～290 ℃;
Described cooling wind-warm syndrome is 20～30 ℃;
The described oil applying rate oiled is 0.42～1.5wt%;
The draft speed of the first hot-rolling of described stretching is 2000～2500m/min; The draft speed of the second hot-rolling is 4000～6000/min, and its heat setting temperature is 135～155 ℃;
The speed of described coiling is 3950～5950m/min;
Described lateral blowing or the ring quenching of being cooled to, temperature is 20 ℃～30 ℃, and humidity is 65% ± 5%, and wind speed is 0.4～0.8m/s.
The described finish oiled is fluorine-containing polyester FDY fiber finish, its component by weight:
Component A: mineral oil 40-60 part;
B component: polyoxyethylene ether 20-35 part;
Component C: phosphate kalium salt 5-10 part;
Component D: cithrol 8-16 part;
Component E: sodium alkyl sulfonate 1-5 part;
Component F: perfluoroalkyl acrylate 1-5 part.
Described fluorine-containing polyester FDY fiber is with in finish, and component A mineral oil is smooth agent: this material is 9
#～17
#mineral oil in a kind of.Mineral oil has good heat resistance, with other component, pretty good compatibility is arranged, and it has and oils evenly, and the characteristics that film strength is high can also effectively reduce the coefficient of friction of fiber and metal, and the cohesive force of increase fiber, be conducive to boundling.
Described fluorine-containing polyester FDY fiber is with in finish, and the B component polyoxyethylene ether is emulsifying agent: this material is a kind of in the pure polyoxyethylene ether of isomery ten, isomerous tridecanol polyoxyethylene ether, ethoxylated dodecyl alcohol, tridecanol polyoxyethylene ether, ten tetracosanol polyoxyethylene ether, tetradecyl alchohol polyoxyethylene ether, hexadecanol polyoxyethylene ether and polyoxyethylene octadecanol.This component has good heat resistance, and its hydrophobic grouping and emulsified thing have good compatibility, can also keep larger hydrophily, can make whole finish form uniform and stable emulsion simultaneously.
Described fluorine-containing polyester FDY 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.Adopt anionic antistatic agent, can realize surface hydrophilic, be beneficial to the displacement of finish and slurry.The heat resistance of phosphate kalium salt is relatively good, good antistatic behaviour, and antistatic effect that can fortifying fibre, be conducive to the boundling of fiber.
Described fluorine-containing polyester FDY fiber is with in finish, and component D cithrol is collecting agent: this material is a kind of in polyethylene glycol stearate monoesters, polyethylene glycol stearate, polyethylene glycol lauric acid monoester, polyethylene glycol laurate dibasic acid esters, polyethylene glycol oleic acid monoester and polyethylene glycol Glycol Oleic Acid Ester.Contain ester group in the large molecule of fluorine-containing polyester fiber, the selected fatty acid ester, have better adhesive force with it.And its flatness excellence, starching and heat resistance are good, can meet the technological requirement of FDY finish.Collecting agent add convergence and the flatness that can improve finish, simultaneously, can play synergy with the phosphate kalium salt antistatic additive, the antistatic effect of fortifying fibre, make the cohesive force of fiber improve, and is conducive to the boundling in the fiber process process.
Described fluorine-containing polyester FDY fiber is with in finish, and component E sodium alkyl sulfonate is additive: this material is a kind of in dodecyl sodium sulfate, pentadecyl sodium sulfonate and sodium cetanesulfonate.Sodium alkyl sulfonate add the penetrating power that can improve finish, make finish to be attached to uniformly in the short period of time on tow, can effectively reduce the appearance of lousiness, broken end.
Described fluorine-containing polyester FDY fiber is with in finish, and component F 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 objective is in order suitably to reduce the surface tension of finish, be easy to form uniform continuous oil film.Perfluoroalkyl and acrylate have lower surface energy, and appropriate interpolation can be lowered the surface tension of finish, makes the wettability of finish and penetrability greatly increase, and are easy to the wetting of fiber and sprawl, and form uniform oil film.
The main implementation procedure of finish for described fluorine-containing polyester FDY fiber: B component, component C, component D, component E and component F normal temperature are mixed, stir 20-30 minute, and then mixture is joined in component A, temperature is controlled as 40-55 ℃, stir 0.5～2h, can obtain the FDY finish of function admirable, be configured to 8～10% emulsion during use with pure water.
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.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.
As preferred technical scheme:
The preparation method of a kind of fluorine polyester FDY 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 FDY 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 FDY 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 FDY 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 FDY 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.
Fracture strength 3～the 5cN/dex of the novel fluorine polyester FDY fiber of gained of the present invention; Elongation at break is 18～45%.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 FDY fiber contain fluorine atoms; strong electronegativity due to fluorine; high C～F bond energy and to make the fluorine polyester FDY 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 smooth softness of the novel fluorine polyester of gained FDY fiber feel, be applicable to weave silk-like fabric.
3, the novel fluorine polyester of gained FDY fiber is introduced fluorine atom by employing, thereby has hydrophobic antifouling characteristic.
4, the novel fluorine polyester of gained FDY 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 FDY fiber, be by the fluorine polyester fondant measure, extrude, cooling, oil, stretch 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 FDY fiber as above, the fracture strength 3～5cN/dex of described fluorine polyester FDY fiber; Elongation at break is 18～45%.
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% zinc oxide of tetrafluoro terephthalic acid (TPA) weight simultaneously, carry out esterification after being made into uniform sizing material; Esterification is in nitrogen atmosphere, and pressure is controlled at 0.4MPa, 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 FDY fiber:
Be by described fluorine polyester fondant directly metering extrude, cooling, oil, stretching and coiling and molding make the FDY fiber; The described temperature of extruding is 275 ℃; Described to be cooled to lateral blowing cooling, and temperature is 20 ℃ ℃, and humidity is 65%, and wind speed is 0.4m/s; The described finish oiled is fluorine-containing polyester FDY fiber finish, its component by weight, get 20 parts of pure polyoxyethylene ether of poly-isomery ten, 10 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, 16 parts of polyethylene glycol stearate monoesters, 4 parts of dodecyl sodium sulfates, 5 parts of perfluoro butyl ethyl propylene acid esters normal temperature mixing, stir 20min.Said mixture is joined to 45 part 9
#in mineral oil, temperature is controlled at 55 ℃, stirs 1h, can obtain the FDY finish of function admirable, and finish adds water while using and is made into the emulsion that solid content is 8wt%; The described oil applying rate oiled is 0.42wt%; The draft speed of the first hot-rolling of described stretching is 2000m/min; The draft speed of the second hot-rolling is 4000m/min, and its heat setting temperature is 135 ℃; The speed of described coiling is 3950m/min; Finally make fluorine polyester FDY fiber, fracture strength 3cN/dex; Elongation at break is 45%.
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 0.04% 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 preparation method of preparation FDY:
Be by described fluorine polyester fondant directly extrude, cooling, oil, the first hot-rolling, the second hot-rolling, coiling and molding make the FDY fiber; The described temperature of extruding is 290 ℃; Described to be cooled to lateral blowing cooling, and temperature is 25 ℃, and humidity is 70%, and wind speed is 0.6m/s; The described finish oiled is fluorine-containing polyester FDY fiber finish, its component by weight, get 35 parts of isomerous tridecanol polyoxyethylene ethers, 5 parts of isomerous tridecanol polyoxyethylene ether phosphate kalium salts, 14 parts of polyethylene glycol stearates, 1 part of pentadecyl sodium sulfonate, 5 parts of perfluoro hexyl ethyl propylene acid esters normal temperature mixing, stir 30min.Said mixture is joined to 40 part 10
#in mineral oil, temperature is controlled at 40 ℃, stirs 0.5h, can obtain the FDY finish of function admirable; The described oil applying rate oiled is 1.5%; The draft speed of the first hot-rolling of described stretching is 2500m/min; The draft speed of the second hot-rolling is 6000m/min, and its heat setting temperature is 155 ℃; The speed of described coiling is 5950m/min; Finally make fluorine polyester FDY fiber, fracture strength 5cN/dex; Elongation at break is 18%.
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 0.02% 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 FDY fiber:
Be by described fluorine polyester fondant directly extrude, cooling, oil, the first hot-rolling, the second hot-rolling, coiling and molding make the FDY fiber; The described temperature of extruding is 280 ℃; Described to be cooled to lateral blowing cooling, and temperature is 30 ℃, and humidity is 60%, and wind speed is 0.8m/s; The described finish oiled is fluorine-containing polyester FDY fiber finish, its component by weight, get 25 parts of laurate polyoxyethylene ether, 7 part of ten tetracosanol phosphate kalium salt, 11 parts of polyethylene glycol lauric acid monoesters, 5 parts of sodium cetanesulfonates, 2 parts of perfluoro capryl ethyl propylene acid esters normal temperature mixing, stir 20min.Said mixture is joined to 50 part 11
#in mineral oil, temperature is controlled at 55 ℃, stirs 2h, can obtain the FDY finish of function admirable; The described oil applying rate oiled is 0.96%; The draft speed of the first hot-rolling of described stretching is 2200m/min; The draft speed of the second hot-rolling is 4500m/min, and its heat setting temperature is 140 ℃; The speed of described coiling is 4450m/min; Finally make fluorine polyester FDY fiber, fracture strength 3.5cN/dex; Elongation at break is 40%.
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 0.03% manganese 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 FDY fiber:
Be by described fluorine polyester fondant directly extrude, cooling, oil, the first hot-rolling, the second hot-rolling, coiling and molding make the FDY fiber; The described temperature of extruding is 280 ℃; Described to be cooled to lateral blowing cooling, and temperature is 20 ℃, and humidity is 65%, and wind speed is 0.4m/s; The described finish oiled is fluorine-containing polyester FDY fiber finish, its component by weight, get 23 parts of tridecanol polyoxyethylene ethers, 5 parts of isomerous tridecanol polyoxyethylene ether phosphate kalium salts, 8 parts of polyethylene glycol laurate dibasic acid esters, 3 parts of pentadecyl sodium sulfonates, 1 part of perfluoro butyl ethyl-methyl acrylate normal temperature mixing, stir 30min.Said mixture is joined to 60 part 12
#in mineral oil, temperature is controlled at 50 ℃, stirs 1.5h, can obtain the FDY finish of function admirable; The described oil applying rate oiled is 1.5%; The draft speed of the first hot-rolling of described stretching is 2300m/min; The draft speed of the second hot-rolling is 5000m/min, and its heat setting temperature is 145 ℃; The speed of described coiling is 4950m/min; Finally make fluorine polyester FDY fiber, fracture strength 4cN/dex; Elongation at break is 30%.
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 0.01% magnesia 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 FDY fiber:
Be by described fluorine polyester fondant directly extrude, cooling, oil, the first hot-rolling, the second hot-rolling, coiling and molding make the FDY fiber; The described temperature of extruding is 290 ℃; Described to be cooled to lateral blowing cooling, and temperature is 30 ℃, and humidity is 70%, and wind speed is 0.8m/s; The described finish oiled is fluorine-containing polyester FDY fiber finish, its component by weight, get 30 parts of polyoxyethylene octadecanols, 8 part of ten tetracosanol phosphate kalium salt, 12 parts of polyethylene glycol oleic acid monoesters, 2 parts of pentadecyl sodium sulfonates, 3 parts of perfluoro hexyl ethyl-methyl acrylate normal temperature mixing, stir 30min.By said mixture and join 45 part 14
#in mineral oil, temperature is controlled at 55 ℃, stirs 50 minutes, can obtain the FDY finish of function admirable; The described oil applying rate oiled is 0.42%; The draft speed of the first hot-rolling of described stretching is 2400m/min; The draft speed of the second hot-rolling is 5500m/min, and its heat setting temperature is 150 ℃; The speed of described coiling is 5450m/min; Finally make fluorine polyester FDY fiber, fracture strength 5cN/dex; Elongation at break is 18%.
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 0.01% 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 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 the fluorine polyester slice.
The method for preparing the FDY fiber:
Be by described fluorine polyester slice through screw rod melt extrude, cooling, oil, the first hot-rolling, the second hot-rolling, coiling and molding make the FDY fiber; The described temperature of extruding is 275 ℃; The described ring quenching that is cooled to, temperature is 20 ℃ ℃, and humidity is 65%, and wind speed is 0.4m/s; The described finish oiled is fluorine-containing polyester FDY fiber finish, its component by weight, get 32 parts of hexadecanol polyoxyethylene ether, 6 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, 14 parts of polyethylene glycol Glycol Oleic Acid Ester, 3 parts of sodium cetanesulfonates, 5 parts of perfluoro capryl ethyl-methyl acrylate normal temperature mixing, stir 20min.Said mixture is joined to 40 part 15
#in mineral oil, temperature is controlled at 40 ℃, stirs 1.5h, can obtain the FDY finish of function admirable; The described oil applying rate oiled is 0.42%; The draft speed of the first hot-rolling stretched is 2400m/min; The draft speed of the second hot-rolling is 4000m/min, and its heat setting temperature is 135 ℃; The speed of described coiling is 3950m/min; Finally make fluorine polyester FDY fiber, fracture strength 3cN/dex; Elongation at break is 45%.
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 0.02% 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 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 the fluorine polyester slice.
The method for preparing the FDY fiber:
Be by described fluorine polyester slice through screw rod melt extrude, cooling, oil, the first hot-rolling, the second hot-rolling, coiling and molding make the FDY fiber; The described temperature of extruding is 290 ℃; The described ring quenching that is cooled to, temperature is 25 ℃, and humidity is 70%, and wind speed is 0.6m/s; The described finish oiled is fluorine-containing polyester FDY fiber finish, its component by weight, get 28 parts of tetradecyl alchohol polyoxyethylene ether, 9 part of ten tetracosanol phosphate kalium salt, 13 parts of polyethylene glycol stearates, 4 parts of dodecyl sodium sulfates, 2 parts of perfluoro butyl ethyl-methyl acrylate normal temperature mixing, stir 20min.Said mixture is joined to 44 part 16
#in mineral oil, temperature is controlled at 45 ℃, stirs 75 minutes, can obtain the FDY finish of function admirable; The described oil applying rate oiled is 1.5%; The draft speed of the first hot-rolling of described stretching is 2500m/min; The draft speed of the second hot-rolling is 6000m/min, and its heat setting temperature is 155 ℃; The speed of described coiling is 5950m/min; Finally make fluorine polyester FDY fiber, fracture strength 5cN/dex; Elongation at break is 18%.
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 0.05% 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 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 the fluorine polyester slice.
The method for preparing the FDY fiber:
Be by described fluorine polyester slice through screw rod melt extrude, cooling, oil, the first hot-rolling, the second hot-rolling, coiling and molding make the FDY fiber; The described temperature of extruding is 285 ℃; The described ring quenching that is cooled to, temperature is 30 ℃, and humidity is 60%, and wind speed is 0.8m/s; The described finish oiled is fluorine-containing polyester FDY fiber finish, its component by weight, getting 24 parts is ten tetracosanol polyoxyethylene ether, 5 parts of isomerous tridecanol phosphate kalium salts, 8 parts of polyethylene glycol laurate dibasic acid esters, 4 parts of sodium cetanesulfonates, 4 parts of perfluoro hexyl ethyl propylene acid esters normal temperature mixing, stirs 20min.Said mixture is joined to 55 part 17
#in mineral oil, temperature is controlled at 50 ℃, stirs 1.5h, can obtain the FDY finish of function admirable; The described oil applying rate oiled is 0.96%; The draft speed of the first hot-rolling of described stretching is 2200m/min; The draft speed of the second hot-rolling is 4500m/min, and its heat setting temperature is 140 ℃; The speed of described coiling is 4450m/min; Finally make fluorine polyester FDY fiber, fracture strength 3.5cN/dex; Elongation at break is 40%.
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 0.03% 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 the fluorine polyester slice.
The method for preparing the FDY fiber:
Be by described fluorine polyester slice through screw rod melt extrude, cooling, oil, the first hot-rolling, the second hot-rolling, coiling and molding make the FDY fiber; The described temperature of extruding is 280 ℃; The described ring quenching that is cooled to, temperature is 20 ℃, and humidity is 65%, and wind speed is 0.4m/s; The described finish oiled is fluorine-containing polyester FDY fiber finish, its component by weight, get 20 parts of pure polyoxyethylene ether of poly-isomery ten, 10 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, 16 parts of polyethylene glycol stearate monoesters, 4 parts of dodecyl sodium sulfates, 5 parts of perfluoro butyl ethyl propylene acid esters normal temperature mixing, stir 20min.Said mixture is joined to 45 part 9
#in mineral oil, temperature is controlled at 55 ℃, stirs 1h, can obtain the FDY finish of function admirable; The described oil applying rate oiled is 1.5%; The draft speed of the first hot-rolling of described stretching is 2300m/min; The draft speed of the second hot-rolling is 5000m/min, and its heat setting temperature is 145 ℃; The speed of described coiling is 4950m/min; Finally make fluorine polyester FDY fiber, fracture strength 4cN/dex; Elongation at break is 30%.
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 0.04% 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 the fluorine polyester slice.
The method for preparing the FDY fiber:
Be by described fluorine polyester slice through screw rod melt extrude, cooling, oil, the first hot-rolling, the second hot-rolling, coiling and molding make the FDY fiber; The described temperature of extruding is 290 ℃; The described ring quenching that is cooled to, temperature is 20 ℃, and humidity is 65%, and wind speed is 0.8m/s; The described finish oiled is fluorine-containing polyester FDY fiber finish, its component by weight, get 35 parts of isomerous tridecanol polyoxyethylene ethers, 5 parts of isomerous tridecanol polyoxyethylene ether phosphate kalium salts, 14 parts of polyethylene glycol stearates, 1 part of pentadecyl sodium sulfonate, 5 parts of perfluoro hexyl ethyl propylene acid esters normal temperature mixing, stir 30min.Said mixture is joined to 40 part 10
#in mineral oil, temperature is controlled at 40 ℃, stirs 0.5h, can obtain the FDY finish of function admirable; The described oil applying rate oiled is 0.42%; The draft speed of the first hot-rolling of described stretching is 2400m/min; The draft speed of the second hot-rolling is 5500m/min, and its heat setting temperature is 150 ℃; The speed of described coiling is 5450m/min; Finally make fluorine polyester FDY fiber, fracture strength 5cN/dex; Elongation at break is 18%.
Claims (10)
1. a fluorine polyester FDY fiber is characterized in that: described fluorine polyester FDY fiber be by the fluorine polyester fondant through measuring, extrude, cooling, oil, stretch 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 FDY fiber according to claim 1, is characterized in that the fracture strength 3～5cN/dex of described fluorine polyester FDY fiber; Elongation at break is 18～45%.
3. the preparation method of a kind of fluorine polyester FDY fiber as claimed in claim 1 is characterized in that: by the fluorine polyester fondant through measuring, extrude, cooling, oil, stretch and the step of reeling, make fluorine polyester FDY fiber;
The described temperature of extruding is 275～290 ℃;
Described cooling wind-warm syndrome is 20～30 ℃;
The described oil applying rate oiled is 0.42～1.5wt%;
The draft speed of the first hot-rolling of described stretching is 2000～2500m/min; The draft speed of the second hot-rolling is 4000～6000/min, and its heat setting temperature is 135～155 ℃;
The speed of described coiling is 3950～5950m/min;
The described finish oiled is fluorine-containing polyester FDY fiber finish, its component by weight:
Component A: mineral oil 40-60 part;
B component: polyoxyethylene ether 20-35 part;
Component C: phosphate kalium salt 5-10 part;
Component D: cithrol 8-16 part;
Component E: sodium alkyl sulfonate 1-5 part;
Component F: perfluoroalkyl acrylate 1-5 part;
The preparation of finish:
B component, component C, component D, component E and component F normal temperature are mixed, stir 20-30 minute, and then mixture is joined in component A, temperature is controlled as 40-55 ℃, stir 0.5～2h, can obtain fluorine-containing polyester FDY 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 FDY 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 humidity is 65% ± 5%, and wind speed is 0.4～0.8m/s.
5. the preparation method of a kind of fluorine polyester 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 FDY 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 FDY 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 FDY 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 FDY 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 FDY fiber according to claim 3, is characterized in that, described mineral oil is 9
#～17
#mineral oil in a kind of; Described polyoxyethylene ether is a kind of in the pure polyoxyethylene ether of isomery ten, isomerous tridecanol polyoxyethylene ether, ethoxylated dodecyl alcohol, tridecanol polyoxyethylene ether, ten tetracosanol polyoxyethylene ether, tetradecyl alchohol polyoxyethylene ether, hexadecanol polyoxyethylene ether and polyoxyethylene octadecanol; 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 cithrol is a kind of in polyethylene glycol stearate monoesters, polyethylene glycol stearate, polyethylene glycol lauric acid monoester, polyethylene glycol laurate dibasic acid esters, polyethylene glycol oleic acid monoester and polyethylene glycol Glycol Oleic Acid Ester; Described sodium alkyl sulfonate is a kind of in dodecyl sodium sulfate, pentadecyl sodium sulfonate and sodium cetanesulfonate; 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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| CN107054789A (en) * | 2015-01-28 | 2017-08-18 | 晋江名仕纺织机械设计有限公司 | Supporting logistics device is packed in FDY digitlizations automatically |
| 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 |
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