CN103469350B - A kind of preparation method of fluorine polyester FDY fiber - Google Patents
A kind of preparation method of fluorine polyester FDY fiber Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of fluorine polyester FDY fiber, comprise the preparation of fluorine polyester fondant and the preparation of fluorine polyester FDY fiber; In the preparation technology of fluorine polyester fondant, adopt fluorine-containing terephthalic acid (TPA) and ethylene glycol as raw material and add inhibitor and prepare fluorine polyester fondant, directly extrude melt or make section and to melt extrude through screw rod, cool, oil, stretch and reel obtained fluorine polyester FDY fiber.The novel fluorine polyester FDY fiber fracture strength 3 ~ 5cN/dex of gained of the present invention; Elongation at break is 18 ~ 45%.Due to the introducing of fluorine atom, improve super-hydrophobic, hydrophobic and oil repellent, the antifouling aspect performance of polyester FDY fiber, at waterproof garment, in the Work Clothes manufacture of the Work Clothes born dirty and some special industry, have huge prospect.
Description
Technical field
The present invention relates to a kind of preparation method of fluorine polyester FDY fiber, particularly relate to the preparation method of the fluorine polyester FDY fiber that a kind of benzene ring hydrogen replaced by fluorine.
Background technology
Polyester (PET) is one of the most widely used synthetic high polymer of the current mankind; PET has just been synthesized 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, packaging, health care, automobile, electronic apparatus, security protection, environmental protection.In spinning process, introduce stretching action, the undrawn yarn with high-orientation and crystalline medium degree can be obtained, be called fullly drawn yarn (FDY), be i.e. FDY.FDY is mainly used as the warp thread of water jet looms fabric, and the conventional fullly drawn yarn (FDY) having terylene and polyamide fibre, all belongs to chemical-fibres filaments.The smooth softness of FDY fabric feel, is often used in and weaves silk-like fabric, has been widely used in clothes and family spin.
Along with the progress of society, the raising of living standards of the people, needs more and more higher to differential, the functionalization of polyester fiber.What therefore the modification of polyester also became particularly is important, and polyester modification object, except being optimized conventional polyester performance, mainly gives 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 introducing fluorine atom in the polymer, thus improving the surface property of material, as hydro-oleophobicity and soil resistance etc., and giving polyester material various function.Because fluoropolymer has low-surface-energy, low-friction coefficient and non-adhesiveness usually, dust dirt is difficult to the characteristics such as attachment, and therefore the anti-soil ABRASION RESISTANCE of fluoropolymer is good.And current fluoropolymer is based on fluoroolefin base polymer (such as: polytetrafluoroethylene (PTFE), Kynoar, fluorinated ethylene propylene copolymer, ethene ~ TFE copolymer etc.); The research of fluorochemical urethane, fluorochemical polyether, fluorine-containing polyester etc. then relatively lags behind.
Many scholars are studied fluorochemical modified poly ester, and achieve certain achievement.The mode of current fluorochemical modified poly ester mainly by adding fluorine-containing end-capping reagent, or adds the fluorochemical such as Fluorinated dihydric alcohol, fluorine-containing binary acid and carrys out modified poly ester as Third monomer.Wang Zhong just waits (Wang Zhonggang, Li Wenjuan, by the industry that continues. fluorine-containing polyester with 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 perfluoro-octanoyl amine, have prepared the low and polyester material that contaminated resistance 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.) principle of MOLECULE DESIGN is utilized, by adding the mode of Fluorinated dihydric alcohol copolymerization, paraphthaloyl chloride, hexafluoro bisphenol-a and fluorine-containing ethohexadiol ternary polymerization are synthesized the polyester of novel high fluorinated volume.This polyester has excellent performance and is applied to optical waveguide material.(the QZZhu such as QingzengZhu, CCHan.Synthesisandcrystalizationbehaviorsofhighlyfluorin atedaromaticpolyesters [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.
But the polyester these being contained fluorine element is applied in weaving and packaging material certain limitation, subject matter is that the molecular weight of polyesters containing fluorine element of prior art is low, can not meet the requirement of spinning and film forming; Prior art mainly gives its water proof anti-soil function by the fluorine-containing Final finishing mode of fabric at present, and the maximum shortcoming of these class methods is to be difficult to solve the problems such as ageing, durability and ABRASION RESISTANCE, and wastes time and energy.
Therefore, developing fluorine-containing polyester fiber for weaving and the modification of super-hydrophobic, hydrophobic and oil repellent, antifouling property of packaging material, important theory significance and using value will be had.
Summary of the invention
The invention provides a kind of preparation method of fluorine polyester FDY fiber, the preparation method of the fluorine polyester FDY fiber particularly providing a kind of benzene ring hydrogen to replaced by fluorine.A kind of fluorine polyester FDY fiber of the present invention adopts fluorine-containing Direct-spinning of PET Fiber, described fluorine-containing polyester introduces fluorine atom on the main chain of polymer, by the novel fluorine polyester that terephthalic acid (TPA) and the ethylene glycol of contain fluorine atoms on phenyl ring obtain through over-churning and polycondensation, by copolymerization method, hydrophobic antifouling modification is carried out to polyester, fundamentally can solve ageing, the problem such as durability and ABRASION RESISTANCE of hydrophobic antifouling polyester, also can well solve this kind of problem that wastes time and energy.
The invention provides following technical scheme:
A kind of fluorine polyester FDY fiber is directly extruded or make section to melt extrude through screw rod, cool, oil, stretch and reel obtained by fluorine polyester fondant; Described fluorine polyester refers to the polyethylene terephthalate that benzene ring hydrogen replaced by fluorine, and its general structure is
Wherein n=80 ~ 200;
Fracture strength 3 ~ the 5cN/dex of described fluorine polyester FDY fiber; Elongation at break is 18 ~ 45%;
Described obtained fluorine polyester FDY fiber that fluorine polyester fondant is measured, extrudes, cools, oils, stretches and reels, wherein:
The described temperature extruded is 275 ~ 290 DEG C;
The wind-warm syndrome of described cooling is 20 ~ 30 DEG C;
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 DEG C;
The speed of described winding is 3950 ~ 5950m/min;
Described is cooled to lateral blowing or ring quenching, and temperature is 20 DEG C ~ 30 DEG C, 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.
In described fluorine-containing polyester FDY fiber finish, component A mineral oil is smooth agent: this material is 9
#~ 17
#mineral oil in one.Mineral oil has good heat resistance, has good compatibility with other component, and it has and oils evenly, and the feature that film strength is high, effectively can also reduce the coefficient of friction of fiber and metal, and the cohesive force of increase fiber, is conducive to boundling.
In described fluorine-containing polyester FDY fiber finish, B component polyoxyethylene ether is emulsifying agent: this material is the one in isomery ten alcohol polyoxyethylene ether, 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 simultaneously, whole finish can be made to form uniform and stable emulsion.
In described fluorine-containing polyester FDY fiber finish, component C phosphate kalium salt is antistatic additive: this material is the one 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 surface hydrophilic be realized, be beneficial to the displacement of finish and slurry.The heat resistance of phosphate kalium salt is relatively good, good antistatic behaviour, can the antistatic effect of fortifying fibre, is conducive to the boundling of fiber.
In described fluorine-containing polyester FDY fiber finish, component D cithrol is collecting agent: this material is the one 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.Containing ester group in the large molecule of fluorine-containing polyester fiber, selected fatty acid ester, has better adhesive force with it.And its flatness is excellent, starching and heat resistance well, can meet the technological requirement of FDY finish.Collecting agent add the convergence and flatness that can improve finish, meanwhile, synergy can be played with phosphate kalium salt antistatic additive, the antistatic effect of fortifying fibre, the cohesive force of fiber be improved, is conducive to the boundling in fiber process.
In described fluorine-containing polyester FDY fiber finish, component E sodium alkyl sulfonate is additive: this material is the one in dodecyl sodium sulfate, pentadecyl sulfonic acid sodium and sodium cetanesulfonate.Sodium alkyl sulfonate add the penetrating power that can improve finish, make finish to be attached on tow in the short period of time uniformly, effectively can reduce the appearance of lousiness, broken end.
In described fluorine-containing polyester FDY fiber finish, component F perfluoroalkyl acrylate is additive: this material is the one in perfluoro butyl ethyl propylene acid esters, perfluoro hexyl ethyl propylene acid esters, perfluorooctylethyl group acrylate, perfluoro butyl ethylmethyl acrylate, perfluoro hexyl ethylmethyl acrylate and perfluorooctylethyl group methacrylate.Its objective is the surface tension in order to suitably reduce finish, being easy to form uniform continuous oil film.Perfluoroalkyl and acrylate have lower surface energy, and appropriate interpolation can lower the surface tension of finish, the wettability of finish and penetrability is greatly increased, is easy to the wetting and spreading at fiber, form uniform oil film.
The main implementation procedure of described fluorine-containing polyester FDY fiber finish: by B component, component C, component D, component E and the mixing of component F normal temperature, stir 20-30 minute, and then mixture is joined in component A, temperature controls as 40-55 DEG C, stir 0.5 ~ 2h, the FDY finish of function admirable can be obtained, during use, be configured to the emulsion of 8 ~ 10% 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 step; Concrete steps are:
Described esterification:
Adopt fluorine-containing terephthalic acid (TPA) and ethylene glycol as raw material, add inhibitor, after being made into uniform sizing material, carry out esterification; Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at normal pressure ~ 0.4MPa, and temperature is at 230 ~ 250 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal;
Described fluorine-containing terephthalic acid (TPA) is tetrafluoro terephthalic acid (TPA) or 2,5-difluoro terephthalic acid (TPA);
Described inhibitor is the one in magnesia, silica, calcium oxide, zinc oxide and manganese oxide; There is fluorine atom in the phenyl ring due to dicarboxylic acids used, the electronegativity of fluorine atom is large, in the conjugation of esterification stage fluorine atom, the acidity of dicarboxylic acids is strengthened, cause the activity of carboxyl in dicarboxylic acids to increase simultaneously, reaction speed is accelerated, and reaction speed increase easily makes side reaction produce, these side reaction products have larger impact to follow-up polycondensation reaction, particularly generate the end-cap product of alkene and aldehyde, constrain the increase of molecular weight of product; From experimental result, if do not add inhibitor, the molecular weight of polyesters of synthesis is on the low side, can not meet the demand of spinning and film forming; The speed added for controlling the esterification stage of inhibitor, decreases side reaction, improves the molecular weight of product, makes fluorine polyester meet spinning requirement.
Usually, it is the hydrogen ion that ionized out by the dicarboxylic acids used catalyst as esterification in polyester esterification process, carry out self-catalyzed reaction, by regulating the temperature of esterification, pressure and the micromolecular speed ejecting its esterification of control, but the prerequisite of carrying out esterification under certain reaction temperature and pressure, just will can carry out esterification.When temperature is too low or pressure is inadequate, esterification can not carry out or speed extremely slow, thus affect follow-up technique.If the Small molecular in esterification is failed timely discharge and is easily caused unnecessary side reaction.In the building-up process of fluorine polyester, due to the conjugation of fluorine, at esterification stage fluorine atom, the acidity of dicarboxylic acids is strengthened, cause the activity of carboxyl in dicarboxylic acids to increase, reaction speed is accelerated, and side reaction increases simultaneously, be difficult to control, and then affect the growth of molecular weight of product, therefore add inhibitor, namely by selecting metal oxide used to regulate.Described metal oxide can dissociate by the following two kinds mode:
Here M is metal ion, if the electronegativity of M is quite large, has stronger attraction, O-H key so just can be made to weaken to the duplet of oxonium ion, is conducive to reacting dissociation; On the contrary, if the electronegativity of M is little, so just alkali center will be generated.M-O-H is similar with amphoteric compound, when there being alkaline matter to exist, reacting and the mode by acid dissociation being carried out; And when acidic materials exist, then undertaken by the mode of alkali formula ionization.The M-O of back reaction from acid dissociation mode and alkali formula ionization mode
-and M
+visible, M
+as acid centre, its intensity only has direct relation with the electronegativity of metal ion, and M-O
-in O ion then 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 metal ion electronegativity is less, and negative charge density is larger.So, acidity and the alkalescence of metal oxide have 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 then 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, in esterification products, add catalyst and stabilizing agent, under the condition of negative pressure, start polycondensation reaction, this staged pressure is steadily evacuated to below absolute pressure 1KPa by normal pressure, temperature controls at 250 ~ 270 DEG C, and the reaction time is 40 ~ 60 minutes;
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 270 ~ 285 DEG C, 1 ~ 2 hour reaction time.Polycondensation reaction to be as the criterion judgement reaction end with reactor stirring motor power or in-line viscometer reading.
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 the one 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 the one 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 by polymerization or obtained through screw rod melting by fluorine polyester slice.
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.
In the esterification stage of the present invention, reaction end reaches theoretical value more than 90% by the water quantity of distillate produced actual in esterification to be grasped.Theoretical value is the quantity of distillate by gained water during chemical equation complete reaction.Because esterification is originally as reversible reaction, moreover raw material has residual in conveyance conduit, and along with the carrying out reacted, the viscosity of system increases, and the shipwreck that esterification can be caused 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 the determination of setting numerical value can by obtaining the analysis of 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, improve 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, have huge prospect.
Beneficial effect:
1, gained novel fluorine polyester FDY fiber contain fluorine atoms; due to the strong electronegativity of fluorine; high C ~ F bond energy and make final obtained fluorine polyester FDY fiber have well heat-resisting, ageing-resistant to the shielding protection effect of carbochain, 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, extend range of application.
2, the smooth softness of gained novel fluorine polyester FDY fiber feel, is applicable to weave silk-like fabric.
3, the novel fluorine polyester FDY fiber of gained introduces fluorine atom by adopting, thus has hydrophobic antifouling characteristic.
4, the novel fluorine polyester FDY fiber of gained is by adopting modification by copolymerization, fundamentally solves the problems such as ageing, the durability of hydrophobic antifouling polyester and ABRASION RESISTANCE.
Detailed description of the invention
Below in conjunction with detailed description of the invention, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
A kind of fluorine polyester FDY fiber is measured, extrudes, cools, oils, stretches and reel obtained by fluorine polyester fondant; Described fluorine polyester refers to the polyethylene terephthalate that benzene ring hydrogen replaced by fluorine, and its general structure is
Wherein n=80 ~ 200.
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 preparation method for fluorine polyester, is divided into esterification and polycondensation reaction two step.Concrete steps are:
Described esterification:
Adopt mol ratio be the ethylene glycol of 1.2:1 and tetrafluoro terephthalic acid (TPA) as raw material, add the zinc oxide of 0.01% of tetrafluoro terephthalic acid (TPA) weight simultaneously, after being made into uniform sizing material, carry out esterification; Esterification is in nitrogen atmosphere, and Stress control is at 0.4MPa, and temperature controls at 250 DEG C, and esterification water quantity of distillate reaches 90% of theoretical value for esterification terminal.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the stabilizing agent triphenyl phosphate of the catalytic antimony trioxide of 0.01% of tetrafluoro terephthalic acid (TPA) weight and 0.01% of tetrafluoro terephthalic acid (TPA) weight is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure by normal pressure and is less than 1KPa, temperature controls at 255 DEG C, and the reaction time is 60 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 270 DEG C, 2 hours reaction time.Polycondensation reaction to be as the criterion judgement reaction end with reactor stirring motor power or in-line viscometer reading.
Prepare the method for FDY fiber:
Directly measured by described fluorine polyester fondant to extrude, cool, oil, to stretch and coiling and molding obtains FDY fiber; The described temperature extruded is 275 DEG C; Described is cooled to lateral blowing cooling, and temperature is 20 DEG C DEG C, 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 poly-isomery ten alcohol polyoxyethylene ether, 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 45 part 9
#in mineral oil, temperature controls at 55 DEG C, stirs 1h, can obtain the FDY finish of function admirable, and adding water when finish uses 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 DEG C; The speed of described winding is 3950m/min; Final obtained fluorine polyester FDY fiber, fracture strength 3cN/dex; Elongation at break is 45%.
Embodiment 2
A preparation method for fluorine polyester, is divided into esterification and polycondensation reaction two step.Concrete steps are:
Described esterification:
Adopt mol ratio be the ethylene glycol of 1.4:1 and 2,5-difluoro terephthalic acid (TPA) as raw material, add the silica of 0.04% of 2,5-difluoro terephthalic acid (TPA) weight simultaneously, after being made into uniform sizing material, carry out esterification; Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at 0.3MPa, and temperature controls at 245 DEG C, and esterification water quantity of distillate reaches 90% of theoretical value for esterification terminal.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, 2 are added in esterification products, 5-difluoro terephthalic acid (TPA) weight 0.02% catalyst glycol antimony and 2,5-difluoro terephthalic acid (TPA) weight 0.02% stabilizing agent trimethyl phosphate, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure by normal pressure and is less than 800Pa, and temperature controls at 250 DEG C, and the reaction time is 50 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 80Pa, and reaction temperature controls at 275 DEG C, 2 hours reaction time.Polycondensation reaction to be as the criterion judgement reaction end with reactor stirring motor power or in-line viscometer reading.
The preparation method of preparation FDY:
Be directly extruded by described fluorine polyester fondant, cool, oil, the first hot-rolling, the second hot-rolling, coiling and molding obtain FDY fiber; The described temperature extruded is 290 DEG C; Described is cooled to lateral blowing cooling, and temperature is 25 DEG C, 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 sulfonic acid sodium, 5 parts of perfluoro hexyl ethyl propylene acid esters normal temperature mixing, stir 30min.Said mixture is joined 40 part 10
#in mineral oil, temperature controls at 40 DEG C, 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 DEG C; The speed of described winding is 5950m/min; Final obtained fluorine polyester FDY fiber, fracture strength 5cN/dex; Elongation at break is 18%.
Embodiment 3
A preparation method for fluorine polyester, is divided into esterification and polycondensation reaction two step.Concrete steps are:
Described esterification:
Adopt mol ratio be the ethylene glycol of 1.6:1 and tetrafluoro terephthalic acid (TPA) as raw material, add the calcium oxide of 0.02% of tetrafluoro terephthalic acid (TPA) weight simultaneously, after being made into uniform sizing material, carry out esterification; Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at 0.2MPa, and temperature controls at 240 DEG C, and esterification water quantity of distillate reaches 90% of theoretical value for esterification terminal.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the stabilizing agent Trimethyl phosphite of the catalyst acetic acid antimony of 0.03% of tetrafluoro terephthalic acid (TPA) weight and 0.03% of tetrafluoro terephthalic acid (TPA) weight is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure by normal pressure and is less than 600Pa, temperature controls at 260 DEG C, and the reaction time is 50 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 60Pa, and reaction temperature controls at 280 DEG C, 1.5 hours reaction time.Polycondensation reaction to be as the criterion judgement reaction end with reactor stirring motor power or in-line viscometer reading.
Prepare the method for FDY fiber:
Be directly extruded by described fluorine polyester fondant, cool, oil, the first hot-rolling, the second hot-rolling, coiling and molding obtain FDY fiber; The described temperature extruded is 280 DEG C; Described is cooled to lateral blowing cooling, and temperature is 30 DEG C, 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 perfluorooctylethyl group acrylate normal temperature mixing, stir 20min.Said mixture is joined 50 part 11
#in mineral oil, temperature controls at 55 DEG C, 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 DEG C; The speed of described winding is 4450m/min; Final obtained fluorine polyester FDY fiber, fracture strength 3.5cN/dex; Elongation at break is 40%.
Embodiment 4
A preparation method for fluorine polyester, is divided into esterification and polycondensation reaction two step.Concrete steps are:
Described esterification:
Adopt mol ratio be the ethylene glycol of 1.8:1 and tetrafluoro terephthalic acid (TPA) as raw material, add the manganese oxide of 0.03% of tetrafluoro terephthalic acid (TPA) weight simultaneously, after being made into uniform sizing material, carry out esterification; Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at 0.2MPa, and temperature controls at 235 DEG C, and esterification water quantity of distillate reaches 90% of theoretical value for esterification terminal.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the stabilizing agent trimethyl phosphate of the catalytic antimony trioxide of 0.04% of tetrafluoro terephthalic acid (TPA) weight and 0.04% of tetrafluoro terephthalic acid (TPA) weight is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure by normal pressure and is less than 500Pa, temperature controls at 265 DEG C, and the reaction time is 50 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 50Pa, and reaction temperature controls at 280 DEG C, 1 hour reaction time.Polycondensation reaction to be as the criterion judgement reaction end with reactor stirring motor power or in-line viscometer reading.
Prepare the method for FDY fiber:
Be directly extruded by described fluorine polyester fondant, cool, oil, the first hot-rolling, the second hot-rolling, coiling and molding obtain FDY fiber; The described temperature extruded is 280 DEG C; Described is cooled to lateral blowing cooling, and temperature is 20 DEG C, 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 sulfonic acid sodium, 1 part of perfluoro butyl ethylmethyl acrylate normal temperature mixing, stir 30min.Said mixture is joined 60 part 12
#in mineral oil, temperature controls at 50 DEG C, 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 DEG C; The speed of described winding is 4950m/min; Final obtained fluorine polyester FDY fiber, fracture strength 4cN/dex; Elongation at break is 30%.
Embodiment 5
A preparation method for fluorine polyester, is divided into esterification and polycondensation reaction two step.Concrete steps are:
Described esterification:
Adopt mol ratio be the ethylene glycol of 2.0:1 and 2,5-difluoro terephthalic acid (TPA) as raw material, add the magnesia of 0.01% of 2,5-difluoro terephthalic acid (TPA) weight simultaneously, after being made into uniform sizing material, carry out esterification; Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at normal pressure, and temperature controls at 230 DEG C, and esterification water quantity of distillate reaches 90% of theoretical value for esterification terminal.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, 2 are added in esterification products, 5-difluoro terephthalic acid (TPA) weight 0.05% the catalytic antimony trioxide and 2,5-difluoro terephthalic acid (TPA) weight 0.05% stabilizing agent triphenyl phosphate, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure by normal pressure and is less than 400Pa, and temperature controls at 270 DEG C, and the reaction time is 40 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 50Pa, and reaction temperature controls at 285 DEG C, 1 hour reaction time.Polycondensation reaction to be as the criterion judgement reaction end with reactor stirring motor power or in-line viscometer reading.
Prepare the method for FDY fiber:
Be directly extruded by described fluorine polyester fondant, cool, oil, the first hot-rolling, the second hot-rolling, coiling and molding obtain FDY fiber; The described temperature extruded is 290 DEG C; Described is cooled to lateral blowing cooling, and temperature is 30 DEG C, 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 sulfonic acid sodium, 3 parts of perfluoro hexyl ethylmethyl acrylate normal temperature mixing, stir 30min.By said mixture and join 45 part 14
#in mineral oil, temperature controls at 55 DEG C, 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 DEG C; The speed of described winding is 5450m/min; Final obtained fluorine polyester FDY fiber, fracture strength 5cN/dex; Elongation at break is 18%.
Embodiment 6
A preparation method for fluorine polyester, is divided into esterification and polycondensation reaction two step.Concrete steps are:
Described esterification:
Adopt mol ratio be the ethylene glycol of 1.2:1 and tetrafluoro terephthalic acid (TPA) as raw material, add the magnesia of 0.01% of tetrafluoro terephthalic acid (TPA) weight simultaneously, after being made into uniform sizing material, carry out esterification; Esterification is in nitrogen atmosphere, and Stress control is at 0.4MPa, and temperature is at 250 DEG C, and esterification water quantity of distillate reaches 90% of theoretical value for esterification terminal.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the stabilizing agent triphenyl phosphate of the catalytic antimony trioxide of 0.01% of tetrafluoro terephthalic acid (TPA) weight and 0.01% of tetrafluoro terephthalic acid (TPA) weight is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure by normal pressure and is less than 1KPa, temperature controls at 255 DEG C, and the reaction time is 60 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 270 DEG C, 2 hours reaction time.Polycondensation reaction to be as the criterion judgement reaction end with reactor stirring motor power or in-line viscometer reading.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine polyester slice.
Prepare the method for FDY fiber:
Be melt extruded through screw rod by described fluorine polyester slice, cool, oil, the first hot-rolling, the second hot-rolling, coiling and molding obtain FDY fiber; The described temperature extruded is 275 DEG C; Described is cooled to ring quenching, and temperature is 20 DEG C DEG C, 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 perfluorooctylethyl group methacrylate normal temperature mixing, stir 20min.Said mixture is joined 40 part 15
#in mineral oil, temperature controls at 40 DEG C, 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 DEG C; The speed of described winding is 3950m/min; Final obtained fluorine polyester FDY fiber, fracture strength 3cN/dex; Elongation at break is 45%.
Embodiment 7
A preparation method for fluorine polyester, is divided into esterification and polycondensation reaction two step.Concrete steps are:
Described esterification:
Adopt mol ratio be the ethylene glycol of 1.4:1 and 2,5-difluoro terephthalic acid (TPA) as raw material, add the silica of 0.02% of 2,5-difluoro terephthalic acid (TPA) weight simultaneously, after being made into uniform sizing material, carry out esterification; Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at 0.3MPa, and temperature is at 245 DEG C, and esterification water quantity of distillate reaches 90% of theoretical value for esterification terminal.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, 2 are added in esterification products, 5-difluoro terephthalic acid (TPA) weight 0.02% catalyst glycol antimony and 2,5-difluoro terephthalic acid (TPA) weight 0.02% stabilizing agent trimethyl phosphate, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure by normal pressure and is less than 800Pa, and temperature controls at 250 DEG C, and the reaction time is 50 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 80Pa, and reaction temperature controls at 275 DEG C, 1.5 hours reaction time.Polycondensation reaction to be as the criterion judgement reaction end with reactor stirring motor power or in-line viscometer reading.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine polyester slice.
Prepare the method for FDY fiber:
Be melt extruded through screw rod by described fluorine polyester slice, cool, oil, the first hot-rolling, the second hot-rolling, coiling and molding obtain FDY fiber; The described temperature extruded is 290 DEG C; Described is cooled to ring quenching, and temperature is 25 DEG C, 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 ethylmethyl acrylate normal temperature mixing, stir 20min.Said mixture is joined 44 part 16
#in mineral oil, temperature controls at 45 DEG C, 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 DEG C; The speed of described winding is 5950m/min; Final obtained fluorine polyester FDY fiber, fracture strength 5cN/dex; Elongation at break is 18%.
Embodiment 8
A preparation method for fluorine polyester, is divided into esterification and polycondensation reaction two step.Concrete steps are:
Described esterification:
Adopt mol ratio be the ethylene glycol of 1.6:1 and tetrafluoro terephthalic acid (TPA) as raw material, add the calcium oxide of 0.05% of tetrafluoro terephthalic acid (TPA) weight simultaneously, after being made into uniform sizing material, carry out esterification; Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at 0.2MPa, and temperature controls at 240 DEG C, and esterification water quantity of distillate reaches 90% of theoretical value for esterification terminal.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the stabilizing agent Trimethyl phosphite of the catalyst acetic acid antimony of 0.03% of tetrafluoro terephthalic acid (TPA) weight and 0.03% of tetrafluoro terephthalic acid (TPA) weight is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure by normal pressure and is less than 600Pa, temperature controls at 260 DEG C, and the reaction time is 50 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 60Pa, and reaction temperature controls at 275 DEG C, 1.5 hours reaction time.Polycondensation reaction to be as the criterion judgement reaction end with reactor stirring motor power or in-line viscometer reading.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine polyester slice.
Prepare the method for FDY fiber:
Be melt extruded through screw rod by described fluorine polyester slice, cool, oil, the first hot-rolling, the second hot-rolling, coiling and molding obtain FDY fiber; The described temperature extruded is 285 DEG C; Described is cooled to ring quenching, and temperature is 30 DEG C, 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 55 part 17
#in mineral oil, temperature controls at 50 DEG C, 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 DEG C; The speed of described winding is 4450m/min; Final obtained fluorine polyester FDY fiber, fracture strength 3.5cN/dex; Elongation at break is 40%.
Embodiment 9
A preparation method for fluorine polyester, is divided into esterification and polycondensation reaction two step.Concrete steps are:
Described esterification:
Adopt mol ratio be the ethylene glycol of 1.8:1 and tetrafluoro terephthalic acid (TPA) as raw material, add the zinc oxide of 0.03% of tetrafluoro terephthalic acid (TPA) weight simultaneously, after being made into uniform sizing material, carry out esterification; Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at 0.2MPa, and temperature controls at 235 DEG C, and esterification water quantity of distillate reaches 90% of theoretical value for esterification terminal.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, the stabilizing agent trimethyl phosphate of the catalytic antimony trioxide of 0.04% of tetrafluoro terephthalic acid (TPA) weight and 0.04% of tetrafluoro terephthalic acid (TPA) weight is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure by normal pressure and is less than 500Pa, temperature controls at 265 DEG C, and the reaction time is 50 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 50Pa, and reaction temperature controls at 280 DEG C, 1 hour reaction time.Polycondensation reaction to be as the criterion judgement reaction end with reactor stirring motor power or in-line viscometer reading.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine polyester slice.
Prepare the method for FDY fiber:
Be melt extruded through screw rod by described fluorine polyester slice, cool, oil, the first hot-rolling, the second hot-rolling, coiling and molding obtain FDY fiber; The described temperature extruded is 280 DEG C; Described is cooled to ring quenching, and temperature is 20 DEG C, 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 poly-isomery ten alcohol polyoxyethylene ether, 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 45 part 9
#in mineral oil, temperature controls at 55 DEG C, 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 DEG C; The speed of described winding is 4950m/min; Final obtained fluorine polyester FDY fiber, fracture strength 4cN/dex; Elongation at break is 30%.
Embodiment 10
A preparation method for fluorine polyester, is divided into esterification and polycondensation reaction two step.Concrete steps are:
Described esterification:
Adopt mol ratio be the ethylene glycol of 2.0:1 and 2,5-difluoro terephthalic acid (TPA) as raw material, add the manganese oxide of 0.04% of 2,5-difluoro terephthalic acid (TPA) weight simultaneously, after being made into uniform sizing material, carry out esterification; Esterification is pressurizeed in nitrogen atmosphere, and Stress control is at normal pressure, and temperature controls at 230 DEG C, and esterification water quantity of distillate reaches 90% of theoretical value for esterification terminal.
Described polycondensation reaction:
Comprise polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:
The described polycondensation reaction low vacuum stage, 2 are added in esterification products, 5-difluoro terephthalic acid (TPA) weight 0.05% the catalytic antimony trioxide and 2,5-difluoro terephthalic acid (TPA) weight 0.05% stabilizing agent triphenyl phosphate, polycondensation reaction is started under the condition of negative pressure, this staged pressure is steadily evacuated to absolute pressure by normal pressure and is less than 400Pa, and temperature controls at 270 DEG C, and the reaction time is 40 minutes.
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 50Pa, and reaction temperature controls at 285 DEG C, 1 hour reaction time.Polycondensation reaction to be as the criterion judgement reaction end with reactor stirring motor power or in-line viscometer reading.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine polyester slice.
Prepare the method for FDY fiber:
Be melt extruded through screw rod by described fluorine polyester slice, cool, oil, the first hot-rolling, the second hot-rolling, coiling and molding obtain FDY fiber; The described temperature extruded is 290 DEG C; Described is cooled to ring quenching, and temperature is 20 DEG C, 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 sulfonic acid sodium, 5 parts of perfluoro hexyl ethyl propylene acid esters normal temperature mixing, stir 30min.Said mixture is joined 40 part 10
#in mineral oil, temperature controls at 40 DEG C, 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 DEG C; The speed of described winding is 5450m/min; Final obtained fluorine polyester FDY fiber, fracture strength 5cN/dex; Elongation at break is 18%.
Claims (8)
1. a preparation method for fluorine polyester FDY fiber, is characterized in that: described fluorine polyester FDY fiber is through measuring, extruding, cool, oil, stretch and reel obtained by fluorine polyester fondant; Described fluorine polyester refers to the polyethylene terephthalate that benzene ring hydrogen replaced by fluorine, and its general structure is
Or
Wherein n=80 ~ 200;
Fracture strength 3 ~ the 5cN/dex of described fluorine polyester FDY fiber; Elongation at break is 18 ~ 45%;
Described by fluorine polyester fondant through measuring, extruding, cool, oil, stretch and winding steps, obtained fluorine polyester FDY fiber,
Wherein:
The described temperature extruded is 275 ~ 290 DEG C;
The wind-warm syndrome of described cooling is 20 ~ 30 DEG C;
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 DEG C;
The speed of described winding 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:
By B component, component C, component D, component E and the mixing of component F normal temperature, stir 20-30 minute, and then mixture is joined in component A, temperature controls as 40-55 DEG C, stir 0.5 ~ 2h, can obtain fluorine-containing polyester FDY fiber finish, adding water when finish uses 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 step; 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 Stress control is at normal pressure ~ 0.4MPa, and temperature is at 230 ~ 250 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for esterification terminal;
Described inhibitor is the one 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, in described esterification products, add catalyst and stabilizing agent, under the condition of negative pressure, start polycondensation reaction, this staged pressure is steadily evacuated to below absolute pressure 1KPa by normal pressure, temperature controls at 250 ~ 270 DEG C, and the reaction time is 40 ~ 60 minutes;
Described polycondensation reaction high vacuum stage of Fig, after the described polycondensation reaction low vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and reaction temperature controls at 270 ~ 285 DEG C, 1 ~ 2 hour reaction time.
2. the preparation method of a kind of fluorine polyester FDY fiber according to claim 1, is characterized in that, described is cooled to lateral blowing or ring quenching, and temperature is 20 DEG C ~ 30 DEG C, and humidity is 65% ± 5%, and wind speed is 0.4 ~ 0.8m/s.
3. the preparation method of a kind of fluorine polyester FDY fiber according to claim 1, is characterized in that, the mol ratio of described ethylene glycol and fluorine-containing terephthalic acid (TPA) is 1.2 ~ 2.0:1.
4. the preparation method of a kind of fluorine polyester FDY fiber according to claim 1, it is characterized in that, described catalyst is selected from the one in antimonous oxide, antimony glycol and antimony acetate, and catalyst amount is 0.01% ~ 0.05% of described fluorine-containing terephthalic acid (TPA) weight.
5. the preparation method of a kind of fluorine polyester FDY fiber according to claim 1, it is characterized in that, described stabilizing agent is selected from the one 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.
6. the preparation method of a kind of fluorine polyester FDY fiber according to claim 1, is characterized in that, the addition of described inhibitor 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 1, is characterized in that, described fluorine polyester fondant is directly obtained by polymerization or obtained through screw rod melting by fluorine polyester slice.
8. the preparation method of a kind of fluorine polyester FDY fiber according to claim 1, is characterized in that, described mineral oil is 9
#~ 17
#mineral oil in one; Described polyoxyethylene ether is the one in isomery ten alcohol polyoxyethylene ether, 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 the one in 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, isomerous tridecanol polyoxyethylene ether phosphate kalium salt and ten tetracosanol phosphate kalium salts; Described cithrol is the one 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 the one in dodecyl sodium sulfate, pentadecyl sulfonic acid sodium and sodium cetanesulfonate; Described perfluoroalkyl acrylate is the one in perfluoro butyl ethyl propylene acid esters, perfluoro hexyl ethyl propylene acid esters, perfluorooctylethyl group acrylate, perfluoro butyl ethylmethyl acrylate, perfluoro hexyl ethylmethyl acrylate and perfluorooctylethyl group methacrylate.
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| CN1171408A (en) * | 1997-06-11 | 1998-01-28 | 中国科学院上海有机化学研究所 | Process for synthesizing fluoric aromatic polyester |
| EP1600797A1 (en) * | 2004-05-28 | 2005-11-30 | Nippon Shokubai Co., Ltd. | Transparent resin material |
| CN101613465A (en) * | 2009-07-21 | 2009-12-30 | 武汉理工大学 | A kind of Weather-proof self-cleaning transparent material and preparation method thereof |
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| CN1171408A (en) * | 1997-06-11 | 1998-01-28 | 中国科学院上海有机化学研究所 | Process for synthesizing fluoric aromatic polyester |
| EP1600797A1 (en) * | 2004-05-28 | 2005-11-30 | Nippon Shokubai Co., Ltd. | Transparent resin material |
| CN101613465A (en) * | 2009-07-21 | 2009-12-30 | 武汉理工大学 | A kind of Weather-proof self-cleaning transparent material and preparation method thereof |
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