CN103469339B - A kind of preparation method of fluorine polyester DTY fiber - Google Patents
A kind of preparation method of fluorine polyester DTY fiber Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of fluorine polyester DTY fiber, comprise the preparation of the preparation of fluorine polyester fondant, fluorine polyester POY fiber and fluorine polyester DTY fiber; Fluorine-containing terephthalic acid (TPA) and ethylene glycol are added inhibitor prepare fluorine polyester fondant as raw material, adopt POY-DTY technique, directly extrude fluorine polyester fondant or make section to melt extrude through screw rod, cool, oil and reel obtained fluorine polyester POY fiber, gained fluorine polyester POY fiber is through heating, false twisting, obtained fluorine polyester DTY fiber of shaping, oil and reel.Gained novel fluorine polyester DTY fiber fracture strength of the present invention is 3.2 ~ 4.0cN/dex; Elongation at break is 20 ~ 40%.Due to the introducing of fluorine atom, improve super-hydrophobic, hydrophobic and oil repellent, the antifouling aspect performance of polyester DTY fiber, in the Work Clothes manufacture of waterproof garment, 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 DTY fiber, particularly relate to the preparation method of the fluorine polyester DTY 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.Low-stretch yarn DTY, refer to carry out continuously on elasticizer device or stretch simultaneously, finished silk after twister deformation processing, also referred to as low elastic polyester filament, be take long filament as raw material, utilize fibrous thermoplastic, through the novel yarn that a kind of high crimp be out of shape and HEAT SETTING process obtains is fluffy.DTY is used on weft machine, and in the daily necessitiess such as fashionable dress, decoration, household articles, have certain application, be the substitute beyond cotton.
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, ethylene-tetrafluoroethylene 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.
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 DTY fiber, fluorine polyester DTY fiber particularly providing a kind of benzene ring hydrogen to replaced by fluorine and preparation method thereof.A kind of fluorine polyester DTY 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 terephthalic acid (TPA) and the ethylene glycol of contain fluorine atoms on phenyl ring, through the novel fluorine polyester that over-churning and polycondensation obtain, 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.
The invention provides following technical scheme:
A kind of fluorine polyester DTY fiber adopts POY-DTY technique, directly extrudes fluorine polyester fondant or make section and to melt extrude through screw rod, cool, oil and reel obtained fluorine polyester POY fiber; Gained fluorine polyester POY fiber is through heating, false twisting, obtained fluorine polyester DTY fiber of shaping, oil and reel.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.
A kind of fluorine polyester DTY fiber as above, the fracture strength of described fluorine polyester DTY fiber is 3.2 ~ 4.0cN/dex; Elongation at break is 20 ~ 40%.
The preparation method of described fluorine polyester DTY fiber, comprises the preparation of the preparation of fluorine polyester fondant, fluorine polyester POY fiber and fluorine polyester DTY fiber:
The preparation method of described fluorine polyester DTY fiber, is added inhibitor by fluorine-containing terephthalic acid (TPA) and ethylene glycol prepare fluorine polyester fondant as raw material; Adopt POY-DTY technique, directly extrude fluorine polyester fondant or make section and to melt extrude through screw rod, cool, oil and reel obtained fluorine polyester POY fiber; Gained fluorine polyester POY fiber is through heating, false twisting, obtained fluorine polyester DTY fiber of shaping, oil and reel;
The described temperature extruded is 285 ~ 295 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 speed of described winding is 2700 ~ 3200m/min;
Described is cooled to lateral blowing or ring quenching, and temperature is 20 DEG C ~ 30 DEG C, and relative humidity is 65% ± 5%, and wind speed is 0.4 ~ 0.8m/s;
The described finish oiled is fluorine-containing polyester POY Finish for fiber, its component by weight:
Atactic polyether, 50 ~ 60 parts;
Cithrol, 20 ~ 32 parts;
Phosphate kalium salt, 10 ~ 15 parts;
Perfluoroalkyl acrylate, 2 ~ 5 parts;
The preparation method of finish:
By atactic polyether, be heated to 40 ~ 60 DEG C, cithrol, phosphate kalium salt and perfluoroalkyl acrylate are uniformly mixed, then join in atactic polyether, stir 1 ~ 2 hour, namely obtain fluorine-containing polyester POY Finish for fiber, adding water when finish uses is made into the emulsion that solid content is 8 ~ 10wt%.
The temperature of described heating is 195 ~ 200 DEG C;
The control drafting multiple of described false twisting is 1.5 ~ 1.8 times;
The temperature of described sizing is 135 ~ 145 DEG C;
The effect components of described fluorine-containing polyester POY Finish for fiber is, by weight, and component A: atactic polyether 50 ~ 60 parts; B component: cithrol, 20 ~ 32 parts; Component C: phosphate kalium salt, 10 ~ 15 parts; Component D: perfluoroalkyl acrylate, 2 ~ 5 parts.
In described fluorine-containing polyester POY Finish for fiber, component A atactic polyether is smooth agent: this material is the one in propylene glycol atactic polyether, butanols atactic polyether, laurate atactic polyether, lauryl alcohol atactic polyether and isomerous tridecanol atactic polyether.The good heat resistance of atactic polyether, be fuming few, coking is few, and flowing temperature is low, good stability, and coefficient of friction is low, and anti-shear ability is strong, and viscosity coefficient is low, can form the highly stable lubricant film with large absorption affinity and bearing capacity in polyester fibre surface.
In described fluorine-containing polyester POY Finish for fiber, B component cithrol is emulsifying agent: this material is the one in polyethylene glycol lauric acid monoester, polyethylene glycol laurate dibasic acid esters, polyethylene glycol oleic acid monoester and polyethylene glycol Glycol Oleic Acid Ester.Cithrol become oil film to have the performances such as good surface tension, interfacial tension, penetrability, dispersiveness and emulsibility, its composition finish can reduce between silk and silk, between silk and metal quiet/kinetic force of friction, for fluorine-containing polyester fiber provides certain antistatic behaviour, improve convergence.
In described fluorine-containing polyester POY Finish for fiber, 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.In spinning process, easily produce a large amount of electrostatic, the generation being reduced static content by the flatness of fiber surface is inadequate, also needs the antistatic additive adding superior performance.Phosphate kalium salt is a kind of good antistatic additive, it is a kind of anion surfactant, is made up of hydrophobic group and hydrophilic radical, and hydrophobic grouping energy and polyester fibre surface combine, hydrophilic radical phosphate group upwards, can form the continuous moisture film of " interfacial agent-water ".Can effectively fall low-fiber coefficient of friction, increase the dielectric constant between friction piece, prevent electrostatic from occurring.
In described fluorine-containing polyester POY Finish for fiber, component D 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 effect is the surface tension suitably reducing finish, makes it be easy to form uniform continuous oil film.Fluorinated acrylate has 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 POY Finish for fiber: by weight, get 50 ~ 60 parts of atactic polyethers, be heated to 40 ~ 60 DEG C, 20 ~ 32 parts of cithrols, 10 ~ 15 parts of phosphate kalium salts and 2 ~ 5 parts of perfluoroalkyl acrylates are uniformly mixed, then join in atactic polyether, stir 1 ~ 2 hour, namely obtain the fluorine-containing polyester fiber POY finish of function admirable.
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 DTY 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 DTY 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 DTY 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 DTY 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.
The filament number of the novel fluorine polyester POY fiber of gained of the present invention is 0.5-3.0dtex; Fracture strength is 1.6 ~ 1.9cN/dtex; Elongation at break is 110 ~ 150%.Due to the introducing of fluorine atom, 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 DTY fiber contain fluorine atoms; due to the strong electronegativity of fluorine; high C-F bond energy and make final obtained copolyesters DTY 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 novel fluorine polyester DTY fiber of gained introduces fluorine atom by adopting, thus has hydrophobic antifouling characteristic.
3, the novel fluorine polyester DTY 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 DTY fiber adopts POY-DTY technique, directly extrudes fluorine polyester fondant or make section and to melt extrude through screw rod, cool, oil and reel obtained fluorine polyester POY fiber; Gained fluorine polyester POY fiber is through heating, false twisting, obtained fluorine polyester DTY fiber of shaping, oil and reel.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.
A kind of fluorine polyester DTY fiber as above, described fluorine polyester DTY fiber fracture strength is 3.2 ~ 4.0cN/dex; Elongation at break is 20 ~ 40%.
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 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 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 POY fiber:
Directly extrude, cool, oil and reel obtained by described fluorine polyester fondant; Wherein, the temperature extruded described in is 285 DEG C; Described is cooled to lateral blowing, and temperature is 30 DEG C, and relative humidity is 60%, and wind speed is 0.4m/s; The emulsion of the described fluorine-containing polyester POY Finish for fiber adopted containing 8wt% that oils; The preparation of fluorine-containing polyester POY Finish for fiber: its component by weight, get 60 parts of propylene glycol atactic polyethers, be heated to 60 DEG C, 20 parts of polyethylene glycol lauric acid monoesters, 15 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluoro butyl ethyl propylene acid esters are uniformly mixed, then join in propylene glycol atactic polyether, stir 1 hour, namely obtain fluorine-containing polyester POY Finish for fiber; The described oil applying rate oiled is 0.42%; The speed of described winding is 2700m/min; Obtained fluorine polyester POY fiber, filament number is 2.0dtex; Fracture strength is 1.6cN/dtex; Elongation at break is 150%.
Prepare the method for DTY fiber:
Through heating, false twisting, obtained fluorine polyester DTY fiber of shaping, oil and reel by described fluorine polyester POY fiber; Wherein, the temperature of described heating is 195 DEG C; The control drafting multiple of described false twisting is 1.5 times; The temperature of described sizing is 135 DEG C; Final obtained fluorine polyester DTY fiber, fracture strength is 3.2cN/dex, and elongation at break is 40%.
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 0.02% 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 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 described fluorine polyester POY fiber:
Directly extrude, cool, oil and reel obtained by described fluorine polyester fondant; Wherein, the temperature extruded described in is 295 DEG C; Described is cooled to lateral blowing, and temperature is 20 DEG C, and relative humidity is 70%, and wind speed is 0.8m/s; The emulsion of the described fluorine-containing polyester POY Finish for fiber adopted containing 9wt% that oils; The preparation of fluorine-containing polyester POY Finish for fiber: its component by weight, get 50 parts of butanols atactic polyethers, be heated to 40 DEG C, 32 parts of polyethylene glycol laurate dibasic acid esters, 15 parts of isomerous tridecanol polyoxyethylene ether phosphate kalium salts and 3 parts of perfluoro hexyl ethyl propylene acid esters are uniformly mixed, then join in butanols atactic polyether, stir 2 hours, namely obtain fluorine-containing polyester POY Finish for fiber; The described oil applying rate oiled is 1.5%; The speed of described winding is 2800m/min; Obtained fluorine polyester POY fiber, filament number is 2.0dtex; Fracture strength is 1.8cN/dtex; Elongation at break is 140%.
Prepare the method for DTY fiber:
Through heating, false twisting, obtained fluorine polyester DTY fiber of shaping, oil and reel by described fluorine polyester POY fiber; Wherein, the temperature of described heating is 200 DEG C; The control drafting multiple of described false twisting is 1.8 times; The temperature of described sizing is 145 DEG C; Final obtained fluorine polyester DTY fiber, fracture strength is 4.0cN/dex, and elongation at break is 20%.
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 0.03% 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 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.
The preparation method of described fluorine polyester POY fiber:
Directly extrude, cool, oil and reel obtained by described fluorine polyester fondant; Wherein, the temperature extruded described in is 290 DEG C; Described is cooled to lateral blowing, and temperature is 25 DEG C, and relative humidity is 65%, and wind speed is 0.6m/s; The emulsion of the described fluorine-containing polyester POY Finish for fiber adopted containing 10wt% that oils; The preparation of fluorine-containing polyester POY Finish for fiber: its component by weight, get 58 parts of laurate atactic polyethers, be heated to 60 DEG C, 30 parts of polyethylene glycol oleic acid monoesters, 10 part of ten tetracosanol phosphate kalium salt and 2 parts of perfluorooctylethyl group acrylate are uniformly mixed, then join in propylene glycol atactic polyether, stir 1 hour, namely obtain fluorine-containing polyester POY Finish for fiber; The described oil applying rate oiled is 0.96%; The speed of described winding is 2900m/min; Obtained fluorine polyester POY fiber, filament number is 1.5dtex; Fracture strength is 2.0cN/dtex; Elongation at break is 135%.
Prepare the method for DTY fiber:
Through heating, false twisting, obtained fluorine polyester DTY fiber of shaping, oil and reel by described fluorine polyester POY fiber; Wherein, the temperature of described heating is 198 DEG C; The control drafting multiple of described false twisting is 1.6 times; The temperature of described sizing is 140 DEG C; Final obtained fluorine polyester DTY fiber, fracture strength is 3.5cN/dex, and elongation at break is 35%.
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 zinc oxide of 0.04% 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 preparation method of described fluorine polyester POY fiber:
Directly extrude, cool, oil and reel obtained by described fluorine polyester fondant; Wherein, the temperature extruded described in is 285 DEG C; Described is cooled to lateral blowing, and temperature is 30 DEG C, and relative humidity is 60%, and wind speed is 0.4m/s; The emulsion of the described fluorine-containing polyester POY Finish for fiber adopted containing 8wt% that oils; The preparation of fluorine-containing polyester POY Finish for fiber: its component by weight, get 50 parts of lauryl alcohol atactic polyethers, be heated to 50 DEG C, 32 parts of polyethylene glycol Glycol Oleic Acid Ester, 13 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluoro butyl ethylmethyl acrylate are uniformly mixed, then join in propylene glycol atactic polyether, stir 1 hour, namely obtain fluorine-containing polyester POY Finish for fiber; The described oil applying rate oiled is 1.5%; The speed of described winding is 3000m/min; Obtained fluorine polyester POY fiber, filament number is 1.5dtex; Fracture strength is 2.2cN/dtex; Elongation at break is 125%.
Prepare the method for DTY fiber:
Through heating, false twisting, obtained fluorine polyester DTY fiber of shaping, oil and reel by described fluorine polyester POY fiber; Wherein, the temperature of described heating is 198 DEG C; The control drafting multiple of described false twisting is 1.7 times; The temperature of described sizing is 140 DEG C; Final obtained fluorine polyester DTY fiber, fracture strength is 3.8cN/dex, and elongation at break is 25%.
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 manganese oxide of 0.05% 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 preparation method of described fluorine polyester POY fiber:
Directly extrude, cool, oil and reel obtained by described fluorine polyester fondant; Wherein, the temperature extruded described in is 295 DEG C; Described is cooled to lateral blowing, and temperature is 20 DEG C, and relative humidity is 70%, and wind speed is 0.8m/s; The emulsion of the described fluorine-containing polyester POY Finish for fiber adopted containing 8wt% that oils; The preparation of fluorine-containing polyester POY Finish for fiber: its component by weight, get 55 parts of isomerous tridecanol atactic polyethers, be heated to 55 DEG C, 25 parts of polyethylene glycol laurate dibasic acid esters, 15 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluoro hexyl ethylmethyl acrylate are uniformly mixed, then join in propylene glycol atactic polyether, stir 2 hours, namely obtain fluorine-containing polyester POY Finish for fiber; The described oil applying rate oiled is 0.42%; The speed of described winding is 3200m/min; Obtained fluorine polyester POY fiber, filament number is 1.0dtex; Fracture strength is 2.5cN/dtex; Elongation at break is 110%.
Prepare the method for DTY fiber:
Through heating, false twisting, obtained fluorine polyester DTY fiber of shaping, oil and reel by described fluorine polyester POY fiber; Wherein, the temperature of described heating is 200 DEG C; The control drafting multiple of described false twisting is 1.8 times; The temperature of described sizing is 145 DEG C; Final obtained fluorine polyester DTY fiber, fracture strength is 4.0cN/dex, and elongation at break is 20%.
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 0.05% 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-containing polyester slice.
The preparation method of described fluorine polyester POY fiber:
Melt extrude through screw rod, cool, oil and reel obtained by described fluorine polyester slice; Wherein, the temperature extruded described in is 285 DEG C; Described is cooled to ring quenching, and temperature is 30 DEG C, and relative humidity is 60%, and wind speed is 0.4m/s; The emulsion of the described fluorine-containing polyester POY Finish for fiber adopted containing 9wt% that oils; The preparation of fluorine-containing polyester POY Finish for fiber: its component by weight, get 60 parts of propylene glycol atactic polyethers, be heated to 45 DEG C, 20 parts of polyethylene glycol oleic acid monoesters, 15 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluorooctylethyl group methacrylates are uniformly mixed, then join in propylene glycol atactic polyether, stir 1 hour, namely obtain fluorine-containing polyester POY Finish for fiber; The described oil applying rate oiled is 0.42%; The speed of described winding is 2700m/min; Obtained fluorine polyester POY fiber, filament number is 2.0dtex; Fracture strength is 1.6cN/dtex; Elongation at break is 150%.
Prepare the method for DTY fiber:
Through heating, false twisting, obtained fluorine polyester DTY fiber of shaping, oil and reel by described fluorine polyester POY fiber; Wherein, the temperature of described heating is 195 DEG C; The control drafting multiple of described false twisting is 1.5 times; The temperature of described sizing is 135 DEG C; Final obtained fluorine polyester DTY fiber, fracture strength is 3.2cN/dex, and elongation at break is 40%.
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 0.03% 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-containing polyester slice.
The preparation method of described fluorine polyester POY fiber:
Melt extrude through screw rod, cool, oil and reel obtained by described fluorine polyester slice; Wherein, the temperature extruded described in is 295 DEG C; Described be cooled to ring quenching, temperature is 20 DEG C, and relative humidity is 70%, and wind speed is 0.8m/s; The emulsion of the described fluorine-containing polyester POY Finish for fiber adopted containing 9wt% that oils; The preparation of fluorine-containing polyester POY Finish for fiber: its component by weight, get 50 parts of butanols atactic polyethers, be heated to 40 DEG C, 32 parts of polyethylene glycol laurate dibasic acid esters, 15 parts of isomerous tridecanol polyoxyethylene ether phosphate kalium salts and 3 parts of perfluoro hexyl ethyl propylene acid esters are uniformly mixed, then join in butanols atactic polyether, stir 2 hours, namely obtain fluorine-containing polyester POY Finish for fiber; The described oil applying rate oiled is 1.5%; The speed of described winding is 2800m/min; Obtained fluorine polyester POY fiber, filament number is 2.0dtex; Fracture strength is 1.8cN/dtex; Elongation at break is 140%.
Prepare the method for DTY fiber:
Through heating, false twisting, obtained fluorine polyester DTY fiber of shaping, oil and reel by described fluorine polyester POY fiber; Wherein, the temperature of described heating is 200 DEG C; The control drafting multiple of described false twisting is 1.8 times; The temperature of described sizing is 145 DEG C; Final obtained fluorine polyester DTY fiber, fracture strength is 4.0cN/dex, and elongation at break is 20%.
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 0.04% 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-containing polyester slice.
The preparation method of described fluorine polyester POY fiber:
Melt extrude through screw rod, cool, oil and reel obtained by described fluorine polyester slice; Wherein, the temperature extruded described in is 290 DEG C; Described is cooled to ring quenching, and temperature is 25 DEG C, and relative humidity is 65%, and wind speed is 0.6m/s; The emulsion of the described fluorine-containing polyester POY Finish for fiber adopted containing 10wt% that oils; The preparation of fluorine-containing polyester POY Finish for fiber: its component by weight, get 60 parts of propylene glycol atactic polyethers, be heated to 60 DEG C, 20 parts of polyethylene glycol lauric acid monoesters, 15 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluoro butyl ethyl propylene acid esters are uniformly mixed, then join in propylene glycol atactic polyether, stir 1 hour, namely obtain fluorine-containing polyester POY Finish for fiber; The described oil applying rate oiled is 0.96%; The speed of described winding is 2900m/min; Obtained fluorine polyester POY fiber, filament number is 1.5dtex; Fracture strength is 2.0cN/dtex; Elongation at break is 135%.
Prepare the method for DTY fiber:
Through heating, false twisting, obtained fluorine polyester DTY fiber of shaping, oil and reel by described fluorine polyester POY fiber; Wherein, the temperature of described heating is 198 DEG C; The control drafting multiple of described false twisting is 1.6 times; The temperature of described sizing is 140 DEG C; Final obtained fluorine polyester DTY fiber, fracture strength is 3.5cN/dex, and elongation at break is 35%.
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-containing polyester slice.
The preparation method of described fluorine polyester POY fiber:
Melt extrude through screw rod, cool, oil and reel obtained by described fluorine polyester slice; Wherein, the temperature extruded described in is 285 DEG C; Described is cooled to ring quenching, and temperature is 30 DEG C, and relative humidity is 60%, and wind speed is 0.4m/s; The emulsion of the described fluorine-containing polyester POY Finish for fiber adopted containing 10wt% that oils; The preparation of fluorine-containing polyester POY Finish for fiber: its component by weight, get 50 parts of lauryl alcohol atactic polyethers, be heated to 50 DEG C, 32 parts of polyethylene glycol Glycol Oleic Acid Ester, 13 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluoro butyl ethylmethyl acrylate are uniformly mixed, then join in propylene glycol atactic polyether, stir 1 hour, namely obtain fluorine-containing polyester POY Finish for fiber; The described oil applying rate oiled is 1.5%; The speed of described winding is 3000m/min; Obtained fluorine polyester POY fiber, filament number is 1.5dtex; Fracture strength is 2.2cN/dtex; Elongation at break is 125%.
Prepare the method for DTY fiber:
Through heating, false twisting, obtained fluorine polyester DTY fiber of shaping, oil and reel by described fluorine polyester POY fiber; Wherein, the temperature of described heating is 198 DEG C; The control drafting multiple of described false twisting is 1.7 times; The temperature of described sizing is 140 DEG C; Final obtained fluorine polyester DTY fiber, fracture strength is 3.8cN/dex, and elongation at break is 25%.
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 0.01% 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.The discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, namely obtain fluorine-containing polyester slice.
The preparation method of described fluorine polyester POY fiber:
Melt extrude through screw rod, cool, oil and reel obtained by described fluorine polyester slice; Wherein, the temperature extruded described in is 295 DEG C; Described is cooled to ring quenching, and temperature is 30 DEG C, and relative humidity is 60%, and wind speed is 0.4m/s; The emulsion of the described fluorine-containing polyester POY Finish for fiber adopted containing 8wt% that oils; The preparation of fluorine-containing polyester POY Finish for fiber: its component by weight, get 60 parts of propylene glycol atactic polyethers, be heated to 45 DEG C, 20 parts of polyethylene glycol oleic acid monoesters, 15 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluorooctylethyl group methacrylates are uniformly mixed, then join in propylene glycol atactic polyether, stir 1 hour, namely obtain fluorine-containing polyester POY Finish for fiber; The described oil applying rate oiled is 0.42%; The speed of described winding is 3200m/min; Obtained fluorine polyester POY fiber, filament number is 1.0dtex; Fracture strength is 2.5cN/dtex; Elongation at break is 110%.
Prepare the method for DTY fiber:
Through heating, false twisting, obtained fluorine polyester DTY fiber of shaping, oil and reel by described fluorine polyester POY fiber; Wherein, the temperature of described heating is 200 DEG C; The control drafting multiple of described false twisting is 1.8 times; The temperature of described sizing is 145 DEG C; Final obtained fluorine polyester DTY fiber, fracture strength is 4.0cN/dex, and elongation at break is 20%.
Claims (7)
1. a preparation method for fluorine polyester DTY fiber, is characterized in that: described fluorine polyester DTY fiber adopts POY-DTY technique, by fluorine polyester fondant through measuring, extruding, cool, oil and reel obtained fluorine polyester POY fiber; Described fluorine polyester POY fiber is through heating, false twisting, obtained fluorine polyester DTY fiber of shaping, oil and reel; Described fluorine polyester refers to the polyethylene terephthalate that benzene ring hydrogen replaced by fluorine, and its general structure is
Wherein n=80 ~ 200;
The fracture strength of described fluorine polyester DTY fiber is 3.2 ~ 4.0cN/dex; Elongation at break is 20 ~ 40%;
Described fluorine polyester DTY fiber adopts POY-DTY technique, and elder generation through measuring, extruding, cool, oil and winding steps, obtains fluorine polyester POY fiber by fluorine polyester fondant;
The described temperature extruded is 260 ~ 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 speed of described winding is 2700 ~ 3200m/min;
The described finish oiled is fluorine-containing polyester POY Finish for fiber, its component by weight:
Atactic polyether, 50 ~ 60 parts;
Cithrol, 20 ~ 32 parts;
Phosphate kalium salt, 10 ~ 15 parts;
Perfluoroalkyl acrylate, 2 ~ 5 parts;
The preparation method of finish:
By atactic polyether, be heated to 40 ~ 60 DEG C, cithrol, phosphate kalium salt and perfluoroalkyl acrylate are uniformly mixed, then join in atactic polyether, stir 1 ~ 2 hour, namely obtain fluorine-containing polyester POY Finish for fiber, adding water when finish uses is made into the emulsion that solid content is 8 ~ 10wt%;
Then, described fluorine polyester POY fiber through heating, false twisting, shape, oil and winding steps, obtained fluorine polyester DTY fiber;
The temperature of described heating is 195 ~ 200 DEG C;
The control drafting multiple of described false twisting is 1.5 ~ 1.8 times;
The temperature of described sizing is 135 ~ 145 DEG C;
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, the addition of described inhibitor is 0.01% ~ 0.05% of described fluorine-containing terephthalic acid (TPA) weight; 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 DTY 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 relative humidity is 65% ± 5%, and wind speed is 0.4 ~ 0.8m/s.
3. the preparation method of a kind of fluorine polyester DTY 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 DTY 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 DTY 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 DTY 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.
7. the preparation method of a kind of fluorine polyester DTY fiber according to claim 1, it is characterized in that, described atactic polyether is the one in propylene glycol atactic polyether, butanols atactic polyether, laurate atactic polyether, lauryl alcohol atactic polyether and isomerous tridecanol atactic polyether; Described cithrol is the one in polyethylene glycol lauric acid monoester, polyethylene glycol laurate dibasic acid esters, polyethylene glycol oleic acid monoester and polyethylene glycol Glycol Oleic Acid Ester; Described phosphate kalium salt is the one in 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, isomerous tridecanol polyoxyethylene ether phosphate kalium salt and ten tetracosanol phosphate kalium salts; Described perfluoroalkyl acrylate is 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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| 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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| CN115369516B (en) * | 2022-09-21 | 2023-10-17 | 无锡市兴盛新材料科技有限公司 | PBT-DTY (polybutylene terephthalate-polyethylene terephthalate) matte fiber material and preparation method thereof |
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| EP1600797A1 (en) * | 2004-05-28 | 2005-11-30 | Nippon Shokubai Co., Ltd. | Transparent resin material |
| CN101139434A (en) * | 2007-09-30 | 2008-03-12 | 大连理工大学 | Fluorinated polyesters with low surface energy and preparation method thereof |
| 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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