CN103469340B

CN103469340B - Fluorine-containing PBT random co-polyester DTY fiber and method for preparing same

Info

Publication number: CN103469340B
Application number: CN201310447203.0A
Authority: CN
Inventors: 张�荣; 吴国旺; 丁建中; 曾晓元; 黄卓旺; 江立平; 宋怀军
Original assignee: JIANGSU LIXIN CHEMICAL FIBER TECHNOLOGY Co Ltd
Current assignee: Hubei Dazhihui New Materials Technology Co ltd
Priority date: 2013-09-26
Filing date: 2013-09-26
Publication date: 2015-07-01
Anticipated expiration: 2033-09-26
Also published as: CN103469340A

Abstract

The invention relates to a fluorine-containing PBT random co-polyester DTY fiber and a method for preparing the fluorine-containing PBT random co-polyester DTY fiber. The method comprises the preparation of a fluorine-containing PBT random co-polyester melt and the preparation of the fluorine-containing PBT random co-polyester POY fiber and random co-polyester DTY fiber. Tetrafluoroterephthalic acid, terephthalic acid and 1, 4-butanediol are adopted as raw material, inhibitor is added to the raw materials to obtain the fluorine-containing PBT random co-polyester melt; a POY-DTY technology is adopted to prepare the fluorine-containing PBT random co-polyester DIY fiber. The breaking strength of the fluorine-containing PBT random co-polyester DIY fiber is 3.2-4.0 cN/dex and the breaking elongation rate is 20%-40%. Due to the introduction of fluorine atoms, super-hydrophobic performance, oleophobic performance and staining- resisting performance of the fluorine-containing PBT random co-polyester DIY fiber are improved, and the fluorine-containing PBT random co-polyester DIY fiber has huge prospects in manufacturing of waterproof clothes, staining-resisting work clothes and work clothes in some special industries.

Description

A kind of fluorine-containing PBT random co-polyester DTY fiber and preparation method thereof

Technical field

The present invention relates to a kind of fluorine-containing PBT random co-polyester DTY fiber and preparation method thereof, particularly relate to fluorine-containing PBT random co-polyester DTY fiber that a kind of benzene ring hydrogen replaced by fluorine and preparation method thereof.

Background technology

Polyester is one of the most widely used synthetic high polymer of the current mankind; ethylene glycol terephthalate (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.

Polybutylene terephthalate (PBT) (PBT) is a kind of crystallinity line style saturated polyester, have high temperature resistant, moisture-proof, electrical insulation capability are good, oil resistant, resistance to chemical attack, the shaping feature such as soon.Its some application examples in the industry demonstrate its superiority that can not be substituted in some aspects, now it has become the fifth-largest general engineering plastic after polyamide (PA), Merlon (PC), polyformaldehyde (POM) and Noryl (MPPO), is widely used in auto industry, electronic apparatus industry, food medicine equipment, packaging material, environmental project, communication apparatus, Sport & Casual apparatus etc.Deepen constantly along with to the research of PBT stuctures and properties, not only develop different stage, dissimilar engineering plastics, as HI high impact, heat-resisting, fire-retardant etc., and its application in synthetic fiber is more and more paid attention to.PBT fibrous elasticity is superior, soft, and dyeing is convenient, has the advantage of terylene, polyamide fibre, spandex three concurrently.

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.Adopt adding of fluorine-containing end-capping reagent in Chinese patent CN 101139434A, 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 fluorine-containing PBT random co-polyester DTY fiber and preparation method thereof, fluorine-containing PBT random co-polyester DTY fiber particularly providing a kind of benzene ring hydrogen to replaced by fluorine and preparation method thereof.Fluorine-containing PBT random co-polyester DTY fiber of the present invention adopts the spinning of fluorine-containing PBT atactic polyester, and described fluorine-containing PBT atactic polyester introduces fluorine atom on the main chain of polymer, can well solve this kind of problem that wastes time and energy.Fluorine-containing PBT atactic polyester described in this present invention is by tetrafluoro terephthalic acid (TPA), terephthalic acid (TPA) and butanediol, through the fluorine-containing PBT atactic polyester that esterification and polycondensation reaction 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-containing PBT random co-polyester DTY fiber adopts POY-DTY technique, fluorine-containing PBT atactic polyester melt directly extruded or made section and to melt extrude through screw rod, cool, oil and reel obtained fluorine-containing PBT atactic polyester POY fiber; Gained fluorine-containing PBT atactic polyester POY fiber is through heating, false twisting, obtained fluorine-containing PBT random co-polyester DTY fiber of shaping, oil and reel.Described fluorine-containing PBT atactic polyester is the fluorine-containing PBT atactic polyester obtained by tetrafluoro terephthalic acid (TPA), terephthalic acid (TPA) and butanediol copolymerization; Described tetrafluoro terephthalic acid (TPA) has following structural formula:

The fluorine-containing PBT random co-polyester DTY fiber of one as above, the fracture strength of described fluorine-containing PBT random co-polyester DTY fiber is 3.2 ~ 4.0cN/dex; Elongation at break is 20 ~ 40%.

The preparation method of described fluorine-containing PBT random co-polyester DTY fiber, comprises the preparation of the preparation of fluorine-containing PBT atactic polyester melt, fluorine-containing PBT atactic polyester POY fiber and fluorine-containing PBT random co-polyester DTY fiber:

The preparation method of described fluorine-containing PBT random co-polyester DTY fiber is the fluorine-containing PBT atactic polyester melt obtained by tetrafluoro terephthalic acid (TPA), terephthalic acid (TPA) and butanediol copolymerization; Adopt POY-DTY technique, fluorine-containing PBT atactic polyester melt is directly extruded or made section and to melt extrude through screw rod, cool, oil and reel obtained fluorine-containing PBT atactic polyester POY fiber; Gained fluorine-containing PBT atactic polyester POY fiber is through heating, false twisting, obtained fluorine-containing PBT random co-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 and isomerous tridecanol polyoxyethylene ether phosphate kalium salt.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 POY Finish for fiber of function admirable.

Described fluorine-containing PBT atactic polyester melt refers to the fluorine-containing PBT atactic polyester after melting, and the preparation method of described fluorine-containing PBT atactic polyester is divided into esterification and polycondensation reaction two step; Concrete steps are:

The esterification stage: employing terephthalic acid (TPA) (PTA), BDO (BG) are main raw material, and fluorine-bearing modifier tetrafluoro terephthalic acid (TPA) (FPTA) carries out esterification after being made into uniform sizing material as Third monomer.Without the need to extra catalyst in esterification, nitrogen atmosphere, under condition of negative pressure, Stress control carries out being less than absolute pressure 1KPa, temperature controls at 160 ~ 220 DEG C, and the reaction time is 2 ~ 3 hours, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.

The polycondensation reaction stage comprises polycondensation reaction low vacuum stage and polycondensation reaction high vacuum stage of Fig:

The 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 controls at below absolute pressure 500Pa, and temperature controls at 260 ~ 270 DEG C, and the reaction time is 40 ~ 60 minutes.

Polycondensation reaction high vacuum stage of Fig:

Above-mentioned material is after the low vacuum stage, continue to vacuumize, make reaction pressure be down to absolute pressure and be less than 100Pa, reaction temperature controls at 270 ~ 275 DEG C, in 3 ~ 4 hours reaction time, 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-containing PBT atactic polyester as above, described starting monomer is terephthalic acid (TPA) (PTA), tetrafluoro terephthalic acid (TPA) (FPTA), BDO (BG).Its mol ratio is: PTA:FPTA=1:0.02 ~ 1; (PTA+FPTA): BG=1:1.4 ~ 2.

The preparation method of a kind of fluorine-containing PBT atactic polyester as above, described catalyst is selected from the one in butyl titanate, metatitanic acid four isopropyl ester, tetraethyl titanate, stannous acetate, dibutyltin diacetate, and catalyst amount is 0.01% ~ 0.03% of dicarboxylic acids gross weight used.

The preparation method of a kind of fluorine-containing PBT atactic polyester as above, described stabilizing agent is selected from the one in triphenyl phosphate, trimethyl phosphate, Trimethyl phosphite, and stabilizing agent dosage is 0.01% ~ 0.03% of dicarboxylic acids gross weight used.

The preparation method of a kind of fluorine-containing PBT atactic polyester as above, when tetrafluoro terephthalic acid (TPA) and terephthalic acid (TPA) mol ratio are 0.5 ~ 1:1, described esterification also adds the one in magnesia, silica, calcium oxide, zinc oxide and manganese oxide, as inhibitor, addition is 0.01% ~ 0.05% of described tetrafluoro terephthalic acid (TPA) and terephthalic acid (TPA) gross weight.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, make to 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 building-up process, 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.

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 PBT atactic 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 PBT random co-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, gained novel fluorine PBT random co-polyester DTY fiber introduces fluorine atom by adopting, thus has hydrophobic antifouling characteristic.

3, gained novel fluorine PBT random co-polyester DTY fiber 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.

The fluorine-containing PBT random co-polyester DTY fiber of one as above, described fluorine-containing PBT random co-polyester DTY fiber fracture strength is 3.2 ~ 4.0cN/dex; Elongation at break is 20 ~ 40%.

Embodiment 1

A preparation method for fluorine-containing PBT atactic polyester, is divided into esterification and polycondensation reaction two step.Concrete steps are:

Described esterification:

Employing terephthalic acid (TPA) (PTA), BDO (BG) are main raw material, and fluorine-bearing modifier tetrafluoro terephthalic acid (TPA) (FPTA) carries out esterification after being made into uniform sizing material as Third monomer.In raw material, terephthalic acid (TPA) (PTA), tetrafluoro terephthalic acid (TPA) (FPTA), BDO (BG) mol ratio are: PTA:FPTA=1:0.02; (PTA+FPTA): BG=1:1.4.Without the need to extra catalyst in esterification, in nitrogen atmosphere, under condition of negative pressure, Stress control is being less than absolute pressure 1KMa, and temperature controls at 220 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.

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 catalyst butyl titanate of 0.01% of binary acid weight used and 0.01% of binary acid weight used is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure controls to be less than 500Pa in absolute pressure, temperature controls at 265 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, 4 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-containing PBT polyester melt; 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-containing PBT 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-containing PBT polyester DTY fiber of shaping, oil and reel by described fluorine-containing PBT 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-containing PBT polyester DTY fiber, fracture strength is 3.2cN/dex, and elongation at break is 40%.

Embodiment 2

Described esterification:

Employing terephthalic acid (TPA) (PTA), BDO (BG) are main raw material, and fluorine-bearing modifier tetrafluoro terephthalic acid (TPA) (FPTA) carries out esterification after being made into uniform sizing material as Third monomer.In raw material, terephthalic acid (TPA) (PTA), tetrafluoro terephthalic acid (TPA) (FPTA), BDO (BG) mol ratio are: PTA:FPTA=1:0.04; (PTA+FPTA): BG=1:1.5.Without the need to extra catalyst in esterification, in nitrogen atmosphere, under condition of negative pressure, Stress control is being less than absolute pressure 900Pa, and temperature controls at 210 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.

Described polycondensation reaction:

The described polycondensation reaction low vacuum stage, the stabilizing agent triphenyl phosphate of catalyst metatitanic acid four isopropyl ester of 0.01% of binary acid weight used and 0.01% of binary acid weight used is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure controls to be less than 400Pa in absolute pressure, temperature controls at 260 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 90Pa, and reaction temperature controls at 270 DEG C, 4 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-containing PBT polyester POY fiber:

Directly extrude, cool, oil and reel obtained by described fluorine-containing PBT polyester melt; 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-containing PBT 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-containing PBT polyester DTY fiber of shaping, oil and reel by described fluorine-containing PBT 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-containing PBT polyester DTY fiber, fracture strength is 4.0cN/dex, and elongation at break is 20%.

Embodiment 3

Described esterification:

Employing terephthalic acid (TPA) (PTA), BDO (BG) are main raw material, and fluorine-bearing modifier tetrafluoro terephthalic acid (TPA) (FPTA) carries out esterification after being made into uniform sizing material as Third monomer.In raw material, terephthalic acid (TPA) (PTA), tetrafluoro terephthalic acid (TPA) (FPTA), BDO (BG) mol ratio are: PTA:FPTA=1:0.1; (PTA+FPTA): BG=1:1.6.Without the need to extra catalyst in esterification, in nitrogen atmosphere, under condition of negative pressure, Stress control is being less than absolute pressure 800Pa, and temperature controls at 200 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.

Described polycondensation reaction:

The described polycondensation reaction low vacuum stage, the stabilizing agent trimethyl phosphate of the catalyst tetraethyl titanate of 0.02% of binary acid weight used and 0.02% of binary acid weight used is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure controls to be less than 400Pa in absolute pressure, 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 80Pa, and reaction temperature controls at 275 DEG C, 3.5 hours reaction time.Polycondensation reaction to be as the criterion judgement reaction end with reactor stirring motor power or in-line viscometer reading.

Directly extrude, cool, oil and reel obtained by described fluorine-containing PBT polyester melt; 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-containing PBT 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-containing PBT polyester DTY fiber of shaping, oil and reel by described fluorine-containing PBT 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-containing PBT polyester DTY fiber, fracture strength is 3.5cN/dex, and elongation at break is 35%.

Embodiment 4

Described esterification:

Employing terephthalic acid (TPA) (PTA), BDO (BG) are main raw material, and fluorine-bearing modifier tetrafluoro terephthalic acid (TPA) (FPTA) carries out esterification after being made into uniform sizing material as Third monomer.In raw material, terephthalic acid (TPA) (PTA), tetrafluoro terephthalic acid (TPA) (FPTA), BDO (BG) mol ratio are: PTA:FPTA=1:0.2; (PTA+FPTA): BG=1:1.8.Without the need to extra catalyst in esterification, in nitrogen atmosphere, under condition of negative pressure, Stress control is being less than absolute pressure 700Pa, and temperature controls at 180 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.

Described polycondensation reaction:

The described polycondensation reaction low vacuum stage, the stabilizing agent trimethyl phosphate of the sub-tin of catalyst acetic acid of 0.02% of binary acid weight used and 0.02% of binary acid weight used is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure controls to be less than 400Pa in absolute pressure, 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 80Pa, and reaction temperature controls at 273 DEG C, 3.5 hours reaction time.Polycondensation reaction to be as the criterion judgement reaction end with reactor stirring motor power or in-line viscometer reading.

Directly extrude, cool, oil and reel obtained by described fluorine-containing PBT polyester melt; 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-containing PBT 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-containing PBT polyester DTY fiber of shaping, oil and reel by described fluorine-containing PBT 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-containing PBT polyester DTY fiber, fracture strength is 3.8cN/dex, and elongation at break is 25%.

Embodiment 5

Described esterification:

Employing terephthalic acid (TPA) (PTA), BDO (BG) are main raw material, and fluorine-bearing modifier tetrafluoro terephthalic acid (TPA) (FPTA) carries out esterification after being made into uniform sizing material as Third monomer.In raw material, terephthalic acid (TPA) (PTA), tetrafluoro terephthalic acid (TPA) (FPTA), BDO (BG) mol ratio are: PTA:FPTA=1:0.4; (PTA+FPTA): BG=1:2.Without the need to extra catalyst in esterification, in nitrogen atmosphere, under condition of negative pressure, Stress control is being less than absolute pressure 600Pa, and temperature controls at 160 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.

Described polycondensation reaction:

The described polycondensation reaction low vacuum stage, the stabilizing agent Trimethyl phosphite of the catalyst dibutyltin diacetate of 0.03% of binary acid weight used and 0.03% of binary acid weight used is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure controls to be less than 300Pa in absolute pressure, temperature controls at 260 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 270 DEG C, 3 hours reaction time.Polycondensation reaction to be as the criterion judgement reaction end with reactor stirring motor power or in-line viscometer reading.

Directly extrude, cool, oil and reel obtained by described fluorine-containing PBT polyester melt; 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-containing PBT 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:

Embodiment 6

Described esterification:

Employing terephthalic acid (TPA) (PTA), BDO (BG) are main raw material, and fluorine-bearing modifier tetrafluoro terephthalic acid (TPA) (FPTA) carries out esterification after being made into uniform sizing material as Third monomer.In raw material, terephthalic acid (TPA) (PTA), tetrafluoro terephthalic acid (TPA) (FPTA), BDO (BG) mol ratio are: PTA:FPTA=1:0.5; (PTA+FPTA): BG=1:1.8.Without the need to extra catalyst in esterification, in nitrogen atmosphere, under condition of negative pressure, Stress control is being less than absolute pressure 500Pa, and temperature controls at 200 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.

Described polycondensation reaction:

The described polycondensation reaction low vacuum stage, the stabilizing agent triphenyl phosphate of the catalyst butyl titanate of 0.03% of binary acid weight used and 0.03% of binary acid weight used is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure controls to be less than 300Pa in absolute pressure, temperature controls at 260 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 30Pa, and reaction temperature controls at 275 DEG C, 3 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 PBT atactic polyester section.

Melt extrude through screw rod, cool, oil and reel obtained by described fluorine-containing PBT polyester section; 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-containing PBT 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:

Embodiment 7

Described esterification:

Adopt terephthalic acid (TPA) (PTA), 1,4-butanediol (BG) is main raw material, fluorine-bearing modifier tetrafluoro terephthalic acid (TPA) (FPTA) is made into uniform sizing material as Third monomer, add the magnesia of 0.01% of dicarboxylic acids gross weight used simultaneously, carry out esterification.In raw material, terephthalic acid (TPA) (PTA), tetrafluoro terephthalic acid (TPA) (FPTA), BDO (BG) mol ratio are: PTA:FPTA=1:0.5; (PTA+FPTA): BG=1:1.4.Without the need to extra catalyst in esterification, in nitrogen atmosphere, under condition of negative pressure, Stress control is being less than absolute pressure 1KMa, and temperature controls at 220 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.

Described polycondensation reaction:

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, 4 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 PBT atactic polyester section.

Melt extrude through screw rod, cool, oil and reel obtained by described fluorine-containing PBT polyester section; 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-containing PBT 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:

Embodiment 8

Described esterification:

Adopt terephthalic acid (TPA) (PTA), 1,4-butanediol (BG) is main raw material, fluorine-bearing modifier tetrafluoro terephthalic acid (TPA) (FPTA) is made into uniform sizing material as Third monomer, add the silica of 0.02% of dicarboxylic acids gross weight used simultaneously, carry out esterification.In raw material, terephthalic acid (TPA) (PTA), tetrafluoro terephthalic acid (TPA) (FPTA), BDO (BG) mol ratio are: PTA:FPTA=1:0.6; (PTA+FPTA): BG=1:1.5.Without the need to extra catalyst in esterification, in nitrogen atmosphere, under condition of negative pressure, Stress control is being less than absolute pressure 900Pa, and temperature controls at 210 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.

Described polycondensation reaction:

The described polycondensation reaction low vacuum stage, the stabilizing agent triphenyl phosphate of catalyst metatitanic acid four isopropyl ester of 0.01% of binary acid weight used and 0.01% of binary acid weight used is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure controls to be less than 400Pa in absolute pressure, temperature controls at 260 DEG C, and the reaction time is 55 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 90Pa, and reaction temperature controls at 270 DEG C, 4 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 PBT atactic polyester section.

Melt extrude through screw rod, cool, oil and reel obtained by described fluorine-containing PBT polyester section; 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-containing PBT 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:

Embodiment 9

Described esterification:

Adopt terephthalic acid (TPA) (PTA), 1,4-butanediol (BG) is main raw material, fluorine-bearing modifier tetrafluoro terephthalic acid (TPA) (FPTA) is made into uniform sizing material as Third monomer, add the calcium oxide of 0.03% of dicarboxylic acids gross weight used simultaneously, carry out esterification.In raw material, terephthalic acid (TPA) (PTA), tetrafluoro terephthalic acid (TPA) (FPTA), BDO (BG) mol ratio are: PTA:FPTA=1:0.8; (PTA+FPTA): BG=1:1.8.Without the need to extra catalyst in esterification, in nitrogen atmosphere, under condition of negative pressure, Stress control is being less than absolute pressure 800Pa, and temperature controls at 200 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.

Described polycondensation reaction:

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, 3.5 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 PBT atactic polyester section.

Melt extrude through screw rod, cool, oil and reel obtained by described fluorine-containing PBT polyester section; 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-containing PBT 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:

Embodiment 10

Described esterification:

Adopt terephthalic acid (TPA) (PTA), 1,4-butanediol (BG) is main raw material, fluorine-bearing modifier tetrafluoro terephthalic acid (TPA) (FPTA) is made into uniform sizing material as Third monomer, add the zinc oxide of 0.04% of dicarboxylic acids gross weight used simultaneously, carry out esterification.In raw material, terephthalic acid (TPA) (PTA), tetrafluoro terephthalic acid (TPA) (FPTA), BDO (BG) mol ratio are: PTA:FPTA=1:0.8; (PTA+FPTA): BG=1:2.Without the need to extra catalyst in esterification, in nitrogen atmosphere, under condition of negative pressure, Stress control is being less than absolute pressure 700Pa, and temperature controls at 200 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.

Described polycondensation reaction:

The described polycondensation reaction low vacuum stage, the stabilizing agent trimethyl phosphate of the sub-tin of catalyst acetic acid of 0.03% of binary acid weight used and 0.03% of binary acid weight used is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure controls to be less than 400Pa in absolute pressure, 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 80Pa, and reaction temperature controls at 273 DEG C, 3.5 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 PBT atactic polyester section.

Melt extrude through screw rod, cool, oil and reel obtained by described fluorine-containing PBT polyester section; 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-containing PBT 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:

Embodiment 11

Described esterification:

Adopt terephthalic acid (TPA) (PTA), 1,4-butanediol (BG) is main raw material, fluorine-bearing modifier tetrafluoro terephthalic acid (TPA) (FPTA) is made into uniform sizing material as Third monomer, add the manganese oxide of 0.05% of dicarboxylic acids gross weight used simultaneously, carry out esterification.In raw material, terephthalic acid (TPA) (PTA), tetrafluoro terephthalic acid (TPA) (FPTA), BDO (BG) mol ratio are: PTA:FPTA=1:1; (PTA+FPTA): BG=1:2.Without the need to extra catalyst in esterification, in nitrogen atmosphere, under condition of negative pressure, Stress control is being less than absolute pressure 500Pa, and temperature controls at 160 DEG C, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end.

Described polycondensation reaction:

The described polycondensation reaction low vacuum stage, the stabilizing agent Trimethyl phosphite of the catalyst dibutyltin diacetate of 0.03% of binary acid weight used and 0.03% of binary acid weight used is added in esterification products, polycondensation reaction is started under the condition of negative pressure, this staged pressure controls to be less than 300Pa in absolute pressure, temperature controls at 265 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 275 DEG C, 3 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 PBT atactic polyester section.

Prepare the method for DTY fiber:

Claims

1. a fluorine-containing PBT random co-polyester DTY fiber, it is characterized in that: described fluorine-containing PBT random co-polyester DTY fiber adopts POY-DTY technique, by fluorine-containing PBT atactic polyester melt through measuring, extruding, cool, oil and reel obtained fluorine-containing PBT atactic polyester POY fiber; Described fluorine-containing PBT atactic polyester POY fiber is through heating, false twisting, obtained fluorine-containing PBT random co-polyester DTY fiber of shaping, oil and reel; Described fluorine-containing PBT atactic polyester is the fluorine-containing PBT atactic polyester obtained by tetrafluoro terephthalic acid (TPA), terephthalic acid (TPA) and butanediol copolymerization; Described tetrafluoro terephthalic acid (TPA) has following structure:

2. the fluorine-containing PBT random co-polyester DTY fiber of one according to claim 1, is characterized in that, the fracture strength of described fluorine-containing PBT random co-polyester DTY fiber is 3.2 ~ 4.0cN/dex; Elongation at break is 20 ~ 40%.

3. the preparation method of a kind of fluorine-containing PBT random co-polyester DTY fiber as claimed in claim 1, it is characterized in that: adopt POY-DTY technique, elder generation through measuring, extruding, cool, oil and winding steps, obtains fluorine-containing PBT atactic polyester POY fiber by fluorine-containing PBT atactic polyester melt;

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;

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-containing PBT atactic polyester POY fiber through heating, false twisting, shape, oil and winding steps, obtained fluorine-containing PBT random co-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 esterification:

Employing terephthalic acid (TPA), BDO are main raw material, and fluorine-bearing modifier tetrafluoro terephthalic acid (TPA) carries out esterification after being made into uniform sizing material as Third monomer; Without the need to extra catalyst in esterification, nitrogen atmosphere, under condition of negative pressure, Stress control carries out being less than absolute pressure 1KPa, temperature controls at 160 ~ 220 DEG C, and the reaction time is 2 ~ 3 hours, and esterification water quantity of distillate reaches more than 90% of theoretical value for reaction end;

Described polycondensation reaction:

In the described polycondensation reaction low vacuum stage, add catalyst and stabilizing agent in described esterification products, under the condition of negative pressure, start polycondensation reaction, described negative pressure refers to below absolute pressure 500Pa, and temperature controls at 260 ~ 270 DEG C, and the reaction time is 40 ~ 60 minutes;

Described polycondensation reaction high vacuum stage of Fig, continue to vacuumize, make reaction pressure be down to absolute pressure and be less than 100Pa, reaction temperature controls at 270 ~ 275 DEG C, in 3 ~ 4 hours reaction time, to be as the criterion judgement reaction end with reactor stirring motor power or in-line viscometer reading.

4. the preparation method of a kind of fluorine-containing PBT random co-polyester DTY fiber according to claim 3, 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.

5. the preparation method of a kind of fluorine-containing PBT random co-polyester DTY fiber according to claim 3, it is characterized in that, the mol ratio of terephthalic acid (TPA) and tetrafluoro terephthalic acid (TPA) is 1:0.02 ~ 1, and the total amount of terephthalic acid (TPA) and tetrafluoro terephthalic acid (TPA) and the mol ratio of 1.4-butanediol are 1:1.4 ~ 2.

6. the preparation method of a kind of fluorine-containing PBT random co-polyester DTY fiber according to claim 3, it is characterized in that, described catalyst is selected from the one in butyl titanate, tetraisopropyl titanate, tetraethyl titanate, stannous acetate, dibutyltin diacetate, and catalyst amount is 0.01% ~ 0.03% of tetrafluoro terephthalic acid (TPA) and terephthalic acid (TPA) gross weight.

7. the preparation method of a kind of fluorine-containing PBT random co-polyester DTY fiber according to claim 3, it is characterized in that, described stabilizing agent is selected from the one in triphenyl phosphate, trimethyl phosphate, Trimethyl phosphite, and stabilizing agent dosage is 0.01% ~ 0.03% of tetrafluoro terephthalic acid (TPA) and terephthalic acid (TPA) gross weight.

8. the preparation method of a kind of fluorine-containing PBT atactic polyester according to claim 3, it is characterized in that, when tetrafluoro terephthalic acid (TPA) and terephthalic acid (TPA) mol ratio are 0.5 ~ 1:1, described esterification also adds magnesia, silica, calcium oxide, zinc oxide or manganese oxide, and addition is 0.01% ~ 0.05% of described tetrafluoro terephthalic acid (TPA) and terephthalic acid (TPA) gross weight.

9. the preparation method of a kind of fluorine-containing PBT random co-polyester DTY fiber according to claim 3, is characterized in that, described fluorine-containing PBT atactic polyester melt is directly obtained by polymerization or cut into slices by fluorine-containing PBT atactic polyester to obtain through screw rod melting.

10. the preparation method of a kind of fluorine-containing PBT random co-polyester DTY fiber according to claim 3, 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 and isomerous tridecanol polyoxyethylene ether phosphate kalium salt; 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.