CN103510184A

CN103510184A - Fluorine-containing PET-PBT (polyethylene terephthalate- polybutylene terephthalate) copolyester DTY (draw texturing yarn) fiber and preparation method thereof

Info

Publication number: CN103510184A
Application number: CN201310445643.2A
Authority: CN
Inventors: 宋怀军; 丁建中; 曾晓元; 黄卓旺; 江立平; 张�荣; 吴国旺
Original assignee: JIANGSU LIXIN CHEMICAL FIBER TECHNOLOGY Co Ltd
Current assignee: Zhejiang Chaoyi Textile Technology Co.,Ltd.
Priority date: 2013-09-26
Filing date: 2013-09-26
Publication date: 2014-01-15
Anticipated expiration: 2033-09-26
Also published as: CN103510184B

Abstract

The invention relates to a fluorine-containing PET-PBT copolyester DTY fiber and a preparation method of the fiber. The preparation method comprises the steps of preparation of a fluorine-containing PET-PBT copolyester flux, preparation of a fluorine-containing PET-PBT copolyester POY (polyester pre-oriented yarn) fiber and preparation of a fluorine-containing PET-PBT copolyester DTY fiber. The detailed steps are as follows: using fluorine-containing terephthalic acid, terephthalic acid, ethylene glycol and 1, 4-butanediol as main raw materials; adding an inhibitor to prepare and obtain the fluorine-containing PET-PBT copolyester flux; using a POY-DTY technology to prepare the fluorine-containing PET-PBT copolyester DTY fiber. The fluorine-containing PET-PBT copolyester DTY fiber has the breaking strength of 3.2-4.0 cN/dex and the elongation at break of 20-40%. As the fluorine atoms are introduced, the super-hydrophobic, hydrophobic and oleophobic, and antifouling performances of the polyester DTY fiber are improved; the fiber has great prospect for manufacturing waterproof clothes, stain resistant work clothes and work clothes in some special industries.

Description

A kind of fluorine-containing PET-PBT copolyesters DTY fiber and preparation method thereof

Technical field

The present invention relates to a kind of fluorine-containing PET-PBT copolyesters DTY fiber and preparation method thereof, particularly relate to copolyesters DTY fiber being formed by fluorine-containing PET and PBT structure on a kind of main chain and preparation method thereof.

Background technology

Polyester is one of the most widely used synthetic high polymer of the current mankind; as far back as twentieth century, just synthesized ethylene glycol terephthalate (PET) forties; and find that it has excellent performance, and be widely used in the fields such as weaving, packing, health care, automobile, electronic apparatus, security protection, environmental protection.Low-stretch yarn DTY, refer on elasticizer device, carry out continuously or stretch simultaneously, the finished silk after twister deformation processing, also referred to as low elastic polyester filament, be to take long filament as raw material, utilize fiber thermoplasticity, through distortion and HEAT SETTING, process the curling fluffy novel yarn of a kind of height making.DTY is used on weft machine, in the daily necessitiess such as fashionable dress, decoration, household articles, has certain application, is the substitute beyond cotton.

Polybutylene terephthalate (PBT) (PBT) is a kind of crystallinity line style saturated polyester, has that high temperature resistant, moisture-proof, electrical insulation capability are good, a feature such as oil resistant, resistance to chemical attack, moulding are fast.Its some application examples in industry demonstrate the superiority that it 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.Along with the research of PBT structure and performance is deepened constantly, not only develop different stage, dissimilar engineering plastics, as HI high impact, heat-resisting, fire-retardant etc., and its application aspect synthetic fiber is more and more paid attention to.PBT fibrous elasticity is superior, soft, and dyeing is convenient, has terylene, polyamide fibre, spandex three's advantage concurrently.

PET polyester is because its excellent mechanical property becomes the main raw material of textile industry, but the drawbacks limit such as its dyeability and resilience be poor its further application.The dyeability of PBT polyester and resilience are extremely excellent, but the difficulty that is shaped in fibre spinning process, woven into fabric body bone is not endured.For comprehensive PET and PBT fiber advantage separately, PET-PBT copolyesters and composite fibre etc. arise at the historic moment.PET-PBT copolyesters is taken into account both advantages, in industries such as clothes and carpets, is with a wide range of applications.

Along with social progress, the raising of living standards of the people, needs more and more higher to differential, the functionalization of polyester fiber.Therefore also become particularly important of the modification of polyester, polyester modification object, except conventional polyester performance is optimized, is mainly to give new polyester differential functional characteristic by modified method.Such as: antistatic, fire-retardant, moisture absorbing and sweat releasing, antifouling deodorization etc.At present, the main new varieties of polyester have: antistatic polyester, high-strength wearable polyester, imitative cotton ultra-soft polyester, super-hydrophobicity polyester, anti-soil polyester etc.

At present, by introduce fluorine atom in polymer, thereby improve the surface property of material, as hydro-oleophobicity and soil resistance etc., and give polyester material various functions.Because fluoropolymer has low-surface-energy, low-friction coefficient and non-adhesiveness conventionally, dust dirt such as is difficult to adhere at the characteristic, so the anti-soil ABRASION RESISTANCE of fluoropolymer is good.And current fluoropolymer be take fluoroolefin base polymer as main (such as polytetrafluoroethylene (PTFE), Kynoar, fluorinated ethylene propylene copolymer, ethylene-tetrafluoroethylene copolymer etc.); The research of fluorochemical urethane, fluorochemical polyether, fluorine-containing polyester etc. relatively lags behind.

Many scholars are studied fluorochemical modified poly ester, and have obtained certain achievement.The mode of fluorochemical modified poly ester is mainly by adding fluorine-containing end-capping reagent at present, or adds the fluorochemicals such as Fluorinated dihydric alcohol, fluorine-containing binary acid to carry out modified poly ester as the 3rd monomer.In Chinese patent CN101139434A, adopt adding of fluorine-containing end-capping reagent, dimethyl isophthalate and butanediol adopt ester-interchange method, add fluorine-containing end-capping reagent N-ethoxy perfluor caprylamide, have prepared the low and polyester material that stain resistant performance is good of fluorinated volume.Hu Juan (Hu Juan. the MOLECULE DESIGN of fluorine-containing polyester and photoresist waveguide material and performance study [D]. Master's thesis, Jilin: Jilin University, 2007.) utilize the principle of MOLECULE DESIGN, by adding the mode of Fluorinated dihydric alcohol copolymerization, paraphthaloyl chloride, hexafluoro bisphenol-a and fluorine-containing ethohexadiol ternary polymerization have been synthesized to the polyester of novel high fluorinated volume.This polyester has excellent performance and is applied to optical waveguide material.

Yet the polyester that these are contained to fluorine element is applied to there is certain limitation in weaving and packaging material, subject matter is that the molecular weight of polyesters that contains fluorine element of prior art is low, can not meet the requirement of spinning and film forming; Prior art is mainly to give its water proof anti-soil function by the fluorine-containing rear Collator Mode of fabric at present, and the problem such as that the shortcoming of this class methods maximum is to be difficult to solve is ageing, durability and ABRASION RESISTANCE, and waste time and energy.

Therefore, develop fluorine-containing polyester fiber for weave and super-hydrophobic, the hydrophobic and oil repellent of packaging material, the modification of antifouling property will have important theory significance and using value.

Summary of the invention

The invention provides a kind of fluorine-containing PET-PBT copolyesters DTY fiber and preparation method thereof, fluorine-containing PET-PBT copolyesters DTY fiber that a kind of benzene ring hydrogen replaced by fluorine and preparation method thereof is particularly provided.Fluorine-containing PET-PBT copolyesters DTY fiber of the present invention adopts the spinning of fluorine-containing PET-PBT copolyesters, and described fluorine-containing PET-PBT copolyesters has been introduced fluorine atom on the main chain of polymer, therefore can well solve this class problem that wastes time and energy.Fluorine-containing PET-PBT copolyesters described in the present invention is the copolyesters obtaining through copolymerization by fluorine-containing ethylene glycol terephthalate and mutual-phenenyl two acid bromide two alcohol ester.By copolymerization method, polyester is carried out to hydrophobic antifouling modification, can fundamentally solve the problems such as ageing, the durability of hydrophobic antifouling polyester and ABRASION RESISTANCE.

The invention provides following technical scheme:

A PET-PBT copolyesters DTY fiber, is to adopt POY-DTY technique, by fluorine-containing PET-PBT copolyesters melt directly extrude or make section through screw rod melt extrude, cooling, oil and coiling makes fluorine-containing PET-PBT copolyesters POY fiber; The fluorine-containing PET-PBT copolyesters of gained POY fiber through heating, false twisting, shape, oil and coiling makes fluorine-containing PET-PBT copolyesters DTY fiber.Described fluorine-containing PET-PBT copolyesters refers to fluorine-containing ethylene glycol terephthalate and mutual-phenenyl two acid bromide two alcohol ester's copolyesters, and its general structure is

Or

M=50～90 wherein, n=40～80.

A kind of fluorine-containing PET-PBT copolyesters DTY fiber as above, the fracture strength of described fluorine-containing PET-PBT copolyesters DTY fiber is 3.2～4.0cN/dex; Elongation at break is 20～40%.

The preparation method of described fluorine-containing PET-PBT copolyesters DTY fiber, comprises the preparation of the preparation of fluorine-containing PET-PBT copolyesters melt, fluorine-containing PET-PBT copolyesters POY fiber and fluorine-containing PET-PBT copolyesters DTY fiber:

The preparation method of described fluorine-containing PET-PBT copolyesters DTY fiber, adopts fluorine-containing terephthalic acid (TPA), terephthalic acid (TPA), ethylene glycol and BDO as main raw material and adds inhibitor to prepare fluorine-containing PET-PBT copolyesters melt; Adopt POY-DTY technique, by fluorine-containing PET-PBT copolyesters melt directly extrude or make section through screw rod melt extrude, cooling, oil and coiling makes fluorine-containing PET-PBT copolyesters POY fiber; The fluorine-containing PET-PBT copolyesters of gained POY fiber through heating, false twisting, shape, oil and coiling makes fluorine-containing PET-PBT copolyesters DTY fiber;

The described temperature of extruding is 285～295 ℃;

Described cooling wind-warm syndrome is 20～30 ℃;

The described oil applying rate oiling is 0.42～1.5wt%;

The speed of described coiling is 2700～3200m/min;

Described is cooled to lateral blowing or encircles quenching, and temperature is 20 ℃～30 ℃, and relative humidity is 65% ± 5%, and wind speed is 0.4～0.8m/s;

The described finish oiling is fluorine-containing polyester POY fiber finish, its component by weight:

Atactic polyether, 50～60 parts;

Cithrol, 20～32 parts;

Phosphate kalium salt, 10～15 parts;

Perfluoroalkyl acrylate, 2～5 parts;

The preparation method of finish:

By atactic polyether, be heated to 40～60 ℃, cithrol, phosphate kalium salt and perfluoroalkyl acrylate are uniformly mixed, then join in atactic polyether, stir 1～2 hour, obtain fluorine-containing polyester POY fiber finish, finish adds water while using and is made into the emulsion that solid content is 8～10wt%.

The temperature of described heating is 195～200 ℃;

The control drafting multiple of described false twisting is 1.5～1.8 times;

The temperature of described sizing is 135～145 ℃;

Described fluorine-containing polyester POY fiber with the effect components of finish is, by weight, and component A: 50～60 parts of atactic polyethers; B component: cithrol, 20～32 parts; Component C: phosphate kalium salt, 10～15 parts; Component D: perfluoroalkyl acrylate, 2～5 parts.

Described fluorine-containing polyester POY fiber is with in finish, and component A atactic polyether is smooth agent: this material is a kind of in propylene glycol atactic polyether, butanols atactic polyether, laurate atactic polyether, lauryl alcohol atactic polyether and isomerous tridecanol atactic polyether.The good heat resistance of atactic polyether, is fuming few, and coking is few, and flowing temperature is low, good stability, and coefficient of friction is low, and anti-shear ability is strong, and viscosity coefficient is low, can form the highly stable lubricant film with large absorption affinity and bearing capacity in polyester fibre surface.

Described fluorine-containing polyester POY fiber is with in finish, and B component cithrol is emulsifying agent: this material is a kind of in polyethylene glycol lauric acid monoester, polyethylene glycol laurate dibasic acid esters, polyethylene glycol oleic acid monoester and polyethylene glycol Glycol Oleic Acid Ester.Oil film that cithrol becomes has the performances such as good surface tension, interfacial tension, penetrability, dispersiveness and emulsibility, its form finish can reduce between silk and silk, thread and metal between quiet/kinetic force of friction, for fluorine-containing polyester fiber provides certain antistatic behaviour, improve convergence.

Described fluorine-containing polyester POY fiber is with in finish, and component C phosphate kalium salt is antistatic additive: this material is a kind of in 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, isomerous tridecanol polyoxyethylene ether phosphate kalium salt and ten tetracosanol phosphate kalium salts.In spinning process, easily produce a large amount of static, the generation that the flatness by fiber surface reduces static content is inadequate, also needs to add the antistatic additive of superior performance.Phosphate kalium salt is a kind of good antistatic additive, it is a kind of anion surfactant, consists of hydrophobic grouping energy and polyester fibre surface combination hydrophobic group and hydrophilic radical, hydrophilic radical phosphate group upwards, can form the continuous moisture film of " interfacial agent-water ".Can effectively fall low-fiber coefficient of friction, increase the dielectric constant between friction piece, prevent that static from occurring.

Described fluorine-containing polyester POY fiber is with in finish, and component D perfluoroalkyl acrylate is additive: this material is a kind of in perfluoro butyl ethyl propylene acid esters, perfluoro hexyl ethyl propylene acid esters, perfluoro capryl ethyl propylene acid esters, perfluoro butyl ethyl-methyl acrylate, perfluoro hexyl ethyl-methyl acrylate and perfluoro capryl ethyl-methyl acrylate.Its effect is the surface tension that suitably reduces finish, makes it be easy to form uniform continuous oil film.Fluorinated acrylate has lower surface energy, and appropriate interpolation can be lowered the surface tension of finish, and the wettability of finish and penetrability are greatly increased, and is easy to the wetting of fiber and sprawls, and forms uniform oil film.

The main implementation procedure of finish for described fluorine-containing polyester POY fiber: by weight, get 50～60 parts of atactic polyethers, be heated to 40～60 ℃, 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, obtain the fluorine-containing polyester POY fiber finish of function admirable.

Described fluorine-containing PET-PBT copolyesters melt refers to the fluorine-containing PET-PBT copolyesters after melting, the preparation method of described fluorine-containing PET-PBT copolyesters

Be divided into the poly-stage of reaction of esterification stage, prepolymerization reaction stage and final minification; Concrete steps are:

Step 1): adopt fluorine-containing terephthalic acid (TPA) and ethylene glycol as raw material, add inhibitor, carry out esterification after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and pressure is controlled at normal pressure～0.4MPa, and temperature is at 230～250 ℃, and what esterification water quantity of distillate reached theoretical value more than 90% is esterification terminal; Add catalyst, continue to vacuumize, by normal pressure, be steadily evacuated to below absolute pressure 1KPa, temperature is controlled at 250～270 ℃, carry out prepolymerization reaction, 1～2 hour reaction time was prepolymerization reaction terminal when architectural characteristic viscosity number reaches 0.3dL/g～0.4dL/g;

Step 2): adopt terephthalic acid (TPA) and BDO as raw material, carrying out esterification after being made into uniform sizing material; Esterification is carried out under condition of negative pressure, and pressure is controlled at and is less than absolute pressure 1KPa, and temperature is at 180～220 ℃, and what esterification water quantity of distillate reached theoretical value more than 90% is esterification terminal; Add catalyst, continue to vacuumize, pressure is controlled at below absolute pressure 500Pa, and temperature is controlled at 260～270 ℃, carries out prepolymerization reaction, and 2～3 hours reaction time was prepolymerization reaction terminal when architectural characteristic viscosity number reaches 0.5dL/g～0.6dL/g;

Step 3): by the precondensation product, the step 2 that make in step 1)) the precondensation product, catalyst and the stabilizing agent that in, make add in reaction unit, stir, then under 270～280 ℃ of temperature conditions, system pressure is controlled at 100Pa and carries out below whole polycondensation reaction, react 1～6 hour, with reactor stirring motor power or in-line viscometer reading, be as the criterion and judge the poly-reaction end of final minification.

As preferred technical scheme:

The preparation method of a kind of fluorine-containing PET-PBT copolyesters as above, described fluorine-containing terephthalic acid (TPA) and the mol ratio of ethylene glycol are 1:1.4～2.0; Described terephthalic acid (TPA) and BDO mol ratio are 1:1.4～2.0; Precondensation product and step 2 that step 1) in described step 3) makes) the precondensation product that makes, its weight ratio is 0.1～0.9:0.9～0.1.

The preparation method of a kind of fluorine-containing PET-PBT copolyesters as above, described fluorine-containing terephthalic acid (TPA) is tetrafluoro terephthalic acid (TPA) or 2,5-difluoro terephthalic acid (TPA).

The preparation method of a kind of fluorine-containing PET-PBT copolyesters as above, the catalyst in described step 1) is selected from a kind of in antimonous oxide, antimony glycol and antimony acetate, and catalyst amount is 0.01%～0.03% of described fluorine-containing terephthalic acid (TPA) weight.

The preparation method of a kind of fluorine-containing PET-PBT copolyesters as above, described step 2) catalyst in is selected from a kind of in butyl titanate, metatitanic acid four isopropyl esters and tetraethyl titanate, and catalyst amount is 0.01%～0.03% of described terephthalic acid (TPA) weight.

The preparation method of a kind of fluorine-containing PET-PBT copolyesters as above, catalyst in described step 3) is selected from a kind of in butyl titanate, metatitanic acid four isopropyl esters and tetraethyl titanate, and catalyst amount is in step 3), to add 0.01%～0.05% of precondensation product gross weight.

The preparation method of a kind of fluorine-containing PET-PBT copolyesters as above, stabilizing agent in described step 3) is selected from a kind of in triphenyl phosphate, trimethyl phosphate and Trimethyl phosphite, and stabilizing agent dosage is in step 3), to add 0.01%～0.05% of precondensation product gross weight.

The preparation method of a kind of fluorine-containing PET-PBT copolyesters as above, described inhibitor is a kind of in magnesia, silica, calcium oxide, zinc oxide and manganese oxide; On phenyl ring due to dicarboxylic acids used, there is fluorine atom, the electronegativity of fluorine atom is large, conjugation at esterification stage fluorine atom strengthens the acidity of dicarboxylic acids, 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, the end-blocking product that particularly generates alkene and aldehyde, has restricted the increase of molecular weight of product; From experimental result, if do not add inhibitor, synthetic molecular weight of polyesters is on the low side, can not meet the demand of spinning and film forming; Adding for controlling the speed in esterification stage of inhibitor, has reduced side reaction, has improved the molecular weight of product, makes to meet spinning requirement.

Conventionally, in polyester esterification process, be that the hydrogen ion that ionizes out by dicarboxylic acids used is as the catalyst of esterification, carry out self-catalyzed reaction, by regulating the temperature, pressure of esterification and micromolecularly ejecting the speed of controlling its esterification, yet the prerequisite of carrying out esterification is under certain reaction temperature and pressure, just can carry out esterification.In the situation that temperature is too low or pressure is inadequate, esterification can not carry out or speed extremely slow, thereby affect follow-up technique.If the little molecule in esterification is failed timely discharge and is easily caused unnecessary side reaction.In building-up process, conjugation due to fluorine, at 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, side reaction increases, be difficult to control, and then affect the growth of molecular weight of product, thus add inhibitor, by selecting metal oxide used to regulate.Described metal oxide can dissociate by following two kinds of modes:

Here M is metal ion, if the electronegativity of M is quite large, the duplet of oxonium ion is had to stronger attraction, so just can make O-H key weaken, and is conducive to react dissociation; On the contrary, if the electronegativity of M is little, so just will generate alkali center.M-O-H is similar with amphoteric compound, and when having alkaline matter to exist, reaction will be undertaken by the mode of acid dissociation; And when acidic materials exist, by the mode of alkali formula ionization, undertaken.The M-O of back reaction from acid dissociation mode and alkali formula ionization mode ^-and M ⁺visible, M ⁺as acid centre, its intensity only has direct relation with the electronegativity of metal ion, and M-O ^-in O ion relevant with the negative charge density on oxygen as the intensity at alkali center, negative charge density is larger, intensity is also larger.Negative charge density on visible oxonium ion and metal ion electronegativity have close relationship, and metal ion electronegativity is less, and negative charge density is just larger.So, the acid and alkalescence of metal oxide has just all connected with the electronegativity of metal ion, and the large oxide of electronegativity of metal ion is mainly acid, and what electronegativity was little is alkalescence.

The preparation method of a kind of fluorine-containing PET-PBT copolyesters as above, the addition of described inhibitor is 0.01%～0.05% of described fluorine-containing terephthalic acid (TPA) weight.

Esterification of the present invention is in the stage, reaction end actual water quantity of distillate producing in esterification reach theoretical value 90% with on grasp.Theoretical value is the quantity of distillate of gained water while pressing chemical equation complete reaction.Due to esterification this as reversible reaction, moreover raw material has residually in conveyance conduit, and along with the carrying out of reaction, the viscosity of system increases, and can cause shipwreck that esterification produces therefrom to discharge.

In the poly-stage of reaction of final minification of the present invention, the numerical value that the poly-reaction end of final minification reaches setting by reactor beater motor power and in-line viscometer calculation value is grasped.The setting numerical value of its reactor beater motor power of different devices and in-line viscometer calculation value is not necessarily identical, and setting determining of numerical value can obtain by the analysis to polyester slice.

The filament number of the novel fluorine PET-PBT copolyesters POY fiber of gained of the present invention is 0.5-3.0dtex; Fracture strength is 1.6～1.9cN/dtex; Elongation at break is 110～150%.Due to the introducing of fluorine atom, improved super-hydrophobic, hydrophobic and oil repellent, the antifouling aspect performance of polyester material, at waterproof garment, in the Work Clothes manufacture of the Work Clothes bearing dirty and some special industry, there is huge prospect.

Beneficial effect:

1, gained novel fluorine PET-PBT copolyesters DTY fiber contain fluorine atoms; strong electronegativity due to fluorine; high C-F bond energy and the copolyesters DTY fiber that the shielding protection effect of carbochain makes finally to make is had well heat-resisting, ageing-resistant, resistance to chemical attack and low electric capacity; low combustible; the performances such as low-refraction also have some special electric property, as low-k simultaneously; the advantages such as high-insulativity, have expanded range of application.

2, gained novel fluorine PET-PBT copolyesters DTY fiber is introduced fluorine atom by employing, thereby has hydrophobic antifouling characteristic.

3, gained novel fluorine PET-PBT copolyesters DTY fiber is by adopting modification by copolymerization, fundamentally solved the problems such as ageing, the durability of hydrophobic antifouling polyester and ABRASION RESISTANCE.

The specific embodiment

Below in conjunction with the specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.

Or

M=50～90 wherein, n=40～80.

A kind of fluorine-containing PET-PBT copolyesters DTY fiber as above, described fluorine-containing PET-PBT copolyesters DTY fibrous fracture intensity is 3.2～4.0cN/dex; Elongation at break is 20～40%.

Embodiment 1

A preparation method for fluorine-containing PET-PBT copolyesters, is divided into the poly-stage of reaction of esterification stage, prepolymerization reaction stage and final minification.Concrete steps are:

Step 1): adopt tetrafluoro terephthalic acid (TPA) that mol ratio is 1:1.4 and ethylene glycol as raw material, add 0.01% magnesia of tetrafluoro terephthalic acid (TPA) weight simultaneously, carry out esterification after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and pressure is controlled at 0.4MPa, and temperature is at 250 ℃, and what esterification water quantity of distillate reached theoretical value more than 90% is esterification terminal; Add the catalytic antimony trioxide, continue to vacuumize, system pressure is controlled at below absolute pressure 1KPa, and temperature is controlled at 260 ℃, carries out prepolymerization reaction, reacts 2 hours, obtains precondensation product; Wherein the consumption of the catalytic antimony trioxide is 0.01% of tetrafluoro terephthalic acid (TPA) weight used.

Step 2): adopt terephthalic acid (TPA) that mol ratio is 1:1.4 and BDO as raw material, carrying out esterification after being made into uniform sizing material; Esterification is carried out under condition of negative pressure, and pressure is controlled at and is less than absolute pressure 1KPa, and temperature is at 220 ℃, and what esterification water quantity of distillate reached theoretical value more than 90% is esterification terminal; Add catalyst metatitanic acid four butyl esters, continue to vacuumize, pressure is controlled at below absolute pressure 500Pa, and temperature is controlled at 265 ℃, carries out prepolymerization reaction, in 3 hours reaction time, obtains precondensation product; Wherein catalyst metatitanic acid four butyl ester consumptions are 0.01% of terephthalic acid (TPA) weight used.

Step 3): by the precondensation product and the step 2 that make in step 1)) the precondensation product making in is by weight joining in reaction unit for 0.1:0.9,0.01% the stabilizing agent triphenyl phosphate that simultaneously adds 0.01% catalyst metatitanic acid four butyl esters of precondensation product gross weight and precondensation product gross weight, stir, then under 270 ℃ of temperature conditions, system pressure is controlled at 100Pa and carries out below whole polycondensation reaction, with reactor stirring motor power or in-line viscometer reading, is as the criterion and judges the poly-reaction end of final minification.

The method of preparing POY fiber:

Be by described fluorine-containing PBT polyester fondant directly extrude, cooling, oil and coiling makes; Wherein, the temperature of extruding described in is 285 ℃; The described lateral blowing that is cooled to, temperature is 30 ℃, and relative humidity is 60%, and wind speed is 0.4m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 8wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 60 parts of propylene glycol atactic polyethers, be heated to 60 ℃, 20 parts of polyethylene glycol lauric acid monoesters, 15 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluoro butyl ethyl propylene acid esters are uniformly mixed, then join in propylene glycol atactic polyether, stir 1 hour, obtain fluorine-containing polyester POY fiber finish; The described oil applying rate oiling is 0.42%; The speed of described coiling is 2700m/min; Make fluorine-containing PBT polyester POY fiber, filament number is 2.0dtex; Fracture strength is 1.6cN/dtex; Elongation at break is 150%.

The method of preparing DTY fiber:

Be by described fluorine-containing PBT polyester POY fiber through heating, false twisting, shape, oil and coiling makes fluorine-containing PBT polyester DTY fiber; Wherein, the temperature of described heating is 195 ℃; The control drafting multiple of described false twisting is 1.5 times; The temperature of described sizing is 135 ℃; Finally make fluorine-containing PBT polyester DTY fiber, fracture strength is 3.2cN/dex, and elongation at break is 40%.

Embodiment 2

Step 1): to adopt mol ratio be 1:1.5 2,5-difluoro terephthalic acid (TPA) and ethylene glycol is as raw material, adds 0.03% silica of 2,5-difluoro terephthalic acid (TPA) weight simultaneously, carries out esterification after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and pressure is controlled at 0.3MPa, and temperature is at 245 ℃, and what esterification water quantity of distillate reached theoretical value more than 90% is esterification terminal; Add catalyst glycol antimony, continue to vacuumize, system pressure is controlled at below absolute pressure 800Pa, and temperature is controlled at 260 ℃, carries out prepolymerization reaction, reacts 2 hours, obtains precondensation product; Wherein the consumption of catalyst glycol antimony is used 2,0.01% of 5-difluoro terephthalic acid (TPA) weight.

Step 2): adopt terephthalic acid (TPA) that mol ratio is 1:1.5 and BDO as raw material, carrying out esterification after being made into uniform sizing material; Esterification is carried out under condition of negative pressure, and pressure is controlled at and is less than absolute pressure 900Pa, and temperature is at 210 ℃, and what esterification water quantity of distillate reached theoretical value more than 90% is esterification terminal; Add catalyst metatitanic acid four isopropyl esters, continue to vacuumize, pressure is controlled at below absolute pressure 500Pa, and temperature is controlled at 260 ℃, carries out prepolymerization reaction, in 3 hours reaction time, obtains precondensation product; Wherein catalyst metatitanic acid four isopropyl ester consumptions are 0.01% of terephthalic acid (TPA) weight used.

Step 3): by the precondensation product and the step 2 that make in step 1)) the precondensation product making in is by weight joining in reaction unit for 0.2:0.8,0.02% the stabilizing agent trimethyl phosphate that simultaneously adds 0.02% catalyst metatitanic acid four isopropyl esters of precondensation product gross weight and precondensation product gross weight, stir, then under 275 ℃ of temperature conditions, system pressure is controlled at 80Pa and carries out below whole polycondensation reaction, with reactor stirring motor power or in-line viscometer reading, is as the criterion and judges the poly-reaction end of final minification.

The preparation method of described fluorine-containing PBT polyester POY fiber:

Be by described fluorine-containing PBT polyester fondant directly extrude, cooling, oil and coiling makes; Wherein, the temperature of extruding described in is 295 ℃; The described lateral blowing that is cooled to, temperature is 20 ℃, and relative humidity is 70%, and wind speed is 0.8m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 9wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 50 parts of butanols atactic polyethers, be heated to 40 ℃, 32 parts of polyethylene glycol laurate dibasic acid esters, 15 parts of isomerous tridecanol polyoxyethylene ether phosphate kalium salts and 3 parts of perfluoro hexyl ethyl propylene acid esters are uniformly mixed, then join in butanols atactic polyether, stir 2 hours, obtain fluorine-containing polyester POY fiber finish; The described oil applying rate oiling is 1.5%; The speed of described coiling is 2800m/min; Make fluorine-containing PBT polyester POY fiber, filament number is 2.0dtex; Fracture strength is 1.8cN/dtex; Elongation at break is 140%.

The method of preparing DTY fiber:

Be by described fluorine-containing PBT polyester POY fiber through heating, false twisting, shape, oil and coiling makes fluorine-containing PBT polyester DTY fiber; Wherein, the temperature of described heating is 200 ℃; The control drafting multiple of described false twisting is 1.8 times; The temperature of described sizing is 145 ℃; Finally make fluorine-containing PBT polyester DTY fiber, fracture strength is 4.0cN/dex, and elongation at break is 20%.

Embodiment 3

Step 1): adopt tetrafluoro terephthalic acid (TPA) that mol ratio is 1:1.8 and ethylene glycol as raw material, add 0.05% calcium oxide of tetrafluoro terephthalic acid (TPA) weight simultaneously, carry out esterification after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and pressure is controlled at 0.2MPa, and temperature is at 240 ℃, and what esterification water quantity of distillate reached theoretical value more than 90% is esterification terminal; Add catalyst acetic acid antimony, continue to vacuumize, system pressure is controlled at below absolute pressure 600Pa, and temperature is controlled at 265 ℃, carries out prepolymerization reaction, reacts 1.5 hours, obtains precondensation product; Wherein the consumption of catalyst acetic acid antimony is 0.02% of tetrafluoro terephthalic acid (TPA) weight used.

Step 2): adopt terephthalic acid (TPA) that mol ratio is 1:1.8 and BDO as raw material, carrying out esterification after being made into uniform sizing material; Esterification is carried out under condition of negative pressure, and pressure is controlled at and is less than absolute pressure 800Pa, and temperature is at 200 ℃, and what esterification water quantity of distillate reached theoretical value more than 90% is esterification terminal; Add catalyst metatitanic acid tetra-ethyl ester, continue to vacuumize, pressure is controlled at below absolute pressure 400Pa, and temperature is controlled at 270 ℃, carries out prepolymerization reaction, in 2.5 hours reaction time, obtains precondensation product; Wherein catalyst metatitanic acid tetra-ethyl ester consumption is 0.02% of terephthalic acid (TPA) weight used.

Step 3): by the precondensation product and the step 2 that make in step 1)) the precondensation product making in is by weight joining in reaction unit for 0.4:0.6,0.03% the stabilizing agent Trimethyl phosphite that simultaneously adds 0.03% catalyst metatitanic acid tetra-ethyl ester of precondensation product gross weight and precondensation product gross weight, stir, then under 280 ℃ of temperature conditions, system pressure is controlled at 60Pa and carries out below whole polycondensation reaction, with reactor stirring motor power or in-line viscometer reading, is as the criterion and judges the poly-reaction end of final minification.

Be by described fluorine-containing PBT polyester fondant directly extrude, cooling, oil and coiling makes; Wherein, the temperature of extruding described in is 290 ℃; The described lateral blowing that is cooled to, temperature is 25 ℃, and relative humidity is 65%, and wind speed is 0.6m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 10wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 58 parts of laurate atactic polyethers, be heated to 60 ℃, 30 parts of polyethylene glycol oleic acid monoesters, 10 part of ten tetracosanol phosphate kalium salt and 2 parts of perfluoro capryl ethyl propylene acid esters are uniformly mixed, then join in propylene glycol atactic polyether, stir 1 hour, obtain fluorine-containing polyester POY fiber finish; The described oil applying rate oiling is 0.96%; The speed of described coiling is 2900m/min; Make fluorine-containing PBT polyester POY fiber, filament number is 1.5dtex; Fracture strength is 2.0cN/dtex; Elongation at break is 135%.

The method of preparing DTY fiber:

Be by described fluorine-containing PBT polyester POY fiber through heating, false twisting, shape, oil and coiling makes fluorine-containing PBT polyester DTY fiber; Wherein, the temperature of described heating is 198 ℃; The control drafting multiple of described false twisting is 1.6 times; The temperature of described sizing is 140 ℃; Finally make fluorine-containing PBT polyester DTY fiber, fracture strength is 3.5cN/dex, and elongation at break is 35%.

Embodiment 4

Step 1): to adopt mol ratio be 1:2.0 2,5-difluoro terephthalic acid (TPA) and ethylene glycol is as raw material, adds 0.04% manganese oxide of 2,5-difluoro terephthalic acid (TPA) weight simultaneously, carries out esterification after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and pressure is controlled at normal pressure, and temperature is at 230 ℃, and what esterification water quantity of distillate reached theoretical value more than 90% is esterification terminal; Add the catalytic antimony trioxide, continue to vacuumize, system pressure is controlled at below absolute pressure 500Pa, and temperature is controlled at 270 ℃, carries out prepolymerization reaction, reacts 1 hour, obtains precondensation product; Wherein the consumption of the catalytic antimony trioxide is used 2,0.02% of 5-difluoro terephthalic acid (TPA) weight.

Step 2): adopt terephthalic acid (TPA) that mol ratio is 1:2.0 and BDO as raw material, carrying out esterification after being made into uniform sizing material; Esterification is carried out under condition of negative pressure, and pressure is controlled at and is less than absolute pressure 600Pa, and temperature is at 180 ℃, and what esterification water quantity of distillate reached theoretical value more than 90% is esterification terminal; Add catalyst metatitanic acid tetra-ethyl ester, continue to vacuumize, pressure is controlled at below absolute pressure 300Pa, and temperature is controlled at 270 ℃, carries out prepolymerization reaction, in 2 hours reaction time, obtains precondensation product; Wherein catalyst metatitanic acid tetra-ethyl ester consumption is 0.02% of terephthalic acid (TPA) weight used.

Step 3): by the precondensation product and the step 2 that make in step 1)) the precondensation product making in is by weight joining in reaction unit for 0.7:0.3,0.05% the stabilizing agent triphenyl phosphate that simultaneously adds 0.05% catalyst metatitanic acid tetra-ethyl ester of precondensation product gross weight and precondensation product gross weight, stir, then under 275 ℃ of temperature conditions, system pressure is controlled at 50Pa and carries out below whole polycondensation reaction, with reactor stirring motor power or in-line viscometer reading, is as the criterion and judges the poly-reaction end of final minification.

Be by described fluorine-containing PBT polyester fondant directly extrude, cooling, oil and coiling makes; Wherein, the temperature of extruding described in is 285 ℃; The described lateral blowing that is cooled to, temperature is 30 ℃, and relative humidity is 60%, and wind speed is 0.4m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 8wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 50 parts of lauryl alcohol atactic polyethers, be heated to 50 ℃, 32 parts of polyethylene glycol Glycol Oleic Acid Ester, 13 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluoro butyl ethyl-methyl acrylate are uniformly mixed, then join in propylene glycol atactic polyether, stir 1 hour, obtain fluorine-containing polyester POY fiber finish; The described oil applying rate oiling is 1.5%; The speed of described coiling is 3000m/min; Make fluorine-containing PBT polyester POY fiber, filament number is 1.5dtex; Fracture strength is 2.2cN/dtex; Elongation at break is 125%.

The method of preparing DTY fiber:

Be by described fluorine-containing PBT polyester POY fiber through heating, false twisting, shape, oil and coiling makes fluorine-containing PBT polyester DTY fiber; Wherein, the temperature of described heating is 198 ℃; The control drafting multiple of described false twisting is 1.7 times; The temperature of described sizing is 140 ℃; Finally make fluorine-containing PBT polyester DTY fiber, fracture strength is 3.8cN/dex, and elongation at break is 25%.

Embodiment 5

Step 1): adopt tetrafluoro terephthalic acid (TPA) that mol ratio is 1:1.8 and ethylene glycol as raw material, add 0.03% zinc oxide of tetrafluoro terephthalic acid (TPA) weight simultaneously, carry out esterification after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and pressure is controlled at 0.2MPa, and temperature is at 240 ℃, and what esterification water quantity of distillate reached theoretical value more than 90% is esterification terminal; Add catalyst glycol antimony, continue to vacuumize, system pressure is controlled at below absolute pressure 800Pa, and temperature is controlled at 250 ℃, carries out prepolymerization reaction, reacts 1.5 hours, obtains precondensation product; Wherein the consumption of catalyst glycol antimony is 0.02% of tetrafluoro terephthalic acid (TPA) weight used.

Step 2): adopt terephthalic acid (TPA) that mol ratio is 1:1.8 and BDO as raw material, carrying out esterification after being made into uniform sizing material; Esterification is carried out under condition of negative pressure, and pressure is controlled at and is less than absolute pressure 600Pa, and temperature is at 200 ℃, and what esterification water quantity of distillate reached theoretical value more than 90% is esterification terminal; Add catalyst metatitanic acid four butyl esters, continue to vacuumize, pressure is controlled at below absolute pressure 300Pa, and temperature is controlled at 265 ℃, carries out prepolymerization reaction, in 2.5 hours reaction time, obtains precondensation product; Wherein catalyst metatitanic acid four butyl ester consumptions are 0.02% of terephthalic acid (TPA) weight used.

Step 3): by the precondensation product and the step 2 that make in step 1)) the precondensation product making in is by weight joining in reaction unit for 0.9:0.1,0.02% the stabilizing agent trimethyl phosphate that simultaneously adds 0.02% catalyst metatitanic acid tetra-ethyl ester of precondensation product gross weight and precondensation product gross weight, stir, then under 270 ℃ of temperature conditions, system pressure is controlled at 100Pa and carries out below whole polycondensation reaction, with reactor stirring motor power or in-line viscometer reading, is as the criterion and judges the poly-reaction end of final minification.

Be by described fluorine-containing PBT polyester fondant directly extrude, cooling, oil and coiling makes; Wherein, the temperature of extruding described in is 295 ℃; The described lateral blowing that is cooled to, temperature is 20 ℃, and relative humidity is 70%, and wind speed is 0.8m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 8wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 55 parts of isomerous tridecanol atactic polyethers, be heated to 55 ℃, 25 parts of polyethylene glycol laurate dibasic acid esters, 15 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluoro hexyl ethyl-methyl acrylate are uniformly mixed, then join in propylene glycol atactic polyether, stir 2 hours, obtain fluorine-containing polyester POY fiber finish; The described oil applying rate oiling is 0.42%; The speed of described coiling is 3200m/min; Make fluorine-containing PBT polyester POY fiber, filament number is 1.0dtex; Fracture strength is 2.5cN/dtex; Elongation at break is 110%.

The method of preparing DTY fiber:

Embodiment 6

Step 3): by the precondensation product and the step 2 that make in step 1)) the precondensation product making in is by weight joining in reaction unit for 0.1:0.9,0.01% the stabilizing agent triphenyl phosphate that simultaneously adds 0.01% catalyst metatitanic acid four butyl esters of precondensation product gross weight and precondensation product gross weight, stir, then under 270 ℃ of temperature conditions, system pressure is controlled at 100Pa and carries out below whole polycondensation reaction, with reactor stirring motor power or in-line viscometer reading, is as the criterion and judges the poly-reaction end of final minification.Discharging ，Jing Cast Strip, cooling, pelletizing when polymer viscosity reaches desirable value, obtain fluorine-containing PET-PBT copolyester section.

Be by described fluorine-containing PBT polyester slice through screw rod melt extrude, cooling, oil and coiling makes; Wherein, the temperature of extruding described in is 285 ℃; The described ring quenching that is cooled to, temperature is 30 ℃, and relative humidity is 60%, and wind speed is 0.4m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 9wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 60 parts of propylene glycol atactic polyethers, be heated to 45 ℃, 20 parts of polyethylene glycol oleic acid monoesters, 15 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluoro capryl ethyl-methyl acrylate are uniformly mixed, then join in propylene glycol atactic polyether, stir 1 hour, obtain fluorine-containing polyester POY fiber finish; The described oil applying rate oiling is 0.42%; The speed of described coiling is 2700m/min; Make fluorine-containing PBT polyester POY fiber, filament number is 2.0dtex; Fracture strength is 1.6cN/dtex; Elongation at break is 150%.

The method of preparing DTY fiber:

Embodiment 7

Step 3): by the precondensation product and the step 2 that make in step 1)) the precondensation product making in is by weight joining in reaction unit for 0.2:0.8,0.02% the stabilizing agent trimethyl phosphate that simultaneously adds 0.02% catalyst metatitanic acid four isopropyl esters of precondensation product gross weight and precondensation product gross weight, stir, then under 275 ℃ of temperature conditions, system pressure is controlled at 80Pa and carries out below whole polycondensation reaction, with reactor stirring motor power or in-line viscometer reading, is as the criterion and judges the poly-reaction end of final minification.Discharging ，Jing Cast Strip, cooling, pelletizing when polymer viscosity reaches desirable value, obtain fluorine-containing PET-PBT copolyester section.

Be by described fluorine-containing PBT polyester slice through screw rod melt extrude, cooling, oil and coiling makes; Wherein, the temperature of extruding described in is 295 ℃; The described ring quenching that is cooled to, temperature is 20 ℃, relative humidity is 70%, wind speed is 0.8m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 9wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 50 parts of butanols atactic polyethers, be heated to 40 ℃, 32 parts of polyethylene glycol laurate dibasic acid esters, 15 parts of isomerous tridecanol polyoxyethylene ether phosphate kalium salts and 3 parts of perfluoro hexyl ethyl propylene acid esters are uniformly mixed, then join in butanols atactic polyether, stir 2 hours, obtain fluorine-containing polyester POY fiber finish; The described oil applying rate oiling is 1.5%; The speed of described coiling is 2800m/min; Make fluorine-containing PBT polyester POY fiber, filament number is 2.0dtex; Fracture strength is 1.8cN/dtex; Elongation at break is 140%.

The method of preparing DTY fiber:

Embodiment 8

Step 3): by the precondensation product and the step 2 that make in step 1)) the precondensation product making in is by weight joining in reaction unit for 0.4:0.6,0.03% the stabilizing agent Trimethyl phosphite that simultaneously adds 0.03% catalyst metatitanic acid tetra-ethyl ester of precondensation product gross weight and precondensation product gross weight, stir, then under 280 ℃ of temperature conditions, system pressure is controlled at 60Pa and carries out below whole polycondensation reaction, with reactor stirring motor power or in-line viscometer reading, is as the criterion and judges the poly-reaction end of final minification.Discharging ，Jing Cast Strip, cooling, pelletizing when polymer viscosity reaches desirable value, obtain fluorine-containing PET-PBT copolyester section.

Be by described fluorine-containing PBT polyester slice through screw rod melt extrude, cooling, oil and coiling makes; Wherein, the temperature of extruding described in is 290 ℃; The described ring quenching that is cooled to, temperature is 25 ℃, and relative humidity is 65%, and wind speed is 0.6m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 10wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 60 parts of propylene glycol atactic polyethers, be heated to 60 ℃, 20 parts of polyethylene glycol lauric acid monoesters, 15 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluoro butyl ethyl propylene acid esters are uniformly mixed, then join in propylene glycol atactic polyether, stir 1 hour, obtain fluorine-containing polyester POY fiber finish; The described oil applying rate oiling is 0.96%; The speed of described coiling is 2900m/min; Make fluorine-containing PBT polyester POY fiber, filament number is 1.5dtex; Fracture strength is 2.0cN/dtex; Elongation at break is 135%.

The method of preparing DTY fiber:

Embodiment 9

Step 3): by the precondensation product and the step 2 that make in step 1)) the precondensation product making in is by weight joining in reaction unit for 0.7:0.3,0.05% the stabilizing agent triphenyl phosphate that simultaneously adds 0.05% catalyst metatitanic acid tetra-ethyl ester of precondensation product gross weight and precondensation product gross weight, stir, then under 275 ℃ of temperature conditions, system pressure is controlled at 50Pa and carries out below whole polycondensation reaction, with reactor stirring motor power or in-line viscometer reading, is as the criterion and judges the poly-reaction end of final minification.Discharging ，Jing Cast Strip, cooling, pelletizing when polymer viscosity reaches desirable value, obtain fluorine-containing PET-PBT copolyester section.

Be by described fluorine-containing PBT polyester slice through screw rod melt extrude, cooling, oil and coiling makes; Wherein, the temperature of extruding described in is 285 ℃; The described ring quenching that is cooled to, temperature is 30 ℃, and relative humidity is 60%, and wind speed is 0.4m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 10wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 50 parts of lauryl alcohol atactic polyethers, be heated to 50 ℃, 32 parts of polyethylene glycol Glycol Oleic Acid Ester, 13 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluoro butyl ethyl-methyl acrylate are uniformly mixed, then join in propylene glycol atactic polyether, stir 1 hour, obtain fluorine-containing polyester POY fiber finish; The described oil applying rate oiling is 1.5%; The speed of described coiling is 3000m/min; Make fluorine-containing PBT polyester POY fiber, filament number is 1.5dtex; Fracture strength is 2.2cN/dtex; Elongation at break is 125%.

The method of preparing DTY fiber:

Embodiment 10

Step 3): by the precondensation product and the step 2 that make in step 1)) the precondensation product making in is by weight joining in reaction unit for 0.9:0.1,0.02% the stabilizing agent trimethyl phosphate that simultaneously adds 0.02% catalyst metatitanic acid tetra-ethyl ester of precondensation product gross weight and precondensation product gross weight, stir, then under 270 ℃ of temperature conditions, system pressure is controlled at 100Pa and carries out below whole polycondensation reaction, with reactor stirring motor power or in-line viscometer reading, is as the criterion and judges the poly-reaction end of final minification.Discharging ，Jing Cast Strip, cooling, pelletizing when polymer viscosity reaches desirable value, obtain fluorine-containing PET-PBT copolyester section.

Be by described fluorine-containing PBT polyester slice through screw rod melt extrude, cooling, oil and coiling makes; Wherein, the temperature of extruding described in is 295 ℃; The described ring quenching that is cooled to, temperature is 30 ℃, and relative humidity is 60%, and wind speed is 0.4m/s; Described oiling adopts the fluorine-containing polyester POY fiber that the contains 8wt% emulsion of finish; The preparation of finish for fluorine-containing polyester POY fiber: its component by weight, get 60 parts of propylene glycol atactic polyethers, be heated to 45 ℃, 20 parts of polyethylene glycol oleic acid monoesters, 15 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and 5 parts of perfluoro capryl ethyl-methyl acrylate are uniformly mixed, then join in propylene glycol atactic polyether, stir 1 hour, obtain fluorine-containing polyester POY fiber finish; The described oil applying rate oiling is 0.42%; The speed of described coiling is 3200m/min; Make fluorine-containing PBT polyester POY fiber, filament number is 1.0dtex; Fracture strength is 2.5cN/dtex; Elongation at break is 110%.

The method of preparing DTY fiber:

Claims

1. a fluorine-containing PET-PBT copolyesters DTY fiber, it is characterized in that: described fluorine-containing PET-PBT copolyesters DTY fiber is to adopt POY-DTY technique, by fluorine-containing PET-PBT copolyesters melt through measuring, extrude, cooling, oil and coiling makes fluorine-containing PET-PBT copolyesters POY fiber; Described fluorine-containing PET-PBT copolyesters POY fiber through heating, false twisting, shape, oil and coiling makes fluorine-containing PET-PBT copolyesters DTY fiber; Described fluorine-containing PET-PBT copolyesters refers to the copolyesters being comprised of fluorine-containing PET and PBT structure on main chain, and the general structure of its products therefrom is

Or

M=50～90 wherein, n=40～80.

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

3. the preparation method of a kind of fluorine-containing PET-PBT copolyesters DTY fiber as claimed in claim 1, it is characterized in that: adopt POY-DTY technique, first by fluorine-containing PET-PBT copolyesters melt through measuring, extrude, cooling, the step that oils and reel, make fluorine-containing PET-PBT copolyesters POY fiber;

The described temperature of extruding is 260～290 ℃;

Described cooling wind-warm syndrome is 20～30 ℃;

The described oil applying rate oiling is 0.42～1.5wt%;

The speed of described coiling 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 ℃, cithrol, phosphate kalium salt and perfluoroalkyl acrylate are uniformly mixed, then join in atactic polyether, stir 1～2 hour, obtain fluorine-containing polyester POY fiber finish, finish adds water while using and is made into the emulsion that solid content is 8～10wt%;

Then, described fluorine-containing PET-PBT copolyesters POY fiber through heating, false twisting, shape, oil and the step of reeling, make fluorine-containing PET-PBT copolyesters DTY fiber;

The temperature of described heating is 195～200 ℃;

The control drafting multiple of described false twisting is 1.5～1.8 times;

The temperature of described sizing is 135～145 ℃;

Described fluorine-containing PET-PBT copolyesters melt refers to the fluorine-containing PET-PBT copolyesters after melting, and the preparation method of described fluorine-containing PET-PBT copolyesters is divided into the poly-stage of reaction of esterification stage, prepolymerization reaction stage and final minification; Concrete steps are:

Step 1): adopt fluorine-containing terephthalic acid (TPA) and ethylene glycol as raw material, and add inhibitor, carry out esterification after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and pressure is controlled at normal pressure～0.4MPa, and temperature is at 230～250 ℃, and what esterification water quantity of distillate reached theoretical value more than 90% is esterification terminal; Add catalyst, continue to vacuumize, by normal pressure, be steadily evacuated to below absolute pressure 1KPa, temperature is controlled at 250～270 ℃, carry out prepolymerization reaction, 1～2 hour reaction time was prepolymerization reaction terminal when architectural characteristic viscosity number reaches 0.3dL/g～0.4dL/g;

Step 3): by the precondensation product, the step 2 that make in step 1)) the precondensation product, catalyst and the stabilizing agent that in, make add in reaction unit, stir, then under 270～280 ℃ of temperature conditions, system pressure is controlled at 100Pa and carries out below whole polycondensation reaction, react 1～6 hour, with reactor stirring motor power or in-line viscometer reading, be as the criterion and judge the poly-reaction end of final minification;

Described inhibitor is a kind of in magnesia, silica, calcium oxide, zinc oxide and manganese oxide.

4. the preparation method of a kind of fluorine-containing PET-PBT copolyesters DTY fiber according to claim 3, is characterized in that, described is cooled to lateral blowing or encircles quenching, and temperature is 20 ℃～30 ℃, and relative humidity is 65% ± 5%, and wind speed is 0.4～0.8m/s.

5. the preparation method of a kind of fluorine-containing PET-PBT copolyesters DTY fiber according to claim 3, is characterized in that, described fluorine-containing terephthalic acid (TPA) is tetrafluoro terephthalic acid (TPA) or 2,5-difluoro terephthalic acid (TPA); The addition of described inhibitor is 0.01%～0.05% of described fluorine-containing terephthalic acid (TPA) weight.

6. the preparation method of a kind of fluorine-containing PET-PBT copolyesters DTY fiber according to claim 3, is characterized in that, described fluorine-containing terephthalic acid (TPA) and ethylene glycol mol ratio are 1:1.4～2.0; Described terephthalic acid (TPA) and BDO mol ratio are 1:1.4～2.0; In described step 3), precondensation product and step 2 that step 1) makes) weight ratio of the precondensation product that makes is 0.1～0.9:0.9～0.1.

7. the preparation method of a kind of fluorine-containing PET-PBT copolyesters DTY fiber according to claim 3, it is characterized in that, catalyst in described step 1) is selected from a kind of in antimonous oxide, antimony glycol and antimony acetate, and catalyst amount is 0.01%～0.03% of described fluorine-containing terephthalic acid (TPA) weight; Described step 2) catalyst in is selected from a kind of in butyl titanate, metatitanic acid four isopropyl esters and tetraethyl titanate, and catalyst amount is 0.01%～0.03% of described terephthalic acid (TPA) weight; Catalyst in described step 3) is selected from a kind of in butyl titanate, metatitanic acid four isopropyl esters and tetraethyl titanate, and catalyst amount is in step 3), to add 0.01%～0.05% of precondensation product gross weight.

8. the preparation method of a kind of fluorine-containing PET-PBT copolyesters DTY fiber according to claim 3, stabilizing agent in described step 3) is selected from a kind of in triphenyl phosphate, trimethyl phosphate and Trimethyl phosphite, and stabilizing agent dosage is in step 3), to add 0.01%～0.05% of precondensation product gross weight.

9. the preparation method of a kind of fluorine-containing PET-PBT copolyesters DTY fiber according to claim 3, is characterized in that, described fluorine-containing PET-PBT copolyesters melt is directly obtained or obtained through screw rod melting by fluorine-containing PET-PBT copolyester section by polymerization.

10. the preparation method of a kind of fluorine-containing PET-PBT copolyesters DTY fiber according to claim 3, it is characterized in that, described atactic polyether is a kind of in propylene glycol atactic polyether, butanols atactic polyether, laurate atactic polyether, lauryl alcohol atactic polyether and isomerous tridecanol atactic polyether; Described cithrol is a kind of in polyethylene glycol lauric acid monoester, polyethylene glycol laurate dibasic acid esters, polyethylene glycol oleic acid monoester and polyethylene glycol Glycol Oleic Acid Ester; Described phosphate kalium salt is a kind of in 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, isomerous tridecanol polyoxyethylene ether phosphate kalium salt and ten tetracosanol phosphate kalium salts; Described perfluoroalkyl acrylate is a kind of in perfluoro butyl ethyl propylene acid esters, perfluoro hexyl ethyl propylene acid esters, perfluoro capryl ethyl propylene acid esters, perfluoro butyl ethyl-methyl acrylate, perfluoro hexyl ethyl-methyl acrylate and perfluoro capryl ethyl-methyl acrylate.