CN109722736A - A kind of fluorine-containing binary acid modified poly ester FDY fiber and preparation method thereof - Google Patents

Abstract

The present invention relates to a kind of fluorine-containing binary acid modified poly ester FDY fibers and preparation method thereof, and fluorine-containing binary acid modified poly ester FDY fiber is made in the progress spinning of fluorine-containing binary acid modified poly ester melt；Fluorine-containing binary acid modified poly ester the preparation method comprises the following steps: Sb that terephthalic acid (TPA), ethylene glycol, fluorine-containing binary acid, the solid heteropoly acid powder by high-temperature roasting and doped metallic oxide is modified₂O₃Powder successively carries out esterification and polycondensation reaction, solid heteropoly acid SiO after mixing₂‑TiO₂、SiO₂‑ZrO₂、B₂O₃‑Al₂O₃、TiO₂- ZnO and SiO₂One or more of-CaO, after fluorine-containing binary acid modified poly ester FDY fiber is placed 60 months under conditions of temperature is 25 DEG C and relative humidity is 65%, inherent viscosity decline 20~26%.The method of the present invention simple process, fluorine-containing binary acid modified poly ester FDY fiber natural degradation are high-efficient and high-quality.

Description

A kind of fluorine-containing binary acid modified poly ester FDY fiber and preparation method thereof

Technical field

The invention belongs to modified fibre technical field, it is related to a kind of fluorine-containing binary acid modified poly ester FDY fiber and its preparation Method.

Background technique

Terylene is the product name of China's polyester fiber, is an important species in synthetic fibers.It is with essence to benzene Dioctyl phthalate (PTA) or dimethyl terephthalate (DMT) (DMT) and ethylene glycol (EG) are raw material through esterification or transesterification and polycondensation reaction Prepared by one polyethylene terephthalate of fiber-forming polymer (PET), through spinning and post-process made of fiber.Polyester is fine Dimension not only has good heat resistance, chemical resistance, mechanical property and electric property, but also has transparent good, insulating properties Advantage good, production cost is low and cost performance is high.

Waste will all be become after a large amount of polyester fiber use, although polyester (PET) directly will not cause to endanger to environment Evil, but it is huge using the amount of its bring waste product, while PET is stronger to repellence, that is, antidecomposition performance of atmosphere and microorganism (the decomposition period of PET is 16~48 years), it can thus be seen that PET waste brings huge pressure to environment, As a kind of global environmental contaminants.The main treating method of PET waste has at present: landfill is burned and is recycled. Although landfill and burning simple and fast, it can cause certain pollution to environment.Benefit is recycled after degrading to PET waste PET waste approach the most scientific is handled with being, but the ratio recycled at present still very little, with the maximum U.S. of accounting For market, average recovery rate is also only up to 13%, this is primarily due to, and PET construction is fine and close, crystallinity is high, nature Degradation time is longer, takes time and effort.

Currently, there are many research modified about PET both at home and abroad, change generally by some chemical properties for changing polyester The processing and service performance for becoming polyester product, so that resulting polyester product be made to reach the certain desired value of people.In general, polyester Method of modifying have that physics (blending) is modified, chemical (copolymerization) is modified, inorganic nanometer modified, reactive extrursion, addition and enhancing change Property and filling with it is composite modified etc., and physics and chemical modification are most common two classes method of modifying, however common modification Method is also not apparent from the natural degradation efficiency for improving PET, therefore improves the natural degradation rate of PET fiber and then improve its recycling Utilization rate is current urgent problem to be solved.

In addition, at this stage, in process of polyester synthesizing frequently with catalyst be antimony-based catalyst, common antimony system on the market Catalyst such as Sb₂O₃Additive amount in process of polyester synthesizing is larger, the larger shadow generated to environment of the additive amount of antimony-based catalyst Sound is also larger, is unfavorable for the environmental protection production of polyester, while antimony-based catalyst can be converted into antimony simple substance in polycondensation reaction, make polyester Color burnt hair brightness reduces, and antimony-based catalyst additive amount is bigger, bigger on influences such as the color of polyester and quality, but additive amount is small Antimony-based catalyst the reaction of all raw materials for participating in polyester synthesis can not be catalyzed, be unable to satisfy the need of production of polyester It wants.

It would therefore be highly desirable to study a kind of high-efficient and high-quality modified polyester fibre and preparation method thereof of natural degradation.

Summary of the invention

The purpose of the invention is to overcome above-mentioned problems of the prior art, it is high-efficient to provide a kind of natural degradation And high-quality fluorine-containing binary acid modified poly ester FDY fiber.

In order to achieve the above object, the technical solution adopted by the present invention are as follows:

A kind of preparation method of fluorine-containing binary acid modified poly ester FDY fiber carries out fluorine-containing binary acid modified poly ester melt Metering, spinneret squeezes out, cools down, oils, stretching, fluorine-containing binary acid modified poly ester FDY fiber is made in thermal finalization and winding；

The fluorine-containing binary acid modified poly ester the preparation method comprises the following steps: by terephthalic acid (TPA), ethylene glycol, fluorine-containing binary acid, warp Cross the solid heteropoly acid powder of high-temperature roasting and the Sb of doping vario-property₂O₃Powder successively carries out esterification and contracting after mixing Poly- reaction；

Fluorine-containing binary acid is the fluoro- 1,3- malonic acid of 2,2- bis-, the fluoro- 1,4- succinic acid of 2,2- bis-, the fluoro- 1,5- penta 2 of 2,2- bis- Acid or the fluoro- 1,4- succinic acid of 2,2,3,3- tetra-；

Fluorine-containing binary acid of the invention is characterized in that fluorine atom on α carbon, contains when introducing this in hydrolytic process When fluorine binary acid, since fluorine atom is on α carbon, electron-withdrawing ability is stronger, so that the cloud density in polyester on C-O key drops Low, the stability decline of tetrahedral anion is conducive to the progress of nucleophilic addition, simultaneously because fluorine-containing binary on α carbon The steric hindrance of acid is less than terephthalic acid (TPA), further promotes the progress of nucleophilic addition, thus significantly improves degradation Rate；

The temperature of solid heteropoly acid high-temperature roasting is 400~700 DEG C, and the purpose of high-temperature roasting is miscellaneous in removing polyester Matter, certain atmosphere and at a temperature of make catalyst intermediate (during the presoma of catalyst is to catalyst, presoma occur Reaction, the catalyst intermediates such as oxidation, reduction just refer to substance during this, and ingredient is uncertain, to refer to) it decomposes and activation, it is warm What the setting of degree mainly met is that catalyst intermediate is decomposed and activation condition, and the temperature of high-temperature roasting can in the appropriate range It is adjusted, but adjusts amplitude and should not be too large, the temperature of high-temperature roasting crosses high part SiO₂It can gasify, influence matching for setting Than the too low requirement that catalyst intermediate is not achieved and decomposes and activates of temperature；

Solid heteropoly acid is SiO₂-TiO₂、SiO₂-ZrO₂、B₂O₃-Al₂O₃、TiO₂- ZnO and SiO₂One of-CaO with On；

The preparation process of above-mentioned solid heteropoly acid of the invention can be as follows:

Solid heteropoly acid SiO₂-TiO₂Specific preparation process are as follows:

By weight, firstly, 1 part of silicon-dioxide powdery and 50-60 parts of water are dispersed with stirring, be added dropwise 2-3 parts it is dense Degree is the titanyl sulfate solution of 4-5wt%, then the sodium hydroxide solution for being 0.5-1.0mol/L with concentration adjusts pH value to neutrality, Then the sulphur acid for adjusting pH value for being 8-10wt% with concentration is 8, and after being aged 1-2h, deionized water is washed to no SO₄ ^2-After filter, Filter cake is repeatedly washed with dehydrated alcohol, then is placed in drying box and is dried under the conditions of 100 DEG C of temperature, and finally sample exists respectively 2-4h is calcined at 400 DEG C -700 DEG C, obtains solid heteropoly acid SiO₂-TiO₂。

Solid heteropoly acid SiO₂-ZrO₂Specific preparation process are as follows:

By weight, firstly, 1 part of silicon-dioxide powdery and 50-60 parts of water are dispersed with stirring, 2-3 parts are added dropwise Concentration is the sulfuric acid zirconium solution of 4-5wt%, then the sodium hydroxide solution for being 0.5-1.0mol/L with concentration adjusts pH value to neutrality, Then the sulphur acid for adjusting pH value for being 8-10wt% with concentration is 8, and after being aged 1-2h, deionized water is washed to no SO₄ ^2-After filter, Filter cake is repeatedly washed with dehydrated alcohol, then is placed in drying box and is dried under the conditions of 100 DEG C of temperature, and finally sample exists respectively 2-4h is calcined at 400 DEG C -700 DEG C, obtains solid heteropoly acid SiO₂-ZrO₂。

Solid heteropoly acid B₂O₃-Al₂O₃Specific preparation process are as follows:

By weight, firstly, it is 4-5wt% aluminum sulfate solution that 2-3 parts of concentration are added dropwise into 1 part of boric acid, then PH value is adjusted to neutrality, the sulfuric acid tune for being then 8-10wt% with concentration with the sodium hydroxide solution that concentration is 0.5-1.0mol/L Saving pH value is 8, and after being aged 1-2h, deionized water is washed to no SO₄ ^2-After filter, filter cake is repeatedly washed with dehydrated alcohol, then is placed in It is dried under the conditions of 100 DEG C of temperature in drying box, sample is finally calcined into 2-4h at 400 DEG C -700 DEG C respectively, obtains solid Heteropoly acid B₂O₃-Al₂O₃。

Solid heteropoly acid TiO₂The specific preparation process of-ZnO are as follows:

By weight, firstly, it is that 4-5wt% titanyl sulfate is molten that 2-3 parts of concentration are added dropwise into 1 part of zinc sulfate Liquid, then the sodium hydroxide solution for being 0.5-1.0mol/L with concentration adjust pH value to neutrality, are then 8-10wt%'s with concentration Sulphur acid for adjusting pH value is 8, and after being aged 1-2h, deionized water is washed to no SO₄ ^2-After filter, filter cake is repeatedly washed with dehydrated alcohol It is placed in drying box and is dried under the conditions of 100 DEG C of temperature again, sample is finally calcined into 2-4h at 400 DEG C -700 DEG C respectively, is obtained To solid heteropoly acid TiO₂-ZnO。

Solid heteropoly acid SiO₂The specific preparation process of-CaO are as follows:

By weight, firstly, 1 part of silicon-dioxide powdery and 50-60 parts of water are dispersed with stirring, 2-3 parts are added dropwise Concentration is 4-5wt% calcium sulphate soln, then the sodium hydroxide solution for being 0.5-1.0mol/L with concentration adjusts pH value to neutrality, connects Be 8-10wt% with concentration sulphur acid for adjusting pH value be 8, be aged 1-2h after, deionized water is washed to no SO₄ ^2-After filter, filter Cake is repeatedly washed to be placed in again in drying box with dehydrated alcohol dries under the conditions of 100 DEG C of temperature, finally by sample respectively 400 2-4h is calcined at DEG C -700 DEG C, obtains solid heteropoly acid SiO₂-CaO。

Since the carboxyl end group in polyester system is that polyester hydrolyzes most first occurred position, on the hydroxyl oxygen atom in carboxyl The pi-electron of unshared electron pair and carbonyl is gripped altogether, occurs the delocalization of electronics, delocalization the result is that hydrogen-oxygen key active force subtracts It is weak, so that carboxylic acid is dissociated into anion and proton, the carboxyl anion generated after dissociation is also due to the delocalization of electronics makes the negative of carboxyl Charge mean allocation increases the stability of carboxyl anion, is conducive to carboxylic acid and is dissociated into ion on two oxygen atoms.This hair It is bright by introducing solid heteropoly acid in polyester preparation process, solid heteropoly acid, which can dissociate, generates H⁺Ion, H⁺Ion can be into It attacks carboxyl anion and generates the tetrahedral intermediate with cation, so that the oxygen of carbonyl protonates, it is positively charged on oxygen, thus Attract the electronics in carbonyl carbon, make carbonyl carbon that there is electropositive, to be easier by the weaker nucleopilic reagent of alkalinity (such as H₂O) Attack, after nucleopilic reagent attack, the acyloxy of tetrahedral intermediate is broken, and is resolved into acid and alcohol, is so recycled, carbonyl It is constantly destroyed, macromolecular chain is constantly broken, and content of carboxyl end group is continuously increased, and is further promoted polyester hydrolysis, is improved water Solve rate.

Sb₂O₃The process of doping vario-property are as follows: first by metal ion N^y+Solution with contain Sb³⁺Solution be uniformly mixed, Then the pH value that precipitating reagent is added dropwise to mixed liquor is 9~10, finally calcines precipitated product；

Metal ion N^y+For Mg²⁺、Ca²⁺、Ba²⁺And Zn²⁺One or more of.

The present invention is by by metal ion N^y+Solution with contain Sb³⁺Solution first be uniformly mixed reprecipitation finally calcine So that the doping and blending of metal oxide and antimony oxide with certain catalytic activity is realized, metal oxide MgO, After one or more of CaO, BaO and ZnO, metal oxide of the invention and antimony oxide doping, metal oxide passes through Inhibit antimony oxide crystallization and cubic crystal antimony oxide crystal grain grow up and same order elements antimony and enter antimony lattice Position makes antimony oxide crystal generate defect, and crystal habit generates variation, and crystallite dimension becomes smaller, improves antimony oxide and urge The specific surface area S of agent_g, while metal can also be enriched in part antimony oxide plane of crystal, make antimony oxide unit table Active r on area_sIncrease, specific surface area S_gWith the active r in per surface area_sBigger, the catalytic activity of catalyst is higher, Therefore the present invention can be in low Sb₂O₃Catalyzing and synthesizing for polyester is realized under additive amount, is good for the environment production and guarantees synthesis polyester Quality.

As a preferred technical scheme:

A kind of preparation method of fluorine-containing binary acid modified poly ester FDY fiber as described above, the time of high-temperature roasting is 2~ 4h；SiO₂-TiO₂、SiO₂-ZrO₂、B₂O₃-Al₂O₃、TiO₂- ZnO and SiO₂TiO in-CaO₂、ZrO₂、Al₂O₃, ZnO and CaO contain Amount is respectively 30~50wt%, 30~50wt%, 20~40wt%, 20~40wt% and 20~50wt%；Solid heteropoly acid exists It is crushed to obtain powder of the average grain diameter less than 0.5 micron after high-temperature roasting；

To Sb₂O₃When being doped modified, the metal ion N^y+Solution concentration be 0.5~1.0mol%, it is molten Agent is water, and the anion in solution is NO₃ ^-；It is described to contain Sb³⁺Solution be 5~10mol% of concentration Sb₂O₃Solution, solvent For oxalic acid；The precipitating reagent is the ammonium hydroxide of concentration 2mol/L；When precipitating starts, metal ion N in mixed solution^y+With Sb³⁺Rub You are than being 1~3:100；Sb₂O₃It is the highest polyester catalyst of current cost performance, the present invention is inhibited by penetrating into metal oxide Antimony oxide (Sb₂O₃) crystallization and cubic crystal antimony oxide crystal grain grow up, while metal ion N^y+Antimony can be replaced and Into the lattice position of antimony, so that antimony oxide crystal generates defect, to improve the catalytic activity of antimony oxide.Such as adulterate gold It is very few (molar ratio is too low) to belong to oxide amount, relatively low on the influence of antimony oxide crystal grain, excessive (molar ratio is excessively high) can to urge The main body Sb of agent³⁺Fall is bigger than normal, unfavorable to antimony oxide catalytic activity is improved；

Precipitated product is washed and is dried before the calcining, dry temperature be 105~110 DEG C, the time be 2~ 3h；The process of the calcining are as follows: keep the temperature 2~3h after being warming up to 400 DEG C first, 1~2h is kept the temperature after then heating to 900 DEG C, most It cools down in air afterwards；Sb₂O₃It is crushed to obtain powder of the average grain diameter less than 0.5 micron after doping vario-property.

A kind of preparation method of fluorine-containing binary acid modified poly ester FDY fiber as described above, the fluorine-containing binary acid are modified The preparation step of polyester is as follows:

(1) esterification；

Terephthalic acid (TPA), ethylene glycol and fluorine-containing binary acid are made into slurry, the solid heteropoly acid Jing Guo high-temperature roasting is added The Sb of powder, doping vario-property₂O₃After mixing, pressurization be esterified anti-in nitrogen atmosphere for powder, delustering agent and stabilizer It answers, moulding pressure is normal pressure~0.3MPa, and the temperature of esterification is 250~260 DEG C, when the water quantity of distillate in esterification reaches To theoretical value 90% or more when be esterification terminal；

(2) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure 30~ Absolute pressure 500Pa being steadily evacuated to by normal pressure in 50min hereinafter, reaction temperature is 250~260 DEG C, the reaction time is 30~ 50min then proceedes to vacuumize, and carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be further reduced to absolute pressure For 100Pa hereinafter, reaction temperature is 270~282 DEG C, the reaction time is 50~90min.

A kind of preparation method of fluorine-containing binary acid modified poly ester FDY fiber as described above, the terephthalic acid (TPA), second two The molar ratio of pure and mild fluorine-containing binary acid is 1:1.2~2.0:0.05~0.07, and the additional amount of the fluorine-containing binary acid of the present invention is simultaneously unlimited In this, those skilled in the art can actual conditions be adjusted, but adjust amplitude should not be too large, additive amount is excessive to divide greatly polyester The regularity of minor structure destroy it is too big, it is excessive to the crystallinity and Effect on Mechanical Properties of fiber, be unfavorable for fiber production and Using additive amount is too low, then effect is unobvious；

The Sb of the solid heteropoly acid powder by high-temperature roasting, doping vario-property₂O₃Powder, delustering agent and stabilizer Additional amount is respectively the 0.13~0.15wt%, 0.012~0.015wt%, 0.20~0.25wt% of terephthalic acid (TPA) additional amount It is not limited to this with the additional amount of 0.01~0.05wt%, solid heteropoly acid of the present invention, those skilled in the art can actual conditions It is adjusted, but adjusts amplitude and should not be too large, the excessive regularity destruction to polyester macromolecule structure of additive amount is too big, to fiber Crystallinity and Effect on Mechanical Properties it is excessive, be unfavorable for the production and application of fiber, additive amount is too low, then effect is unobvious；

Sb in process of polyester synthesizing in the prior art₂O₃Additional amount be usually terephthalic acid (TPA) additional amount 0.02~ The additional amount of 0.04wt%, antimony-based catalyst are high, and this is mainly due to undoped Sb₂O₃Active r in per surface area_sIt is low And specific surface area S_gIt is small, therefore Sb₂O₃Whole catalytic activity is lower, and the present invention passes through to Sb₂O₃It is doped modification, is improved Sb₂O₃Activity, therefore significantly reduce Sb in process of polyester synthesizing₂O₃Additive amount.

A kind of preparation method of fluorine-containing binary acid modified poly ester FDY fiber as described above, the delustering agent are titanium dioxide Titanium, the stabilizer are triphenyl phosphate, trimethyl phosphate or Trimethyl phosphite.

A kind of fluorine-containing binary acid modified poly ester FDY fiber as described above, the equal molecule of number of fluorine-containing binary acid modified poly ester Amount is 25000~30000, and molecular weight distributing index is 1.8~2.2.

A kind of preparation method of fluorine-containing binary acid modified poly ester FDY fiber as described above, the fluorine-containing binary acid are modified The spinning technology parameter of polyester FDY fiber are as follows: 280~290 DEG C of spinning temperature, 20~25 DEG C of cooling temperature, network pressure 0.20 ~0.30MPa, a 2200~2600m/min of roller speed, 75~90 DEG C of a roll temperature, two roller speed 3600~3900m/min, two 115~135 DEG C of roll temperature, 3560~3830m/min of winding speed.

The present invention also provides using as made from a kind of preparation method of above-mentioned fluorine-containing binary acid modified poly ester FDY fiber A kind of fluorine-containing binary acid modified poly ester FDY fiber, the strand of fluorine-containing binary acid modified poly ester include terephthalic acid (TPA) segment, second Glycol segment and fluorine-containing binary acid segment；

The solid heteropoly acid powder by high-temperature roasting and described is dispersed in the fluorine-containing binary acid modified poly ester The Sb of doping vario-property₂O₃Powder.

As a preferred technical scheme:

A kind of fluorine-containing binary acid modified poly ester FDY fiber as described above, the list of fluorine-containing binary acid modified poly ester FDY fiber Silk size is 1.5~3.0dtex, and breaking strength >=3.5cN/dtex, elongation at break is 25.0 ± 3.0%, internet pricing 12 ± 3/m, line density deviation ratio≤1.0%, breaking strength CV value≤5.0%, extension at break CV value≤8.0%, boiling shrinkage Rate is 8.0 ± 0.5%；The above-mentioned mechanical property of fiber obtained by the present invention does not decline, suitable with the prior art；

A kind of fluorine-containing binary acid modified poly ester FDY fiber as described above, fluorine-containing binary acid modified poly ester FDY fiber is in temperature Degree for 25 DEG C and relative humidity be 65% under conditions of places 60 months after, inherent viscosity declines 20~26%；The same terms Under, the inherent viscosity decline 4.6% of comparative sample, the difference of comparative sample and fluorine-containing binary acid modified poly ester FDY fiber of the invention It is that its material is conventional polyester and is not added with solid heteropoly acid powder by high-temperature roasting.

Invention mechanism:

The present invention in process of polyester synthesizing by adding the Sb of fluorine-containing binary acid, doping vario-property₂O₃Powder and solid are miscellaneous more Acid, to significantly improve the natural degradation efficiency of polyester, specific mechanism on the basis of guaranteeing polyester fiber quality are as follows:

(1) for the Sb of doping vario-property₂O₃Powder:

The Sb of doping vario-property of the invention₂O₃Powder primarily serves the effect of catalyst, existing skill in process of polyester synthesizing Polyester catalyst in art is mainly based on antimonial, such as antimony oxide, antimony glycol and antimony acetate, industrial polyester The additional amount of antimony is greater than 200ppm in synthesis, since antimony is heavy metal, the progress in epoch, for antimony catalyst restriction increasingly It sternly,, still can not be in a short time due to color and activity control etc. are various although the catalysis of titanium system is applied Replace antimony system.

The catalytic activity of catalyst and the specific surface area S of catalyst_g, in utilization rate of inner surface f and per surface area Active r_sDirectly proportional, certain for component catalyst, catalytic activity depend on the specific surface area S of the catalyst_gAnd inner surface Utilization rate f, the active r in catalyst per surface area_sOne timing, specific surface area is bigger, and catalytic activity is higher.

The present invention is co-precipitated to calcine again again by first solution blending realizes the gold with certain catalyzed polycondensation reactivity Belong to the doping and blending of oxide and antimony oxide, one or more of metal oxide MgO, CaO, BaO and ZnO, valence Position and the price of antimony have a certain difference, and there is also certain difference, these differences can change for ionic radius and antimony The crystal plane structure of antimony oxide, to influence correlated performance.In addition, MgO, CaO, BaO, ZnO are white crystal, as poly- Ester catalyst will not bring the variation on color.

Influence of the metal oxide to antimony oxide is mainly reflected in: on the one hand, metal oxide can inhibit three oxidations The crystallization of two antimony and growing up for cubic crystal antimony oxide crystal grain make the specific surface area S of antimony oxide catalyst_gIt improves, mentions The high catalytic activity of antimony oxide；On the other hand, metal understands the lattice position of same order elements antimony and entrance antimony, makes three oxidations two Antimony crystal generates defect, and crystal habit generates variation, and crystallite dimension becomes smaller, specific surface area S_gIncrease, while in partial crystals table Face makes metal enrichment, makes the active r in its per surface area_sIt improves, improves the catalytic activity of antimony oxide.As will be only had There is the metal oxide of certain catalyzed polycondensation reactivity to be blended with antimony oxide simple physical, the catalysis of antimony oxide is living Property will not significantly improve because simple physical be blended, crystal defect will not be generated, crystal habit does not generate variation, crystal grain Size remains unchanged, and the total surface area of crystal is constant, will not have an impact to catalytic activity.

The present invention improves the catalytic activity of antimony trioxide, three oxygen by being doped to antimony trioxide in a degree The catalytic activity for changing antimony, which improves, advantageously reduces the usage amount of antimony trioxide, in process of polyester synthesizing, protects in polycondensating process condition It holds in the case that constant and polyester reaches identical index, after being doped using metal oxide to antimony trioxide, three oxidations The usage amount of antimony can reduce 30% or more, efficiently solve the problems, such as that additive amount existing for current antimony trioxide is big, while can Meet the needs of production of polyester, guarantees production of polyester quality.

(2) the fluorine-containing binary acid for being introduced in polyester molecule chain:

The hydrolytic degradation process of polyester under alkaline condition is nucleophilic addition-elimination process, when hydrolysis starts, OH^-Nucleophilic addition occurs for the C atom of attack ester carbonyl group RCOOR`, is formed intermediate (i.e. tetrahedral anion), four sides The anion of body can eliminate OR` and obtain carboxylic acid RCOOH, make ester linkage breaking, while OR` and H<sup>+</sup>In conjunction with obtaining alcohol HOR`.However, Since the tetrahedral anion structure formed in hydrolytic process is more crowded, steric hindrance is big, and it is anti-to be unfavorable for nucleophilic addition The progress answered, therefore the degradation rate of polyester is slower.

The present invention significantly improves the degradation of polyester by introducing the fluorine-containing binary acid of special construction in polyester molecule chain Rate, fluorine-containing binary acid is characterized in that fluorine atom on α carbon, when introducing the fluorine-containing binary acid in hydrolytic process, Since fluorine atom is on α carbon, electron-withdrawing ability is stronger, so that the cloud density in polyester on C-O key reduces, it is tetrahedral The stability of anion declines, and is conducive to the progress of nucleophilic addition, simultaneously because on α carbon fluorine-containing binary acid steric hindrance Less than terephthalic acid (TPA), the progress of nucleophilic addition is further promoted, thus significantly improves degradation rate.Such as in polyester Fluorine atom is introduced in strand in the fluorine-containing binary acid of β carbon, then the degradation rate of polyester will not be significantly improved, this is because in β There are when electron-withdrawing group on carbon, generated influence is limited only on adjacent carbons, and the influence to C-O key generation in ester bond is very It is small, thus for OH^-The reaction that nucleophilic addition occurs for attack ester carbonyl group influences smaller.

(3) solid heteropoly acid for being added in polyester:

The hydrolysis of polyester is the back reaction of esterification, and its essence is the fracture processes of acyl-oxygen key in ester bond, i.e., close Nucleophilic addition occurs on carbonyl for core reagent, eliminates anion completion hydrolysis after forming tetrahedral intermediate.Conventional polyester hydrolysis A slower major reason of rate be carbonylic carbon atom in polyester receive nucleopilic reagent attack ability it is low, this is because poly- All it is electron donating group around carbonylic carbon atom in ester, lacks electron-withdrawing group, the carbonylic carbon atom in polyester is caused to connect Ability by nucleopilic reagent attack is low, and nucleophilic could be occurred with the carbonylic carbon atom in polyester by generally requiring stronger nucleophilic group Reaction.

The present invention is added solid heteropoly acid and significantly improves carbonylic carbon atom in polyester by preparing in polyester in raw material Receive the ability of nucleopilic reagent attack, and then improves the hydrolysis rate of polyester.The solid heteropoly acid that the present invention selects is a kind of It is urged by the highly acid multicore complex acid that oxygen atom bridging hetero atom (central atom) and metallic atom (coordination atom) form Agent, high temperature resistant and resistance to catalytic performance are strong, and catalysis is from the acid present on the surface of solids with catalytic activity Property position, due to its high temperature resistant, thus solid heteropoly acid can be added in polyester synthesis；Since the esterification of polyester is in acid It is carried out under the conditions of property, acid can be used as polyester esterification catalyst, thus the addition of solid heteropoly acid will not generate polymerization reaction Adverse effect only may consequently contribute to the esterification of terephthalic acid (TPA) and ethylene glycol, reduce esterification reaction temperature, reduce esterification process Side reaction.

Carboxyl end group in polyester system is that polyester hydrolyzes most first occurred position, untotal on the hydroxyl oxygen atom in carboxyl Gripped altogether with electronics pair and the pi-electron of carbonyl, occur the delocalization of electronics, delocalization the result is that hydrogen-oxygen key reaction force attenuation, makes Carboxylic acid is dissociated into anion and proton, and the carboxyl anion generated after dissociation is also due to the delocalization of electronics keeps the negative electrical charge of carboxyl flat It is allocated on two oxygen atoms, increases the stability of carboxyl anion, be conducive to carboxylic acid and be dissociated into ion.Solid heteropoly acid It can dissociate and generate H⁺Ion, H⁺Ion can attack carboxyl anion generate the tetrahedral intermediate with cation so that carbonyl The oxygen of base protonates, positively charged on oxygen, to attract the electronics in carbonyl carbon, so that carbonyl carbon is had electropositive, to more hold Easily by the weaker nucleopilic reagent of alkalinity (such as H₂O) attack, after nucleopilic reagent attack, the acyloxy of tetrahedral intermediate occurs Fracture is resolved into acid and alcohol, is so recycled, and carbonyl is constantly destroyed, and macromolecular chain is constantly broken, and content of carboxyl end group constantly increases Add, further promotes polyester hydrolysis, improve hydrolysis rate.

The utility model has the advantages that

(1) preparation method of fluorine-containing binary acid modified poly ester FDY fiber of the invention, by with certain catalytic activity Metal oxide improves antimony oxide specific surface area S to the doping vario-property of antimony oxide_gWith the work in per surface area Property r_s, to improve the catalytic activity of antimony oxide, improve polymerization efficiency；And then production of polyester needs can met While reduce synthesis polyester when antimony-based catalyst additive amount, effectively reduce be made thereafter fiber antimony discharge, be conducive to Realize environmental protection production；

(2) preparation method of fluorine-containing binary acid modified poly ester FDY fiber of the invention, by adding fluorine-containing binary acid to poly- Ester is modified, and reduces the cloud density in polyester on C-O key, simultaneously because on α carbon fluorine-containing binary acid space bit Resistance is less than terephthalic acid (TPA), further promotes the progress of nucleophilic addition, improves the degradation rate of polyester, is used for clothes Weaving can effectively solve the problems, such as that waste and old clothes recycle；

(3) preparation method of fluorine-containing binary acid modified poly ester FDY fiber of the invention, by the preparation process of polyester Addition solid heteropoly acid significantly improves the ability that the carbonylic carbon atom in polyester receives nucleopilic reagent attack, and then improves poly- Ester hydrolysis rate can effectively solve the problems, such as that waste and old clothes recycle；

(4) fluorine-containing binary acid modified poly ester FDY fiber and preparation method thereof of the invention, modified poly ester FDY obtained are fine Dimension natural degradation is high-efficient, and good mechanical performance is high-quality.

Specific embodiment

The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Fixed range.

Embodiment 1

A kind of preparation method of fluorine-containing binary acid modified poly ester FDY fiber, the specific steps are as follows:

(1) fluorine-containing binary acid modified poly ester is prepared；

(1.1) Sb of doping vario-property is prepared₂O₃；

Mg (the NO that concentration is 0.8mol% by (1.1.1)₃)₂The Sb that aqueous solution and concentration are 8mol%₂O₃Solution mixing Uniformly, Sb₂O₃The solvent of solution be oxalic acid, Mg in mixed liquor²⁺With Sb³⁺Molar ratio be 2:100；

The pH value that ammonium hydroxide to mixed liquor that concentration is 2mol/L is added dropwise in (1.1.2) is 9 to obtain precipitated product, then to precipitating Product is washed and is dried, and dry temperature is 105 DEG C, time 2.5h；

(1.1.3) keeps the temperature 2.5h after the product after drying is warming up to 400 DEG C first, keeps the temperature after then heating to 900 DEG C 1.5h is crushed after finally cooling down in air and is obtained the Sb for the doping vario-property that average grain diameter is 0.4 micron₂O₃Powder；

(1.2) solid heteropoly acid SiO is prepared₂-TiO₂Powder；

By weight, firstly, 1 part of silicon-dioxide powdery and 55 parts of water are dispersed with stirring, 2 parts of concentration, which are added dropwise, is The titanyl sulfate solution of 4.5wt%, then the sodium hydroxide solution for being 1.0mol/L with concentration adjust pH value to neutrality, then with dense The sulphur acid for adjusting pH value that degree is 10wt% is 8, and after being aged 2h, deionized water is washed to no SO₄ ^2-After filter, the anhydrous second of filter cake Alcohol repeatedly washs, then is placed in drying box and dries under the conditions of 100 DEG C of temperature, and sample is finally calcined 2h at 500 DEG C respectively It is crushed to obtain the solid heteropoly acid SiO that average grain diameter is 0.4 micron afterwards₂-TiO₂Powder, SiO₂-TiO₂Middle TiO₂Content For 42wt%；

(1.3) esterification；

By terephthalic acid (TPA), ethylene glycol and 2, fluoro- 1, the 3- malonic acid of 2- bis- is made into slurry, and solid heteropoly acid SiO is added₂- TiO₂The Sb of powder, doping vario-property₂O₃Powder, titanium dioxide and triphenyl phosphate after mixing, pressurize in nitrogen atmosphere into Row esterification, moulding pressure 0.3MPa, the temperature of esterification is 250 DEG C, when the water quantity of distillate in esterification reaches Theoretical value 90% when be esterification terminal, the molar ratio of terephthalic acid (TPA), ethylene glycol and 2, fluoro- 1, the 3- malonic acid of 2- bis- is 1:1.5:0.03 solid heteropoly acid SiO₂-TiO₂The Sb of powder, doping vario-property₂O₃Powder, titanium dioxide and triphenyl phosphate Additional amount is respectively 0.15wt%, 0.012wt%, 0.20wt% and 0.01wt% of terephthalic acid (TPA) additional amount；

(1.4) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 30min Interior that absolute pressure 499Pa is steadily evacuated to by normal pressure, reaction temperature is 250 DEG C, and reaction time 30min then proceedes to vacuumize, The polycondensation reaction for carrying out high vacuum stage of Fig makes reaction pressure be further reduced to absolute pressure 99Pa, and reaction temperature is 270 DEG C, instead It is 50min between seasonable, it is 25000 that number-average molecular weight, which is made, the fluorine-containing binary acid modified poly ester that molecular weight distributing index is 1.8；

(2) fluorine-containing binary acid modified poly ester melt is measured, spinneret is squeezed out, cools down, oils, stretched, thermal finalization Fluorine-containing binary acid modified poly ester FDY fiber, spinning technology parameter is made with winding are as follows: 280 DEG C of spinning temperature, cooling temperature 20 DEG C, network pressure 0.20MPa, a roller speed 2200m/min, 75 DEG C of a roll temperature, two roller speed 3600m/min, two roll temperatures 115 DEG C, winding speed 3560m/min.

The filament number of final fluorine-containing binary acid modified poly ester FDY fiber obtained is 3.0dtex, and breaking strength is 3.8cN/dtex, elongation at break 28.0%, internet pricing are 15/m, and line density deviation ratio is 0.8%, breaking strength CV value It is 4.0%, extension at break CV value is 6.4%, boiling water shrinkage 8.5%；It is 25 DEG C in temperature and relative humidity is 65% Under conditions of place 60 months after, inherent viscosity decline 20%.

Comparative example 1

A kind of modified poly ester FDY preparation methods, specific steps are substantially the same manner as Example 1, and difference is, step (1) the fluoro- 1,3- malonic acid of 2,2- bis- and solid heteropoly acid SiO are not added in₂-TiO₂Powder, while using routine Sb₂O₃Replacement The Sb of doping vario-property₂O₃Powder, conventional Sb₂O₃Additive amount be terephthalic acid (TPA) additional amount 0.03wt%.Change made from final Property polyester FDY filament number be 3.0dtex, breaking strength 3.7cN/dtex, elongation at break 29.0%, internet pricing For 15/m, line density deviation ratio is 0.8%, and breaking strength CV value is 4.0%, and extension at break CV value is 6.4%, boiling shrinkage Rate is 8.5%；After it is placed 60 months under conditions of temperature is 25 DEG C and relative humidity is 65%, inherent viscosity decline 4.3%.

Comparative example 2

A kind of modified poly ester FDY preparation methods, specific steps are substantially the same manner as Example 1, and difference is, step (1) the fluoro- 1,3- malonic acid of 2,2- bis- is not added in.The filament number of final modified poly ester FDY obtained is 3.0dtex, is broken Resistance to spalling is 3.6cN/dtex, and elongation at break 30.0%, internet pricing is 15/m, and line density deviation ratio is 0.8%, fracture Intensity CV value is 4.0%, and extension at break CV value is 6.4%, boiling water shrinkage 8.5%；It is for 25 DEG C and relatively wet in temperature After degree is placed 60 months under conditions of being 65%, inherent viscosity decline 10.7%.

Comparative example 3

A kind of modified poly ester FDY preparation methods, specific steps are substantially the same manner as Example 1, and difference is, step (1) solid heteropoly acid SiO is not added in₂-TiO₂Powder.The filament number of final modified poly ester FDY obtained is 3.0dtex, Breaking strength is 3.5cN/dtex, and elongation at break 27.0%, internet pricing is 15/m, and line density deviation ratio is 0.8%, is broken Resistance to spalling CV value is 4.0%, and extension at break CV value is 6.4%, boiling water shrinkage 8.6%；It is for 25 DEG C and opposite in temperature After humidity is placed 60 months under conditions of being 65%, inherent viscosity decline 13%.

Comparative example 4

A kind of modified poly ester FDY preparation methods, specific steps are substantially the same manner as Example 1, and difference is, step (1) routine Sb is used in₂O₃Replace the Sb of doping vario-property₂O₃Powder, conventional Sb₂O₃Additive amount be terephthalic acid (TPA) additional amount 0.03wt%.The filament number of final modified poly ester FDY obtained is 3.0dtex, breaking strength 3.7cN/dtex, fracture Elongation is 29.0%, and internet pricing is 15/m, and line density deviation ratio is 0.8%, and breaking strength CV value is 4.0%, and fracture is stretched Long CV value is 6.4%, boiling water shrinkage 8.5%；It places 60 under conditions of temperature is 25 DEG C and relative humidity is 65% After a month, inherent viscosity decline 20.7%.

Comprehensive analysis embodiment 1 and comparative example 1~4 are it can be found that the present invention passes through addition fluoro- 1, the 3- malonic acid of 2,2- bis- With solid heteropoly acid SiO₂-TiO₂Powder has been obviously improved the natural degradation performance of fiber, wherein 2,2- bis- fluoro- 1,3- malonic acid With solid heteropoly acid SiO₂-TiO₂Powder mutually cooperates with, and 2,2- bis- fluoro- 1,3- malonic acid reduce the electronics in polyester on C-O key Cloud density promotes natural degradation reaction, solid heteropoly acid SiO₂-TiO₂Powder improves the receiving of the carbonylic carbon atom in polyester The ability of nucleopilic reagent attack further improves natural degradation performance.In addition, 2,2- bis- fluoro- 1,3- malonic acid and solid are miscellaneous Polyacid SiO₂-TiO₂The addition of powder is smaller on the influence of other performances of fiber, has no effect on its processing performance and mechanical performance.This Invention uses the Sb of doping vario-property₂O₃Powder replaces routine Sb₂O₃It significantly reduces and urges while ensure that same catalytic activity The additional amount of agent has achieved the purpose that reduce antimony discharge.

Comparative example 5

A kind of modified poly ester FDY preparation methods, specific steps are substantially the same manner as Example 1, and difference is, step (1) the fluoro- 1,3- malonic acid of 2,2- bis- is substituted using 3,3- difluoro glutaric acid in.The monofilament of final modified poly ester FDY obtained Fiber number is 3.0dtex, and breaking strength 3.6cN/dtex, elongation at break 30.0%, internet pricing is 15/m, and line density is inclined Rate is 0.8%, and breaking strength CV value is 4.0%, and extension at break CV value is 6.4%, boiling water shrinkage 8.5%；It is in temperature Degree for 25 DEG C and relative humidity be 65% under conditions of places 60 months after, inherent viscosity declines 10.5%.

With embodiment 1 comparison it can be found that fluorine atom α carbon fluorine-containing binary acid relative to fluorine atom in the fluorine-containing of β carbon Binary acid is more advantageous to the natural degradation performance for promoting fiber, this is because on β carbon there are when electron-withdrawing group, it is generated Influence is limited only on adjacent carbons, and to the influence very little that C-O key in ester bond generates, thus for OH^-Attack ester carbonyl group occurs The reaction of nucleophilic addition influences smaller and then smaller on the influence of the natural degradation process of fiber.

Embodiment 2

A kind of preparation method of fluorine-containing binary acid modified poly ester FDY fiber, the specific steps are as follows:

(1) fluorine-containing binary acid modified poly ester is prepared；

(1.1) Sb of doping vario-property is prepared₂O₃；

Ca (the NO that concentration is 0.5mol% by (1.1.1)₃)₂The Sb that aqueous solution and concentration are 5mol%₂O₃Solution mixing Uniformly, Sb₂O₃The solvent of solution be oxalic acid, Ca in mixed liquor²⁺With Sb³⁺Molar ratio be 1:100；

The pH value that ammonium hydroxide to mixed liquor that concentration is 2mol/L is added dropwise in (1.1.2) is 10 to obtain precipitated product, then to heavy Shallow lake product is washed and is dried, and dry temperature is 110 DEG C, time 2h；

(1.1.3) keeps the temperature 2h after the product after drying is warming up to 400 DEG C first, keeps the temperature 1h after then heating to 900 DEG C, It is crushed after finally cooling down in air and obtains the Sb for the doping vario-property that average grain diameter is 0.4 micron₂O₃Powder；

(1.2) solid heteropoly acid SiO is prepared₂-ZrO₂Powder；

By weight, firstly, 1 part of silicon-dioxide powdery and 58 parts of water are dispersed with stirring, 2 parts of concentration, which are added dropwise, is The sulfuric acid zirconium solution of 5wt%, then the sodium hydroxide solution for being 1.0mol/L with concentration adjust pH value to neutrality, are then with concentration The sulphur acid for adjusting pH value of 10wt% is 8, and after being aged 1h, deionized water is washed to no SO₄ ^2-After filter, filter cake dehydrated alcohol is more Secondary washing, then be placed in drying box and dried under the conditions of 100 DEG C of temperature, after sample is finally calcined 4h at 400 DEG C DEG C respectively It is crushed to obtain the solid heteropoly acid SiO that average grain diameter is 0.45 micron₂-ZrO₂Powder, SiO₂-ZrO₂Middle ZrO₂Content be 45wt%；

(1.3) esterification；

By terephthalic acid (TPA), ethylene glycol and 2, the fluoro- 1, 4- succinic acid of 2- bis- is made into slurry, and solid heteropoly acid SiO is added₂- ZrO₂The Sb of powder, doping vario-property₂O₃Powder, titanium dioxide and trimethyl phosphate after mixing, in normal pressure in nitrogen atmosphere Lower carry out esterification, the temperature of esterification is 260 DEG C, when the water quantity of distillate in esterification reaches the 95% of theoretical value For esterification terminal, terephthalic acid (TPA), ethylene glycol and 2, the molar ratio of the fluoro- 1, 4- succinic acid of 2- bis- is 1:1.2.0:0.055, Solid heteropoly acid SiO₂-ZrO₂The Sb of powder, doping vario-property₂O₃The additional amount of powder, titanium dioxide and trimethyl phosphate is respectively 0.13wt%, 0.012wt%, 0.25wt% and 0.05wt% of terephthalic acid (TPA) additional amount；

(1.4) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 50min Interior that absolute pressure 450Pa is steadily evacuated to by normal pressure, reaction temperature is 260 DEG C, and reaction time 50min then proceedes to vacuumize, The polycondensation reaction for carrying out high vacuum stage of Fig makes reaction pressure be further reduced to absolute pressure 90Pa, and reaction temperature is 282 DEG C, instead It is 90min between seasonable, it is 30000 that number-average molecular weight, which is made, the fluorine-containing binary acid modified poly ester that molecular weight distributing index is 2.2；

(2) fluorine-containing binary acid modified poly ester melt is measured, spinneret is squeezed out, cools down, oils, stretched, thermal finalization Fluorine-containing binary acid modified poly ester FDY fiber, spinning technology parameter is made with winding are as follows: 290 DEG C of spinning temperature, cooling temperature 25 DEG C, network pressure 0.30MPa, a roller speed 2600m/min, 90 DEG C of a roll temperature, two roller speed 3900m/min, two roll temperatures 135 DEG C, winding speed 3830m/min.

The filament number of final fluorine-containing binary acid modified poly ester FDY fiber obtained is 1.6dtex, and breaking strength is 3.73cN/dtex, elongation at break 22.5%, internet pricing are 10/m, and line density deviation ratio is 0.92%, breaking strength CV Value is 4.9%, and extension at break CV value is 7.9%, boiling water shrinkage 7.6%；It is 25 DEG C in temperature and relative humidity is After being placed 60 months under conditions of 65%, inherent viscosity decline 26%.

Embodiment 3

A kind of preparation method of fluorine-containing binary acid modified poly ester FDY fiber, the specific steps are as follows:

(1) fluorine-containing binary acid modified poly ester is prepared；

(1.1) Sb of doping vario-property is prepared₂O₃；

Ba (the NO that concentration is 1.0mol% by (1.1.1)₃)₂The Sb that aqueous solution and concentration are 10mol%₂O₃Solution it is mixed It closes uniformly, Sb₂O₃The solvent of solution be oxalic acid, Ba in mixed liquor²⁺With Sb³⁺Molar ratio be 3:100；

The pH value that ammonium hydroxide to mixed liquor that concentration is 2mol/L is added dropwise in (1.1.2) is 9.5 to obtain precipitated product, then to heavy Shallow lake product is washed and is dried, and dry temperature is 105 DEG C, time 3h；

(1.1.3) keeps the temperature 3h after the product after drying is warming up to 400 DEG C first, keeps the temperature 2h after then heating to 900 DEG C, It is crushed after finally cooling down in air and obtains the Sb for the doping vario-property that average grain diameter is 0.5 micron₂O₃Powder；

(1.2) solid heteropoly acid B is prepared₂O₃-Al₂O₃Powder；

By weight, it firstly, it is 4wt% aluminum sulfate solution that 2.5 parts of concentration are added dropwise into 1 part of boric acid, then uses The sodium hydroxide solution that concentration is 1.0mol/L adjusts pH value to neutrality, and the sulphur acid for adjusting pH value for being then 9wt% with concentration is 8, after being aged 1.5h, deionized water is washed to no SO₄ ^2-After filter, filter cake is repeatedly washed with dehydrated alcohol, then is placed in drying box It is dried under the conditions of 100 DEG C of temperature, is crushed to obtain solid heteropoly acid after sample is finally calcined 2h at 700 DEG C respectively B₂O₃-Al₂O₃Powder, B₂O₃-Al₂O₃Middle Al₂O₃Content be respectively 30wt%；

(1.3) esterification；

By terephthalic acid (TPA), ethylene glycol and 2, fluoro- 1, the 5- glutaric acid of 2- bis- is made into slurry, and solid heteropoly acid B is added₂O₃- Al₂O₃The Sb of powder, doping vario-property₂O₃Powder, titanium dioxide and Trimethyl phosphite after mixing, add in nitrogen atmosphere Pressure carries out esterification, and moulding pressure 0.2MPa, the temperature of esterification is 255 DEG C, when the water quantity of distillate in esterification It is esterification terminal, terephthalic acid (TPA), ethylene glycol and 2, mole of fluoro- 1, the 5- glutaric acid of 2- bis- when reaching the 95% of theoretical value Than for 1:1.5:0.06, solid heteropoly acid B₂O₃-Al₂O₃The Sb of powder, doping vario-property₂O₃Powder, titanium dioxide and phosphorous acid three The additional amount of methyl esters is respectively 0.14wt%, 0.013wt%, 0.22wt% and 0.03wt% of terephthalic acid (TPA) additional amount；

(1.4) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 40min Interior that absolute pressure 480Pa is steadily evacuated to by normal pressure, reaction temperature is 255 DEG C, and reaction time 40min then proceedes to vacuumize, The polycondensation reaction for carrying out high vacuum stage of Fig makes reaction pressure be further reduced to absolute pressure 95Pa, and reaction temperature is 272 DEG C, instead It is 70min between seasonable, it is 27000 that number-average molecular weight, which is made, the fluorine-containing binary acid modified poly ester that molecular weight distributing index is 2.0；

(2) fluorine-containing binary acid modified poly ester melt is measured, spinneret is squeezed out, cools down, oils, stretched, thermal finalization Fluorine-containing binary acid modified poly ester FDY fiber, spinning technology parameter is made with winding are as follows: 285 DEG C of spinning temperature, cooling temperature 22 DEG C, network pressure 0.25MPa, a roller speed 2400m/min, 80 DEG C of a roll temperature, two roller speed 3750m/min, two roll temperatures 125 DEG C, winding speed 3700m/min.

The filament number of final fluorine-containing binary acid modified poly ester FDY fiber obtained is 2.4dtex, and breaking strength is 3.6cN/dtex, elongation at break 25.0%, internet pricing are 12/m, and line density deviation ratio is 0.9%, breaking strength CV value It is 4.5%, extension at break CV value is 7.2%, boiling water shrinkage 8.0%；It is 25 DEG C in temperature and relative humidity is 65% Under conditions of place 60 months after, inherent viscosity decline 23%.

Embodiment 4

A kind of preparation method of fluorine-containing binary acid modified poly ester FDY fiber, the specific steps are as follows:

(1) fluorine-containing binary acid modified poly ester is prepared；

(1.1) Sb of doping vario-property is prepared₂O₃；

Zn (the NO that concentration is 0.6mol% by (1.1.1)₃)₂The Sb that aqueous solution and concentration are 6mol%₂O₃Solution mixing Uniformly, Sb₂O₃The solvent of solution be oxalic acid, Zn in mixed liquor²⁺With Sb³⁺Molar ratio be 1.2:100；

The pH value that ammonium hydroxide to mixed liquor that concentration is 2mol/L is added dropwise in (1.1.2) is 10 to obtain precipitated product, then to heavy Shallow lake product is washed and is dried, and dry temperature is 110 DEG C, time 2.5h；

(1.1.3) keeps the temperature 2.5h after the product after drying is warming up to 400 DEG C first, keeps the temperature after then heating to 900 DEG C 1h is crushed after finally cooling down in air and is obtained the Sb for the doping vario-property that average grain diameter is 0.4 micron₂O₃Powder；

(1.2) solid heteropoly acid TiO is prepared₂- ZnO powder；

By weight, firstly, the titanyl sulfate solution that 3 parts of concentration are 5wt% is added dropwise into 1 part of zinc sulfate, PH value is adjusted to neutrality, the sulphur acid for adjusting pH for being then 10wt% with concentration with the sodium hydroxide solution that concentration is 1.0mol/L again Value is 8, and after being aged 2h, deionized water is washed to no SO₄ ^2-After filter, filter cake is repeatedly washed with dehydrated alcohol and is placed in drying box again In dried under the conditions of 100 DEG C of temperature, finally by sample respectively at 600 DEG C calcine 2.5h after crushed to obtain average grain diameter For 0.45 micron of solid heteropoly acid TiO₂- ZnO powder, TiO₂The content of ZnO is respectively 35wt% in-ZnO；

(1.3) esterification；

By terephthalic acid (TPA), ethylene glycol and 2, fluoro- 1, the 5- glutaric acid of 2- bis- is made into slurry, and solid heteropoly acid TiO is added₂- The Sb of ZnO powder, doping vario-property₂O₃Powder, titanium dioxide and triphenyl phosphate after mixing, pressurize in nitrogen atmosphere into Row esterification, moulding pressure 0.25MPa, the temperature of esterification is 250 DEG C, when the water quantity of distillate in esterification reaches Theoretical value 95% when be esterification terminal, the molar ratio of terephthalic acid (TPA), ethylene glycol and 2, fluoro- 1, the 5- glutaric acid of 2- bis- is 1:1.4:0.055 solid heteropoly acid TiO₂The Sb of-ZnO powder, doping vario-property₂O₃Powder, titanium dioxide and triphenyl phosphate Additional amount is respectively 0.135wt%, 0.014wt%, 0.24wt% and 0.04wt% of terephthalic acid (TPA) additional amount；

(1.4) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 35min Interior that absolute pressure 480Pa is steadily evacuated to by normal pressure, reaction temperature is 258 DEG C, and reaction time 45min then proceedes to vacuumize, The polycondensation reaction for carrying out high vacuum stage of Fig makes reaction pressure be further reduced to absolute pressure 96Pa, and reaction temperature is 270 DEG C, instead It is 55min between seasonable, it is 26000 that number-average molecular weight, which is made, the fluorine-containing binary acid modified poly ester that molecular weight distributing index is 1.9；

(2) fluorine-containing binary acid modified poly ester melt is measured, spinneret is squeezed out, cools down, oils, stretched, thermal finalization Fluorine-containing binary acid modified poly ester FDY fiber, spinning technology parameter is made with winding are as follows: 280 DEG C of spinning temperature, cooling temperature 25 DEG C, network pressure 0.25MPa, a roller speed 2500m/min, 85 DEG C of a roll temperature, two roller speed 3700m/min, two roll temperatures 120 DEG C, winding speed 3800m/min.

The filament number of final fluorine-containing binary acid modified poly ester FDY fiber obtained is 2.5dtex, and breaking strength is 3.65cN/dtex, elongation at break 25.5%, internet pricing are 13/m, and line density deviation ratio is 0.86%, breaking strength CV Value is 4.3%, and extension at break CV value is 7.0%, boiling water shrinkage 8.1%；It is 25 DEG C in temperature and relative humidity is After being placed 60 months under conditions of 65%, inherent viscosity decline 22%.

Embodiment 5

A kind of preparation method of fluorine-containing binary acid modified poly ester FDY fiber, the specific steps are as follows:

(1) fluorine-containing binary acid modified poly ester is prepared；

(1.1) Sb of doping vario-property is prepared₂O₃；

Mg (the NO that concentration is 0.7mol% by (1.1.1)₃)₂The Sb that aqueous solution and concentration are 8mol%₂O₃Solution mixing Uniformly, Sb₂O₃The solvent of solution be oxalic acid, Mg in mixed liquor²⁺With Sb³⁺Molar ratio be 2:100；

The pH value that ammonium hydroxide to mixed liquor that concentration is 2mol/L is added dropwise in (1.1.2) is 10 to obtain precipitated product, then to heavy Shallow lake product is washed and is dried, and dry temperature is 110 DEG C, time 2.5h；

(1.1.3) keeps the temperature 2.5h after the product after drying is warming up to 400 DEG C first, keeps the temperature after then heating to 900 DEG C 2h is crushed after finally cooling down in air and is obtained the Sb for the doping vario-property that average grain diameter is 0.5 micron₂O₃Powder；

(1.2) solid heteropoly acid SiO is prepared₂- CaO powder；

By weight, firstly, 1 part of silicon-dioxide powdery and 50 parts of water are dispersed with stirring, 3 parts of concentration, which are added dropwise, is 5wt% calcium sulphate soln, then the sodium hydroxide solution for being 1.0mol/L with concentration adjust pH value to neutrality, are then with concentration The sulphur acid for adjusting pH value of 10wt% is 8, and after being aged 2h, deionized water is washed to no SO₄ ^2-After filter, filter cake dehydrated alcohol is more Secondary washing is placed in again in drying box dries under the conditions of 100 DEG C of temperature, and it is laggard that sample is finally calcined to 3.5h at 650 DEG C respectively It is 0.45 micron of solid heteropoly acid SiO that row, which crushes and obtains average grain diameter,₂- CaO powder, SiO₂The content of CaO is in-CaO 45wt%；

(1.3) esterification；

By terephthalic acid (TPA), ethylene glycol and 2,2,3,3- tetra- fluoro- 1, 4- succinic acids are made into slurry, and solid heteropoly acid is added SiO₂The Sb of-CaO powder, doping vario-property₂O₃Powder, titanium dioxide and triphenyl phosphate after mixing, add in nitrogen atmosphere Pressure carries out esterification, and moulding pressure 0.15MPa, the temperature of esterification is 260 DEG C, when the water quantity of distillate in esterification It is esterification terminal when reaching the 94% of theoretical value, terephthalic acid (TPA), ethylene glycol and 2,2,3,3- tetra- fluoro- 1, 4- succinic acids Molar ratio is 1:1.5:0.06, solid heteropoly acid SiO₂The Sb of-CaO powder, doping vario-property₂O₃Powder, titanium dioxide and tricresyl phosphate The additional amount of phenyl ester is respectively 0.014wt%, 0.015wt%, 0.25wt% and 0.05wt% of terephthalic acid (TPA) additional amount；

(1.4) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 50min Interior that absolute pressure 480Pa is steadily evacuated to by normal pressure, reaction temperature is 255 DEG C, and reaction time 50min then proceedes to vacuumize, The polycondensation reaction for carrying out high vacuum stage of Fig makes reaction pressure be further reduced to absolute pressure 95Pa, and reaction temperature is 282 DEG C, instead It is 80min between seasonable, it is 29000 that number-average molecular weight, which is made, the fluorine-containing binary acid modified poly ester that molecular weight distributing index is 2.1；

(2) fluorine-containing binary acid modified poly ester melt is measured, spinneret is squeezed out, cools down, oils, stretched, thermal finalization Fluorine-containing binary acid modified poly ester FDY fiber, spinning technology parameter is made with winding are as follows: 290 DEG C of spinning temperature, cooling temperature 20 DEG C, network pressure 0.30MPa, a roller speed 2200m/min, 90 DEG C of a roll temperature, two roller speed 3900m/min, two roll temperatures 135 DEG C, winding speed 3560m/min.

The filament number of final fluorine-containing binary acid modified poly ester FDY fiber obtained is 2.5dtex, and breaking strength is 3.62cN/dtex, elongation at break 24.9%, internet pricing are 12/m, and line density deviation ratio is 0.89%, breaking strength CV Value is 4.4%, and extension at break CV value is 7.1%, boiling water shrinkage 7.9%；It is 25 DEG C in temperature and relative humidity is After being placed 60 months under conditions of 65%, inherent viscosity decline 23%.

Embodiment 6

A kind of preparation method of fluorine-containing binary acid modified poly ester FDY fiber, the specific steps are as follows:

(1) fluorine-containing binary acid modified poly ester is prepared；

(1.1) Sb of doping vario-property is prepared₂O₃；

Concentration is the Mg (NO of 0.8mol% by (1.1.1)₃)₂Aqueous solution and Ca (NO₃)₂1:1 is mixed by volume for aqueous solution Conjunction obtains metal ion M^x+Aqueous solution, metal ion M^x+Aqueous solution and concentration be 8mol% Sb₂O₃Solution it is mixed It closes uniformly, Sb₂O₃The solvent of solution be oxalic acid, M in mixed liquor^x+With Sb³⁺Molar ratio be 2.5:100；

The pH value that ammonium hydroxide to mixed liquor that concentration is 2mol/L is added dropwise in (1.1.2) is 10 to obtain precipitated product, then to heavy Shallow lake product is washed and is dried, and dry temperature is 105 DEG C, time 3h；

(1.1.3) keeps the temperature 3h after the product after drying is warming up to 400 DEG C first, keeps the temperature after then heating to 900 DEG C 1.5h is crushed after finally cooling down in air and is obtained the Sb for the doping vario-property that average grain diameter is 0.4 micron₂O₃Powder；

(1.2) solid heteropoly acid powder is prepared；

Solid heteropoly acid powder is 0.45 micron of SiO by average grain diameter₂-TiO₂Powder and SiO₂-ZrO₂Powder presses matter Amount is mixed to get than 1:1, wherein SiO₂-TiO₂And SiO₂-ZrO₂Middle TiO₂And ZrO₂Content be respectively 30wt% and 50wt%, SiO₂-TiO₂Powder and SiO₂-ZrO₂Raw powder's production technology is essentially identical with Examples 1 and 2, is different only in that it Raw material additive amount；

(1.3) esterification；

By terephthalic acid (TPA), ethylene glycol and 2,2,3,3- tetra- fluoro- 1, 4- succinic acids are made into slurry, and solid heteropoly acid powder is added The Sb of body, doping vario-property₂O₃Powder, titanium dioxide and triphenyl phosphate after mixing, pressurize in nitrogen atmosphere and are esterified Reaction, moulding pressure 0.3MPa, the temperature of esterification is 250 DEG C, when the water quantity of distillate in esterification reaches theoretical value 94% when be esterification terminal, terephthalic acid (TPA), ethylene glycol and 2, the molar ratios of 2,3,3- tetra- fluoro- 1, 4- succinic acids is 1: 1.6:0.065 the Sb of solid heteropoly acid powder, doping vario-property₂O₃The additional amount of powder, titanium dioxide and triphenyl phosphate is distinguished For 0.14wt%, 0.012wt%, 0.20wt% and 0.01wt% of terephthalic acid (TPA) additional amount；

(1.4) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 30min Interior that absolute pressure 450Pa is steadily evacuated to by normal pressure, reaction temperature is 260 DEG C, and reaction time 30min then proceedes to vacuumize, The polycondensation reaction for carrying out high vacuum stage of Fig makes reaction pressure be further reduced to absolute pressure 92Pa, and reaction temperature is 272 DEG C, instead It is 85min between seasonable, it is 28000 that number-average molecular weight, which is made, the fluorine-containing binary acid modified poly ester that molecular weight distributing index is 1.8；

(2) fluorine-containing binary acid modified poly ester melt is measured, spinneret is squeezed out, cools down, oils, stretched, thermal finalization Fluorine-containing binary acid modified poly ester FDY fiber, spinning technology parameter is made with winding are as follows: 280 DEG C of spinning temperature, cooling temperature 25 DEG C, network pressure 0.20MPa, a 2200~2600m/min of roller speed, 80 DEG C of a roll temperature, two roller speed 3800m/min, two 120 DEG C of roll temperature, winding speed 3600m/min.

The filament number of final fluorine-containing binary acid modified poly ester FDY fiber obtained is 1.9dtex, and breaking strength is 3.5cN/dtex, elongation at break 23.0%, internet pricing are 10/m, and line density deviation ratio is 0.95%, breaking strength CV Value is 4.7%, and extension at break CV value is 7.6%, boiling water shrinkage 7.5%；It is 25 DEG C in temperature and relative humidity is After being placed 60 months under conditions of 65%, inherent viscosity decline 24%.

Embodiment 7

A kind of preparation method of fluorine-containing binary acid modified poly ester FDY fiber, the specific steps are as follows:

(1) fluorine-containing binary acid modified poly ester is prepared；

(1.1) Sb of doping vario-property is prepared₂O₃；

Concentration is the Mg (NO of 0.5mol% by (1.1.1)₃)₂Aqueous solution, Ba (NO₃)₂Aqueous solution and Ca (NO₃)₂It is water-soluble 1:1:1 is mixed to get metal ion M to liquid by volume^x+Aqueous solution, metal ion M^x+Aqueous solution be with concentration The Sb of 10mol%₂O₃Solution be uniformly mixed, Sb₂O₃The solvent of solution be oxalic acid, metal ions M in mixed liquor^x+With Sb³⁺'s Molar ratio is 2:100；

The pH value that ammonium hydroxide to mixed liquor that concentration is 2mol/L is added dropwise in (1.1.2) is 9 to obtain precipitated product, then to precipitating Product is washed and is dried, and dry temperature is 108 DEG C, time 2.5h；

(1.1.3) keeps the temperature 2.5h after the product after drying is warming up to 400 DEG C first, keeps the temperature after then heating to 900 DEG C 2h is crushed after finally cooling down in air and is obtained the Sb for the doping vario-property that average grain diameter is 0.4 micron₂O₃Powder；

(1.2) solid heteropoly acid powder is prepared；

Solid heteropoly acid powder is 0.45 micron of SiO by average grain diameter₂-TiO₂Powder, B₂O₃-Al₂O₃Powder and SiO₂-ZrO₂Powder 1:1:1 in mass ratio is mixed to get, wherein SiO₂-TiO₂、B₂O₃-Al₂O₃And SiO₂-ZrO₂Middle TiO₂、 Al₂O₃And ZrO₂Content be respectively 50wt%, 20wt% and 20wt%, SiO₂-TiO₂Powder, B₂O₃-Al₂O₃Powder and SiO₂- ZrO₂Raw powder's production technology and embodiment 1,3 and 2 are essentially identical, are different only in that its raw material additive amount；

(1.3) esterification；

By terephthalic acid (TPA), ethylene glycol and 2, fluoro- 1, the 3- malonic acid of 2- bis- is made into slurry, be added solid heteropoly acid powder, The Sb of doping vario-property₂O₃After mixing, pressurization be esterified anti-in nitrogen atmosphere for powder, titanium dioxide and triphenyl phosphate It answers, moulding pressure 0.2MPa, the temperature of esterification is 255 DEG C, when the water quantity of distillate in esterification reaches theoretical value It is esterification terminal when 94%, the molar ratio of terephthalic acid (TPA), ethylene glycol and 2, fluoro- 1, the 3- malonic acid of 2- bis- is 1:2.0: 0.07, the Sb of solid heteropoly acid powder, doping vario-property₂O₃The additional amount of powder, titanium dioxide and triphenyl phosphate is respectively to benzene 0.145wt%, 0.012wt%, 0.20wt% and 0.03wt% of dioctyl phthalate additional amount；

(1.4) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 50min Interior that absolute pressure 490Pa is steadily evacuated to by normal pressure, reaction temperature is 255 DEG C, and reaction time 50min then proceedes to vacuumize, The polycondensation reaction for carrying out high vacuum stage of Fig makes reaction pressure be further reduced to absolute pressure 95Pa, and reaction temperature is 275 DEG C, instead It is 55min between seasonable, it is 25000 that number-average molecular weight, which is made, the fluorine-containing binary acid modified poly ester that molecular weight distributing index is 2.2；

(2) fluorine-containing binary acid modified poly ester melt is measured, spinneret is squeezed out, cools down, oils, stretched, thermal finalization Fluorine-containing binary acid modified poly ester FDY fiber, spinning technology parameter is made with winding are as follows: 290 DEG C of spinning temperature, cooling temperature 20 DEG C, network pressure 0.30MPa, a roller speed 2200m/min, 90 DEG C of a roll temperature, two roller speed 3600m/min, two roll temperatures 115 DEG C, winding speed 3830m/min.

The filament number of final fluorine-containing binary acid modified poly ester FDY fiber obtained is 1.5dtex, and breaking strength is 3.5cN/dtex, elongation at break 22.0%, internet pricing are 9/m, and line density deviation ratio is 1.0%, breaking strength CV value It is 5.0%, extension at break CV value is 8.0%, boiling water shrinkage 7.6%；It is 25 DEG C in temperature and relative humidity is 65% Under conditions of place 60 months after, inherent viscosity decline 26%.

Claims (10)

1. a kind of preparation method of fluorine-containing binary acid modified poly ester FDY fiber, it is characterized in that: fluorine-containing binary acid modified poly ester is melted Body is measured, spinneret squeezes out, cools down, oil, stretching, fluorine-containing binary acid modified poly ester FDY fibre is made in thermal finalization and winding Dimension；

The fluorine-containing binary acid modified poly ester the preparation method comprises the following steps: by terephthalic acid (TPA), ethylene glycol, fluorine-containing binary acid, through excessively high The solid heteropoly acid powder of temperature roasting and the Sb of doping vario-property₂O₃Powder successively carries out esterification after mixing and polycondensation is anti- It answers；

Fluorine-containing binary acid be the fluoro- 1,3- malonic acid of 2,2- bis-, the fluoro- 1,4- succinic acid of 2,2- bis-, the fluoro- 1,5- glutaric acid of 2,2- bis- or The fluoro- 1,4- succinic acid of 2,2,3,3- tetra-；

The temperature of solid heteropoly acid high-temperature roasting is 400~700 DEG C, solid heteropoly acid SiO₂-TiO₂、SiO₂-ZrO₂、B₂O₃- Al₂O₃、TiO₂- ZnO and SiO₂One or more of-CaO；

Sb₂O₃The process of doping vario-property are as follows: first by metal ion N^y+Solution with contain Sb³⁺Solution be uniformly mixed, then The pH value that precipitating reagent is added dropwise to mixed liquor is 9~10, finally calcines precipitated product；

Metal ion N^y+For Mg²⁺、Ca²⁺、Ba²⁺And Zn²⁺One or more of.

2. a kind of preparation method of fluorine-containing binary acid modified poly ester FDY fiber according to claim 1, which is characterized in that The time of high-temperature roasting is 2~4h；SiO₂-TiO₂、SiO₂-ZrO₂、B₂O₃-Al₂O₃、TiO₂- ZnO and SiO₂TiO in-CaO₂、 ZrO₂、Al₂O₃, ZnO and CaO content be respectively 30~50wt%, 30~50wt%, 20~40wt%, 20~40wt% and 20 ~50wt%；Solid heteropoly acid is crushed to obtain powder of the average grain diameter less than 0.5 micron after high-temperature roasting；

To Sb₂O₃When being doped modified, the metal ion N^y+The concentration of solution be 0.5~1.0mol%, solvent is Water, the anion in solution are NO₃ ^-；It is described to contain Sb³⁺Solution be 5~10mol% of concentration Sb₂O₃Solution, solvent be grass Acid；The precipitating reagent is the ammonium hydroxide of concentration 2mol/L；When precipitating starts, metal ion N in mixed solution^y+With Sb³⁺Molar ratio For 1~3:100；Precipitated product is washed and dried before the calcining, dry temperature is 105~110 DEG C, the time 2 ~3h；The process of the calcining are as follows: 2~3h is kept the temperature after being warming up to 400 DEG C first, and 1~2h is kept the temperature after then heating to 900 DEG C, Finally cool down in air；Sb₂O₃It is crushed to obtain powder of the average grain diameter less than 0.5 micron after doping vario-property.

3. a kind of preparation method of fluorine-containing binary acid modified poly ester FDY fiber according to claim 2, which is characterized in that The preparation step of the fluorine-containing binary acid modified poly ester is as follows:

(1) esterification；

Terephthalic acid (TPA), ethylene glycol and fluorine-containing binary acid are made into slurry, be added solid heteropoly acid powder Jing Guo high-temperature roasting, The Sb of doping vario-property₂O₃After mixing, pressurization carries out esterification, pressurization in nitrogen atmosphere for powder, delustering agent and stabilizer Pressure is normal pressure~0.3MPa, and the temperature of esterification is 250~260 DEG C, when the water quantity of distillate in esterification reaches theoretical Value 90% or more when be esterification terminal；

(2) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 30~50min Interior to be steadily evacuated to absolute pressure 500Pa hereinafter, reaction temperature is 250~260 DEG C by normal pressure, the reaction time is 30~50min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, so that reaction pressure is further reduced to absolute pressure 100Pa hereinafter, Reaction temperature is 270~282 DEG C, and the reaction time is 50~90min.

4. a kind of preparation method of fluorine-containing binary acid modified poly ester FDY fiber according to claim 3, which is characterized in that The molar ratio of the terephthalic acid (TPA), ethylene glycol and fluorine-containing binary acid is 1:1.2~2.0:0.05~0.07, described to pass through high temperature The Sb of the solid heteropoly acid powder of roasting, doping vario-property₂O₃The additional amount of powder, delustering agent and stabilizer is respectively terephthaldehyde 0.13~0.15wt%, 0.012~0.015wt%, 0.20~0.25wt% and the 0.01~0.05wt% of sour additional amount.

5. a kind of preparation method of fluorine-containing binary acid modified poly ester FDY fiber according to claim 4, which is characterized in that The delustering agent is titanium dioxide, and the stabilizer is triphenyl phosphate, trimethyl phosphate or Trimethyl phosphite.

6. a kind of preparation method of fluorine-containing binary acid modified poly ester FDY fiber according to claim 5, which is characterized in that The number-average molecular weight of fluorine-containing binary acid modified poly ester is 25000~30000, and molecular weight distributing index is 1.8~2.2.

7. a kind of preparation method of fluorine-containing binary acid modified poly ester FDY fiber according to claim 1, which is characterized in that The spinning technology parameter of the fluorine-containing binary acid modified poly ester FDY fiber are as follows: 280~290 DEG C of spinning temperature, cooling temperature 20~ 25 DEG C, network pressure 0.20~0.30MPa, a 2200~2600m/min of roller speed, 75~90 DEG C of a roll temperature, two roller speeds 3600~3900m/min, two 115~135 DEG C of roll temperatures, 3560~3830m/min of winding speed.

8. using a kind of preparation method system of fluorine-containing binary acid modified poly ester FDY fiber as described in any one of claims 1 to 7 A kind of fluorine-containing binary acid modified poly ester FDY fiber obtained, it is characterized in that: the strand of fluorine-containing binary acid modified poly ester includes to benzene Dioctyl phthalate segment, ethylene glycol segment and fluorine-containing binary acid segment；

The solid heteropoly acid powder by high-temperature roasting and the doping are dispersed in the fluorine-containing binary acid modified poly ester Modified Sb₂O₃Powder.

9. a kind of fluorine-containing binary acid modified poly ester FDY fiber according to claim 8, which is characterized in that fluorine-containing binary acid The filament number of modified poly ester FDY fiber is 1.5~3.0dtex, breaking strength >=3.5cN/dtex, elongation at break 25.0 ± 3.0%, internet pricing is 12 ± 3/m, line density deviation ratio≤1.0%, breaking strength CV value≤5.0%, extension at break CV Value≤8.0%, boiling water shrinkage are 8.0 ± 0.5%.

10. a kind of fluorine-containing binary acid modified poly ester FDY fiber according to claim 8, which is characterized in that fluorine-containing binary acid After modified poly ester FDY fiber is placed 60 months under conditions of temperature is 25 DEG C and relative humidity is 65%, under inherent viscosity Drop 20~26%.