CN109750374A

CN109750374A - Low elastic polyester filament semi-dull and preparation method thereof

Info

Publication number: CN109750374A
Application number: CN201811614007.7A
Authority: CN
Inventors: 汤方明; 周文龙; 张元华
Original assignee: Jiangsu Hengli Chemical Fiber Co Ltd
Current assignee: Jiangsu Hengli Chemical Fiber Co Ltd
Priority date: 2018-12-27
Filing date: 2018-12-27
Publication date: 2019-05-14
Anticipated expiration: 2038-12-27
Also published as: CN109750374B

Abstract

The present invention relates to a kind of low elastic polyester filaments semi-dull and preparation method thereof, the preparation method comprises the following steps: being made modified poly ester POY by modified poly ester melt by POY technique, DTY technique is pressed again by modified poly ester POY obtained modified poly ester DTY to get low elastic polyester filament semi-dull；The strand of modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment and fluorine-containing binary acid segment；The ZrO of delustering agent, doping vario-property is dispersed in modified poly ester₂The Sb of powder and doping vario-property₂O₃Powder.Product is made after placing 60 months under conditions of temperature is 25 DEG C and relative humidity is 65%, inherent viscosity decline 15~18%.Preparation method of the invention, simple process and low cost reduce the additive amount of antimony-based catalyst, reduce antimony discharge；Product obtained, natural degradation rate is fast, and application prospect is good.

Description

Low elastic polyester filament semi-dull and preparation method thereof

Technical field

The invention belongs to modified polyester fiber technical field, it is related to a kind of low elastic polyester filament semi-dull and preparation method thereof.

Background technique

Terylene industrializes the latest in three big synthetic fibers (terylene, polyamide fibre and polypropylene fibre), but with the fastest developing speed.Currently, Global terylene demand is still increased with annual 6~7% speed, and it is so fast why the demand of terylene increases, mainly Itself having the following characteristics that 1) terylene is had excellent performance, modulus is high, and it is heat-resist, it is more satisfactory textile fiber material；2) The mechanical mechanics property plasticity of terylene is big, can produce cotton, wool type staple fiber, long filament or work by different processing methods Industry purposes product；3) due to the development of petro chemical industry, raw material required for PET production can be more economical and convenient It obtains, the manufacturing enterprise substantially reduced enters the threshold of this industry；4) cheap, the price of terylene, which is lower than, at present removes polypropylene fibre Every other synthetic fibers in addition.

With social progress and improvement of living standard, people are also higher and higher to the requirement for taking fiber, from initial It is securely endurable to develop to current comfort and functionality.The differentiation and functionalization of polyester fiber be its development must It asks.

Since the shape of conventional polyester is regular, surface is smooth and has certain transparency, anti-under the irradiation of light The intensity for penetrating light is very big, has apparent reflective and scintillation, and the visual comfort of fiber is not high.It is added in fiber few The different substance of refractive index is measured, light is made to carry out diffusing reflection to different directions, fiber glossiness will be reduced, improve its euphorosia Degree, here it is the delustring of fiber product processing.Titanium dioxide is commonly called as titanium white, due to its refractive index height (TiO₂Refractive index be 2.60, air 1.00), added and can be realized delustring using the refringence of itself and polyester in the polyester, be a kind of reason The polyester delustring additive thought.

In addition, elastic force is one important performance of fiber, elastic filament is divided into high stretch yarn and two kinds of low stretch yarn.Low elastic polyester filament is As for raw material, spinning terylene pre-oriented fiber (POY) using high speed, then be process through drafting false twisting with polyester slice (PET) Fiber.It removes high breaking strength and high elastic modulus, excellent heat setting, excellent resilience with general terylene Energy, excellent heat resistance, good light resistance, good corrosion resistance and it is quick-drying washable the features such as outside, also have bulkiness it is high, Thermal insulation is good, comfortable feel and the characteristics of soft glossy.In addition, its processing flow is short, and it is high in machining efficiency, it is a kind of widely used Polyester fiber.

But with the fast development of PET industry, although PET will not directly cause damages to environment, after its use Waste product huge amount and very strong to the repellence of atmosphere and microorganism reagent, it is discarded not easy to handle to be made fiber, can give ring Border causes damages indirectly.The processing method of PET fiber waste mainly has at present: landfill is burned and is recycled.From environment angle For degree, although landfill and burning are simplest methods, there are many defects, and certain pollution is also resulted in environment.Change Learning degradation recycling is to handle PET waste effectively and the approach of science, main method include alcoholysis, ammonolysis etc., chemical degradation Product such as alcohol, acid, ester etc. is also used as chemical raw material re-using.But it since PET construction is fine and close, crystallinity is high, drops naturally The solution time is very long (degradation cycle of conventional PET fiber was up to 16~48 years), and it is useless in PET which greatly limits chemical degradation recycling The application of gurry process field.

Therefore, a kind of great realistic meaning of low elastic polyester filament semi-dull for capableing of high efficiency degradation recovery processing is developed.

Summary of the invention

It is fast to provide a kind of natural degradation rate for the defect that the purpose of the present invention is overcome prior art natural degradation rate slow Low elastic polyester filament semi-dull and preparation method thereof.

In order to achieve the above objectives, The technical solution adopted by the invention is as follows:

The preparation method of low elastic polyester filament semi-dull is made modified poly ester POY by modified poly ester melt by POY technique, DTY technique is pressed again by modified poly ester POY obtained modified poly ester DTY to get low elastic polyester filament semi-dull；

The modified poly ester the preparation method comprises the following steps: terephthalic acid (TPA), ethylene glycol, fluorine-containing binary acid, delustering agent, doping are changed The ZrO of property₂The Sb of powder and doping vario-property₂O₃Powder successively carries out esterification and polycondensation reaction after mixing；

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-；

The content of delustering agent is 0.20~0.25wt% in the modified poly ester；

ZrO₂The process of doping vario-property are as follows: first by metal ion M^x+Solution with contain Zr⁴⁺Solution be uniformly mixed, so The pH value that precipitating reagent is added dropwise to mixed liquor afterwards is 9~10, finally calcines precipitated product；

Metal ions M^x+For Mg²⁺、Li⁺And Zn²⁺One or more of；

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 co-precipitated the method calcined again by first solution blending again realizes metal oxide (magnesia, oxidation One or more of lithium and zinc oxide) and ZrO₂Doping, and then to ZrO₂Hydrogen reduction catalytic process have an impact, improve The degradation rate of polyester, the ZrO for having selected ionic conductivity high due to the present invention₂As oxygen reduction catalyst substrate, pass through Adulterate the metal ion (Mg of lower valency²⁺、Li⁺And Zn²⁺) stable cubic phase can be obtained, while to a certain extent, doping Ionic radius is more conducive to the formation of Lacking oxygen, is more conducive to the conduction of oxonium ion, this hair closer to the ionic radius being doped Bright selection doping and Zr⁴⁺Identical metal ion (the Mg of ionic radius²⁺、Li⁺And Zn²⁺, ionic radius is 0.103nm) and to it It is doped, this can be improved the conduction velocity of oxonium ion, and then improve the degree of oxygen reduction reaction；

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, And then reduce Sb in preparation process₂O₃Additive amount to reduce cost；

The fluorine-containing binary acid that the present invention adds is characterized in that fluorine atom on α carbon, when introducing in hydrolytic process When the fluorine-containing 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 It reduces, the stability decline of tetrahedral anion is conducive to the progress of nucleophilic addition, simultaneously because fluorine-containing two on α carbon The steric hindrance of first acid is less than terephthalic acid (TPA), further promotes the progress of nucleophilic addition, thus significantly improves drop Solve rate；

The ZrO of fluorine-containing binary acid and doping vario-property that the present invention introduces in polyester molecule chain₂Powder can also play collaboration Effect, for fluorine-containing binary acid since fluorine atom is on α carbon, electron-withdrawing ability is stronger, so that the electron cloud in polyester on C-O key is close Degree reduces, and the stability decline of tetrahedral anion is conducive to the progress of degradation reaction, the ZrO of doping vario-property₂Powder can The conduction velocity of oxonium ion is improved, accelerates oxygen reduction reaction, further promotes the progress of degradation reaction, thus is further improved Natural degradation rate；

Second heater temperature of the DTY technique is 160~180 DEG C, is not heated with the second hot tank generally high-elastic Silk, the generally low stretch yarn heated with the second hot tank, produced by the present invention is low stretch yarn.

As a preferred technical scheme:

The preparation method of low elastic polyester filament semi-dull as described above, to ZrO₂It is described to contain metal when being doped modified Ion M^x+Solution concentration be 1~2wt%, solvent is water, the anion in solution be NO₃ ^-；It is described to contain Zr⁴⁺Solution be The ZrO of 20~25wt% of concentration₂Solution, solvent is nitric acid；The precipitating reagent is the ammonium hydroxide of concentration 2mol/L；Precipitating starts When, metal ions M in mixed liquor^x+With Zr⁴⁺Molar ratio be 5~8:100；Before the calcining to precipitated product carry out washing and Dry, dry temperature is 105~110 DEG C, and the time is 2~3h；The process of the calcining are as follows: protected after being warming up to 400 DEG C first 2~3h of temperature keeps the temperature 1~2h, finally cools down in air after then heating to 700 DEG C；ZrO₂It is crushed after doping vario-property Obtain powder of the average grain diameter less than 0.5 micron；Metal ions M of the present invention^x+With Zr⁴⁺Molar ratio be not limited to this, this field Technical staff can be adjusted according to the actual situation, but adjust amplitude and should not be too large, this is because ZrO in catalyst₂It is main body, Metal ions M^x+Introducing be around ZrO₂Expansion, it is therefore an objective to improve the conduction velocity of oxonium ion, and then it is anti-to improve hydrogen reduction The degree answered confeuses the parimary with secondary if molar ratio crosses conference, excessively few to act on deficiency to the conduction velocity for improving oxonium ion.

The preparation method of low elastic polyester filament semi-dull as described above, to Sb₂O₃It is described to contain metal when being doped modified Ion N^y+Solution concentration be 0.5~1.0mol%, solvent is water, the anion in solution be NO₃ ^-；It is described to contain Sb³⁺It is molten Liquid is the Sb of 5~10mol% of concentration₂O₃Solution, solvent is oxalic acid；The precipitating reagent is the ammonium hydroxide of concentration 2mol/L；Precipitating is opened When the beginning, metal ion N in mixed solution^y+With Sb³⁺Molar ratio be 1~3:100, Sb₂O₃It is the highest polyester of current cost performance Catalyst, the present invention is by penetrating into metal oxide (i.e. M₂O_X) inhibit antimony oxide (Sb₂O₃) three oxygen of crystallization and cubic crystal Change growing up for two antimony crystal grain, while metal ion N^y+The lattice position of antimony and entrance antimony can be replaced, so that antimony oxide crystal produces Raw defect, to improve the catalytic activity of antimony oxide；If blended metal oxide amount is very few (molar ratio is too low), aoxidized to three The influence of two antimony crystal grain is relatively low, and excessive (molar ratio is excessively high) can make the main body Sb of catalyst³⁺Fall is bigger than normal, to raising Antimony oxide catalytic activity is unfavorable；Precipitated product is washed and is dried before the calcining, dry temperature be 105~ 110 DEG C, the time is 2~3h, and the present invention includes but are not limited to this to the treatment process of precipitated product before calcining after precipitating, only Want to guarantee the OH for sufficiently removing precipitated product surface^-With moisture therein, impurity and hydrone can be avoided to calcining Dysgenic treatment process is suitable for the present invention；The process of the calcining are as follows: 2~3h is kept the temperature after being warming up to 400 DEG C first, 1~2h is kept the temperature after then heating to 900 DEG C, is finally cooled down in air；Sb₂O₃It is crushed and is averaged after doping vario-property Powder of the partial size less than 0.5 micron, calcination process of the invention include but are not limited to this, other can be realized metal oxide The doping of (MgO, CaO, BaO and ZnO) and antimony oxide are realized to Sb₂O₃The calcine technology of doping vario-property be suitable for this Invention.

The preparation method of low elastic polyester filament semi-dull as described above, the preparation step of the modified poly ester are as follows:

(1) esterification；

Terephthalic acid (TPA), ethylene glycol and fluorine-containing binary acid are made into slurry, the ZrO of doping vario-property is added₂Powder, doping change The Sb of property₂O₃After mixing, pressurization carries out esterification in nitrogen atmosphere for powder, delustering agent and stabilizer, and moulding pressure is Normal pressure~0.3MPa, the temperature of esterification is 250~260 DEG C, when the water quantity of distillate in esterification reaches theoretical value It is esterification terminal when 90% or more；

(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.

The preparation method of low elastic polyester filament semi-dull as described above, the terephthalic acid (TPA), ethylene glycol and fluorine-containing binary The molar ratio of acid is 1:1.2~2.0:0.03~0.05, the ZrO of the doping vario-property₂The Sb of powder, doping vario-property₂O₃Powder, The additional amount of delustering agent and stabilizer be respectively 0.04~0.07wt% of terephthalic acid (TPA) additional amount, 0.012~ 0.015wt%, 0.20~0.25wt% and 0.01~0.05wt% (mass percent).The additional amount of the fluorine-containing binary acid of the present invention Be not limited to this, those skilled in the art can actual conditions be adjusted, but adjust amplitude and should not be too large, additive amount is excessive to poly- The regularity destruction of ester large molecule structure is too big, excessive to the crystallinity and Effect on Mechanical Properties of fiber, is unfavorable for fiber Production and application, additive amount is too low, then unobvious to the promotion effect of degradation property.The ZrO of doping vario-property of the present invention₂Powder Additional amount is not limited to this, those skilled in the art can actual conditions be adjusted, but adjust amplitude should not be too large, additive amount mistake It is affected to the gloss of fiber and mechanical property etc. greatly, is unfavorable for the production and application of fiber, additive amount is too low, then to drop The promotion effect for solving performance is unobvious.Sb in process of polyester synthesizing in the prior art₂O₃Additional amount be usually that terephthalic acid (TPA) adds Enter 0.02~0.04wt% of amount, the additional amount of antimony-based catalyst is high, and this is mainly due to undoped Sb₂O₃Per surface area On active r_sLow and specific surface area S_gIt is small, therefore Sb₂O₃Whole catalytic activity is lower, and the present invention passes through to Sb₂O₃It is mixed Miscellaneous modification, improves Sb₂O₃Activity, therefore significantly reduce Sb in process of polyester synthesizing₂O₃Additive amount.

The preparation method of low elastic polyester filament semi-dull as described above, the delustering agent are titanium dioxide, the stabilizer For triphenyl phosphate, trimethyl phosphate or Trimethyl phosphite.

The preparation method of low elastic polyester filament semi-dull as described above, the number-average molecular weight of modified poly ester is 25000~ 30000, molecular weight distributing index is 1.8~2.2.

The preparation method of low elastic polyester filament semi-dull as described above, the process of the POY technique are as follows: metering, spinneret It squeezes out, is cooling, oiling and wind；

The parameter of the POY technique are as follows: 280~290 DEG C of spinning temperature, 18~22 DEG C of cooling temperature, winding speed 3200 ~3600m/min；

The process of the DTY technique are as follows: seal wire, heating stretching, false twisting, thermal finalization and winding；

The parameter of the DTY technique are as follows: 600~900m/min of spinning speed, overfeed rate of setting 3.5~5.5%, winding are super Feed rate 2.5~5.0%, the first 200~220 DEG C of heater temperature, draw ratio 1.6~1.8.The tool of POY and DTY technique of the invention Body parameter is not limited to that, only provides a feasible technological parameter herein.

Low elastic polyester filament semi-dull made from preparation method using low elastic polyester filament semi-dull as described above, for modification Polyester DTY；

The strand of the modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment and fluorine-containing binary acid segment；

The ZrO of delustering agent, the doping vario-property is dispersed in the modified poly ester₂The Sb of powder and the doping vario-property₂O₃ Powder, the content of delustering agent are 0.20~0.25wt%.

As a preferred technical scheme:

Low elastic polyester filament semi-dull as described above, the filament number of low elastic polyester filament semi-dull are 0.5~1.5dtex, Breaking strength >=3.5cN/dtex, elongation at break are 25.0 ± 3.0%, and crimp contraction is 10.0 ± 1.0%, and curling is stablized Degree >=77%, internet pricing are 95 ± 5/m, line density deviation ratio≤2.0%, breaking strength CV value≤8.0%, extension at break CV Value≤8.0%, crimp contraction coefficient of variation CV value≤9.0%, boiling water shrinkage are 5.0 ± 0.5%, of the invention fluorine-containing two The ZrO of first acid, doping vario-property₂The Sb of powder and doping vario-property₂O₃The additive amount of powder is smaller, processing to polyester fiber and The influence of mechanical performance is smaller, and processing performance and mechanical performance and the conventional polyester fiber of polyester fiber of the invention (are not added with The ZrO of fluorine-containing binary acid, doping vario-property₂The Sb of powder and doping vario-property₂O₃Powder) quite；

It is special after low elastic polyester filament semi-dull is placed 60 months under conditions of temperature is 25 DEG C and relative humidity is 65% Property viscosity decline 15~18%, in the same circumstances, inherent viscosity descends below 5% to conventional PET fiber, imitative hair of the invention Type polyester filament is dramatically increased compared to conventional PET fiber natural degradation rate, the ZrO of fluorine-containing binary acid and doping vario-property₂Powder The addition of body can be obviously improved the natural degradation rate of PET fiber.

Invention mechanism:

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⁺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.

To significantly promote nucleophilic addition anti-by introducing the fluorine-containing binary acid of special construction in polyester molecule chain by the present invention The progress answered, and then improve the degradation rate of polyester, fluorine-containing binary acid be characterized in that fluorine atom on α carbon, when When introducing the fluorine-containing binary acid in hydrolytic process, since fluorine atom is on α carbon, electron-withdrawing ability is stronger, so that C-O key in polyester On cloud density reduce, the decline of the stability of tetrahedral anion is conducive to the progress of nucleophilic addition, simultaneously Since the steric hindrance of fluorine-containing binary acid on α carbon is less than terephthalic acid (TPA), the progress of nucleophilic addition is further promoted, because And significantly improve degradation rate.Fluorine atom is introduced such as in polyester molecule chain in the fluorine-containing binary acid of β carbon, then will not significantly be mentioned The degradation rate of superpolyester, this is because, there are when electron-withdrawing group, generated influence is limited only to adjacent carbons on β carbon On, and to the influence very little that C-O key in ester bond generates, thus for OH^-The reaction that nucleophilic addition occurs for attack ester carbonyl group influences It is smaller.

When containing a certain amount of oxygen reduction catalyst in polyester, since polyester is chronically exposed in air, in air Oxygen can be penetrated into inside polyester by the free volume (narrow slit free volume and/or empty free volume) in polyester material, Oxygen reduction catalyst adsorption oxygen, oxygen gradually move to the oxygen reduction catalyst surface inside polyester, reach certain oxygen Absorption oxygen is formed after concentration gradient, and oxygen reduction reaction (oxygen ionized) occurs on oxygen reduction catalyst surface, reacted at this Cheng Zhong, oxygen are partially reduced to peroxide, the ester bond in oxygen molecule and a polyester after oxygen reduction catalyst absorption Form RCOOOR` in conjunction with and catalyst surface, after in conjunction with a proton and disconnect oxygen-oxygen bond, generate a RCOOH, make ester Key fracture, while OR` and H⁺In conjunction with alcohol HOR` is obtained, to accelerate polyester degradation.

The present invention is co-precipitated the method calcined again by first solution blending again realizes metal oxide (magnesia, oxidation One or more of lithium and zinc oxide) and ZrO₂Doping, and then to ZrO₂Hydrogen reduction catalytic process have an impact, improve The degradation rate of polyester.The ZrO for having selected ionic conductivity high due to the present invention₂As oxygen reduction catalyst substrate, pass through Adulterate the metal ion (Mg of lower valency²⁺、Li⁺And Zn²⁺) stable cubic phase can be obtained, while to a certain extent, doping Ionic radius is more conducive to the formation of Lacking oxygen, is more conducive to the conduction of oxonium ion, this hair closer to the ionic radius being doped Bright selection doping and Zr⁴⁺Identical metal ion (the Mg of ionic radius²⁺、Li⁺And Zn²⁺, ionic radius is 0.103nm) and to it It is doped, this can be improved the conduction velocity of oxonium ion, and then improve the degree of oxygen reduction reaction.Doping is to ZrO₂Influence It is as follows:

On the one hand, ZrO can be destroyed using doping way of the invention₂Crystal plane structure, increase its specific surface area, into And improve unit mass ZrO₂Oxygen Adsorption amount；

On the other hand, ZrO can be changed using doping way of the invention₂Suction type and oxygen reduction reaction mechanism, Before doping vario-property, suction type is monocline ZrO₂The end formula on surface is adsorbed, and O atom is in different monocline ZrO₂When crystal face adsorbs, all can " space steric effect " by surface Zr atom influences, O₂Molecule is by the weaker physical absorption of intensity or weak is chemisorbed on The absorption of Zr atom position, and in different monocline ZrO₂Crystal face O₂Molecule is all reduced to peroxide, and after doping vario-property, suction type is Adulterate ZrO₂The side formula on surface is adsorbed, and is not influenced by " space steric effect ", is enhanced O₂Chemistry of the molecule in Zr atom position is inhaled It is attached, moreover it is possible to promote O₂The O -- O bond of molecule is broken, it can promotes O₂Molecule reduction generates peroxide, improves hydrogen reduction catalysis Efficiency improves polyester degradation rate in turn.As only by metal oxide (one of magnesia, lithia and zinc oxide with On) and ZrO₂Physical blending, metal oxide will not influence ZrO₂Crystal plane structure, can also change its suction type and hydrogen reduction Reaction mechanism, because can not also improve polyester degradation rate without improving hydrogen reduction catalytic efficiency.

Due to the presence of oxygen reduction catalyst inside polyester, oxygen can stop for a long time inside polyester, can be right Most weak ester group carries out oxidation reaction in polyester, accelerates the degree of polyester degradation.The degradation polyester of the prior art be from What surface of polyester started, and the present invention is by being mixed into polyester for oxygen reduction catalyst, it provides and a kind of degrades inside polyester New approaches.

The ZrO of fluorine-containing binary acid and doping vario-property that the present invention introduces in polyester molecule chain₂Powder can also play collaboration Effect, for fluorine-containing binary acid since fluorine atom is on α carbon, electron-withdrawing ability is stronger, so that the electron cloud in polyester on C-O key is close Degree reduces, and the stability decline of tetrahedral anion is conducive to the progress of degradation reaction, the ZrO of doping vario-property₂Powder can The conduction velocity of oxonium ion is improved, accelerates oxygen reduction reaction, further promotes the progress of degradation reaction, thus is further improved Natural degradation rate.

The present invention also improves polyester catalyst, improves catalyst activity, reduces catalyst amount, saves Cost.

Current polyester catalyst is mainly based on antimonial, such as antimony oxide, antimony glycol and antimony acetate, work The additional amount of antimony is greater than 200ppm in polyester synthesis in industry, since antimony is heavy metal, the progress in epoch, for the system of antimony catalyst It is about increasingly tighter, it, still can not be due to color and activity control etc. are various although the catalysis of titanium system is applied Replace antimony system in short time.

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.

The utility model has the advantages that

(1) preparation method of a kind of low elastic polyester filament semi-dull of the invention, simple process and low cost, by poly- The ZrO of fluorine-containing binary acid and doping vario-property is introduced in ester₂Powder is modified polyester, significantly improves the degradability of fiber Energy；

(2) preparation method of a kind of low elastic polyester filament semi-dull of the invention, passes through the metal with certain catalytic activity Oxide improves antimony oxide specific surface area S to the doping vario-property of antimony oxide_gWith the active r in per surface area_s, To improve the catalytic activity of antimony oxide, polymerization efficiency is improved；And then the same of production of polyester needs can met When reduce synthesis polyester when antimony-based catalyst additive amount, effectively reduce be made thereafter fiber antimony discharge, be advantageously implemented Environmental protection production；

(3) a kind of low elastic polyester filament semi-dull of the invention, natural degradation rate is fast, is easy degradation recycling and quality It does not reduce, good mechanical property, application prospect is good.

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 low elastic polyester filament semi-dull, steps are as follows:

(1) modified poly ester is prepared；

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

(a) Mg (NO for being 0.8mol% by concentration₃)₂The Sb that aqueous solution and concentration are 8mol%₂O₃Solution mixing it is equal It is even, Sb₂O₃The solvent of solution be oxalic acid, Mg in mixed liquor²⁺With Sb³⁺Molar ratio be 2:100；

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

(c) 2.5h is kept the temperature after the product after drying being warming up to 400 DEG C first, keeps the temperature 1.5h 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) ZrO of doping vario-property is prepared₂Powder；

(a) Mg (NO for being 1.5wt% by concentration₃)₂The ZrO that aqueous solution and concentration are 22wt%₂Solution be uniformly mixed, ZrO₂The solvent of solution be nitric acid, Mg in mixed liquor²⁺With Zr⁴⁺Molar ratio be 6:100；

(b) pH value that ammonium hydroxide to the mixed liquor of concentration 2mol/L is added dropwise obtains precipitated product for 9, washes to precipitated product It washs and dries, dry temperature is 108 DEG C, time 2.5h；

(c) 2.5h is kept the temperature after desciccate being warming up to 400 DEG C, 1.5h is kept the temperature after then heating to 700 DEG C, finally in sky It is crushed after cooling in gas and obtains the ZrO for the doping vario-property that partial size is 0.4 micron₂Powder；

(1.3) esterification；

By terephthalic acid (TPA), ethylene glycol and 2, fluoro- 1, the 3- malonic acid of 2- bis- is made into slurry, the ZrO of doping vario-property is added₂Powder 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 90% when be esterification terminal, terephthalic acid (TPA), ethylene glycol and 2, the molar ratio of fluoro- 1, the 3- malonic acid of 2- bis- is 1:1.5: 0.05, the ZrO of doping vario-property₂The Sb of powder, doping vario-property₂O₃The additional amount of powder, titanium dioxide and triphenyl phosphate is respectively 0.07wt%, 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 modified poly ester that molecular weight distributing index is 1.8；

(2) modified poly ester POY are prepared；

Modified poly ester melt squeezes out through metering, spinneret, is cooling, oiling and obtaining modified poly ester POY after winding, POY The parameter of technique are as follows: 285 DEG C of spinning temperature, 20 DEG C of cooling temperature, winding speed 3200m/min；

(3) modified poly ester DTY are prepared；

Modified poly ester POY obtain modified poly ester DTY after seal wire, heating stretching, false twisting, thermal finalization and winding, i.e., Obtain low elastic polyester filament semi-dull, the parameter of DTY technique are as follows: spinning speed 700m/min, overfeed rate of setting 4.5% wind overfeeding Rate 3%, the first 210 DEG C of heater temperature, the second 170 DEG C of heater temperature, draw ratio 1.7.

The filament number of low elastic polyester filament semi-dull obtained is 1.0dtex, breaking strength 3.5cN/dtex, and fracture stretches Long rate is 22%, crimp contraction 9%, and curling stability is 77%, and internet pricing is 95/m, and line density deviation ratio is 1.9%, breaking strength CV value is 7.8%, and extension at break CV value is 7.8%, and crimp contraction coefficient of variation CV value is 8.8%, Boiling water shrinkage is 5.4%；

It is special after low elastic polyester filament semi-dull is placed 60 months under conditions of temperature is 25 DEG C and relative humidity is 65% Property viscosity decline 15%.

Comparative example 1

A kind of preparation method of dacron thread, it is almost the same with embodiment 1, the difference is that, step is not added in (1.3) The ZrO of 2,2- bis- fluoro- 1,3- malonic acid and doping vario-property₂Powder.The filament number of final dacron thread obtained is 1.0dtex, Breaking strength is 3.6cN/dtex, and elongation at break 22.5%, crimp contraction 9%, curling stability is 77%, network Degree is 95/m, and line density deviation ratio is 1.9%, and breaking strength CV value is 7.5%, and extension at break CV value is 7.5%, and curling is received Shrinkage coefficient of variation CV value is 9.0%, boiling water shrinkage 5.5%；Dacron thread is 25 DEG C in temperature and relative humidity is 65% Under conditions of place 60 months after, inherent viscosity decline 4%.Embodiment 1 is compared with comparative example 1 it is found that the present invention is led to It crosses and polyester is modified, substantially increase the degradability of polyester fiber and mechanical property is unaffected.

Comparative example 2

A kind of preparation method of dacron thread, it is almost the same with embodiment 1, the difference is that, 3 are used in step (1.3), The 3- difluoro glutaric acid substitution fluoro- 1,3- malonic acid of 2,2- bis- and the ZrO for not adding doping vario-property₂Powder, final terylene obtained After silk is placed 60 months under conditions of temperature is 25 DEG C and relative humidity is 65%, inherent viscosity decline 4.7%.It will implement Example 1 and comparative example 1 compare it is found that ZrO due to being not added with doping vario-property₂The fluorine-containing binary acid of powder and fluorine atom in β carbon β carbon on there are when electron-withdrawing group, generated influence is limited only on adjacent carbons, and in ester bond C-O key generate shadow Very little is rung, thus for OH^-The reaction influence that nucleophilic addition occurs for attack ester carbonyl group is smaller, and then to the natural degradation mistake of fiber Journey influences smaller therefore of the invention fluorine atom in the fluorine-containing binary acid of α carbon and the ZrO of doping vario-property₂Powder, which is more advantageous to, to be mentioned Rise the natural degradation performance of fiber.

Embodiment 2

(1) modified poly ester is prepared；

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

(a) Ca (NO for being 0.5mol% by concentration₃)₂The Sb that aqueous solution and concentration are 5mol%₂O₃Solution mixing it is equal It is even, Sb₂O₃The solvent of solution be oxalic acid, Ca in mixed liquor²⁺With Sb³⁺Molar ratio be 1:100；

(b) pH value that ammonium hydroxide to mixed liquor that concentration is 2mol/L is added dropwise is 10 to obtain precipitated product, is then produced to precipitating Object is washed and is dried, and dry temperature is 110 DEG C, time 2h；

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

(1.2) ZrO of doping vario-property is prepared₂Powder；

(a) LiNO for being 1wt% by concentration₃The ZrO that aqueous solution and concentration are 20wt%₂Solution be uniformly mixed, ZrO₂'s The solvent of solution is nitric acid, Li in mixed liquor⁺With Zr⁴⁺Molar ratio be 5:100；

(b) pH value that ammonium hydroxide to the mixed liquor of concentration 2mol/L is added dropwise obtains precipitated product for 10, carries out to precipitated product Washing and drying, dry temperature are 105 DEG C, time 3h；

(c) 2h is kept the temperature after desciccate being warming up to 400 DEG C, 1h is kept the temperature after then heating to 700 DEG C, finally in air It is crushed after cooling and obtains the ZrO for the doping vario-property that partial size is 0.4 micron₂Powder；

(1.3) esterification；

By terephthalic acid (TPA), ethylene glycol and 2, the fluoro- 1, 4- succinic acid of 2- bis- is made into slurry, the ZrO of doping vario-property is added₂Powder The Sb of body, doping vario-property₂O₃Powder, titanium dioxide and trimethyl phosphate after mixing, pressurize in nitrogen atmosphere and are esterified Reaction, moulding pressure are normal pressure, and the temperature of esterification is 260 DEG C, when the water quantity of distillate in esterification reaches theoretical value It is esterification terminal when 95%, the molar ratio of terephthalic acid (TPA), ethylene glycol and 2, the fluoro- 1, 4- succinic acid of 2- bis- is 1:1.2.0: 0.032, the ZrO of doping vario-property₂The Sb of powder, doping vario-property₂O₃The additional amount of powder, titanium dioxide and trimethyl phosphate is distinguished For 0.04wt%, 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 modified poly ester that molecular weight distributing index is 2.2；

(2) modified poly ester POY are prepared；

Modified poly ester melt squeezes out through metering, spinneret, is cooling, oiling and obtaining modified poly ester POY after winding, POY The parameter of technique are as follows: 285 DEG C of spinning temperature, 22 DEG C of cooling temperature, winding speed 2900m/min；

(3) modified poly ester DTY are prepared；

The filament number of low elastic polyester filament semi-dull obtained is 0.5dtex, breaking strength 3.8cN/dtex, and fracture stretches Long rate is 28%, crimp contraction 9%, and curling stability is 82%, and internet pricing is 90/m, and line density deviation ratio is 1.8%, breaking strength CV value is 7.2%, and extension at break CV value is 7.2%, and crimp contraction coefficient of variation CV value is 8.1%, Boiling water shrinkage is 4.5%；

Embodiment 3

(1) modified poly ester is prepared；

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

(a) Ba (NO for being 1.0mol% by concentration₃)₂The Sb that aqueous solution and concentration are 10mol%₂O₃Solution mixing it is equal It is even, Sb₂O₃The solvent of solution be oxalic acid, Ba in mixed liquor²⁺With Sb³⁺Molar ratio be 3:100；

(b) pH value that ammonium hydroxide to mixed liquor that concentration is 2mol/L is added dropwise is 9.5 to obtain precipitated product, is then produced to precipitating Object is washed and is dried, and dry temperature is 105 DEG C, time 3h；

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

(1.2) ZrO of doping vario-property is prepared₂Powder；

(a) Zn (NO for being 2wt% by concentration₃)₂The ZrO that aqueous solution and concentration are 25wt%₂Solution be uniformly mixed, ZrO₂The solvent of solution be nitric acid, Zn in mixed liquor²⁺With Zr⁴⁺Molar ratio be 8:100；

(b) pH value that ammonium hydroxide to the mixed liquor of concentration 2mol/L is added dropwise obtains precipitated product for 10, carries out to precipitated product Washing and drying, dry temperature are 110 DEG C, time 2h；

(c) 3h is kept the temperature after desciccate being warming up to 400 DEG C, 2h is kept the temperature after then heating to 700 DEG C, finally in air It is crushed after cooling and obtains the ZrO for the doping vario-property that partial size is 0.4 micron₂Powder；

(1.3) esterification；

By terephthalic acid (TPA), ethylene glycol and 2, fluoro- 1, the 5- glutaric acid of 2- bis- is made into slurry, the ZrO of doping vario-property is added₂Powder The Sb of body, doping vario-property₂O₃After mixing, pressurization carries out ester in nitrogen atmosphere for powder, titanium dioxide and Trimethyl phosphite Change reaction, moulding pressure 0.2MPa, the temperature of esterification is 255 DEG C, when the water quantity of distillate in esterification reaches theoretical Value 95% when be esterification terminal, terephthalic acid (TPA), ethylene glycol and 2, the molar ratio of fluoro- 1, the 5- glutaric acid of 2- bis- is 1: 1.5.:0.034 the ZrO of doping vario-property₂The Sb of powder, doping vario-property₂O₃The addition of powder, titanium dioxide and Trimethyl phosphite Amount is respectively 0.045wt%, 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 modified poly ester that molecular weight distributing index is 2.0；

(2) modified poly ester POY are prepared；

Modified poly ester melt squeezes out through metering, spinneret, is cooling, oiling and obtaining modified poly ester POY after winding, POY The parameter of technique are as follows: 285 DEG C of spinning temperature, 20 DEG C of cooling temperature, winding speed 2900m/min；

(3) modified poly ester DTY are prepared；

The filament number of low elastic polyester filament semi-dull obtained is 1.5dtex, breaking strength 3.8cN/dtex, and fracture stretches Long rate is 27%, crimp contraction 10%, and curling stability is 81%, and internet pricing is 100/m, and line density deviation ratio is 1.8%, breaking strength CV value is 7.3%, and extension at break CV value is 7.4%, and crimp contraction coefficient of variation CV value is 8.2%, Boiling water shrinkage is 4.7%；

It is special after low elastic polyester filament semi-dull is placed 60 months under conditions of temperature is 25 DEG C and relative humidity is 65% Property viscosity decline 16%.

Embodiment 4

(1) modified poly ester is prepared；

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

(a) Zn (NO for being 0.6mol% by concentration₃)₂The Sb that aqueous solution and concentration are 6mol%₂O₃Solution mixing it is equal It is even, Sb₂O₃The solvent of solution be oxalic acid, Zn in mixed liquor²⁺With Sb³⁺Molar ratio be 1.2:100；

(b) pH value that ammonium hydroxide to mixed liquor that concentration is 2mol/L is added dropwise is 10 to obtain precipitated product, is then produced to precipitating Object is washed and is dried, and dry temperature is 110 DEG C, time 2.5h；

(c) 2.5h is kept the temperature after the product after drying being warming up to 400 DEG C first, 1h is kept the temperature after then heating to 900 DEG C, most It is crushed after cooling down in air afterwards and obtains the Sb for the doping vario-property that average grain diameter is 0.4 micron₂O₃Powder；

(1.2) ZrO of doping vario-property is prepared₂Powder；

(a) Mg (NO for being 1.2wt% by concentration₃)₂The ZrO that aqueous solution and concentration are 22wt%₂Solution be uniformly mixed, ZrO₂The solvent of solution be nitric acid, Mg in mixed liquor²⁺With Zr⁴⁺Molar ratio be 6:100；

(b) pH value that ammonium hydroxide to the mixed liquor of concentration 2mol/L is added dropwise obtains precipitated product for 9, washes to precipitated product It washs and dries, dry temperature is 106 DEG C, time 2.5h；

(1.3) esterification；

By terephthalic acid (TPA), ethylene glycol and 2, fluoro- 1, the 5- glutaric acid of 2- bis- is made into slurry, the ZrO of doping vario-property is added₂Powder The Sb of body, doping vario-property₂O₃Powder, titanium dioxide and triphenyl phosphate after mixing, pressurize in nitrogen atmosphere and are esterified Reaction, moulding pressure 0.25MPa, the temperature of esterification is 250 DEG C, when the water quantity of distillate in esterification reaches theoretical value 95% when be esterification terminal, terephthalic acid (TPA), ethylene glycol and 2, the molar ratio of fluoro- 1, the 5- glutaric acid of 2- bis- is 1:1.4: 0.036, the ZrO of doping vario-property₂The Sb of powder, doping vario-property₂O₃The additional amount of powder, titanium dioxide and triphenyl phosphate is distinguished For 0.05wt%, 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 modified poly ester that molecular weight distributing index is 1.9；

(2) modified poly ester POY are prepared；

Modified poly ester melt squeezes out through metering, spinneret, is cooling, oiling and obtaining modified poly ester POY after winding, POY The parameter of technique are as follows: 280 DEG C of spinning temperature, 20 DEG C of cooling temperature, winding speed 3200m/min；

(3) modified poly ester DTY are prepared；

Modified poly ester POY obtain modified poly ester DTY after seal wire, heating stretching, false twisting, thermal finalization and winding, i.e., Obtain low elastic polyester filament semi-dull, the parameter of DTY technique are as follows: spinning speed 600m/min, overfeed rate of setting 3.5% wind overfeeding Rate 2.5%, the first 200 DEG C of heater temperature, the second 160 DEG C of heater temperature, draw ratio 1.6.

The filament number of low elastic polyester filament semi-dull obtained is 0.7dtex, breaking strength 3.7cN/dtex, and fracture stretches Long rate is 26%, crimp contraction 10%, and curling stability is 81%, and internet pricing is 95/m, and line density deviation ratio is 1.9%, breaking strength CV value is 7.5%, and extension at break CV value is 7.4%, and crimp contraction coefficient of variation CV value is 8.4%, Boiling water shrinkage is 4.8%；

Embodiment 5

(1) modified poly ester is prepared；

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

(a) Mg (NO for being 0.7mol% by concentration₃)₂The Sb that aqueous solution and concentration are 8mol%₂O₃Solution mixing it is equal It is even, Sb₂O₃The solvent of solution be oxalic acid, Mg in mixed liquor²⁺With Sb³⁺Molar ratio be 2:100；

(c) 2.5h is kept the temperature after the product after drying being warming up to 400 DEG C first, 2h is kept the temperature after then heating to 900 DEG C, most It is crushed after cooling down in air afterwards and obtains the Sb for the doping vario-property that average grain diameter is 0.5 micron₂O₃Powder；

(1.2) ZrO of doping vario-property is prepared₂Powder；

(a) LiNO for being 1.6wt% by concentration₃The ZrO that aqueous solution and concentration are 24wt%₂Solution be uniformly mixed, ZrO₂ The solvent of solution be nitric acid, Li in mixed liquor⁺With Zr⁴⁺Molar ratio be 7:100；

(b) pH value that ammonium hydroxide to the mixed liquor of concentration 2mol/L is added dropwise is 9~10 to obtain precipitated product, to precipitated product into Row washing and drying, dry temperature are 110 DEG C, time 2h；

(c) 3h is kept the temperature after desciccate being warming up to 400 DEG C, 2h is kept the temperature after then heating to 700 DEG C, finally in air It is crushed after cooling and obtains the ZrO for the doping vario-property that partial size is 0.45 micron₂Powder；

(1.3) esterification；

By terephthalic acid (TPA), ethylene glycol and 2,2,3,3- tetra- fluoro- 1, 4- succinic acids are made into slurry, doping vario-property are added ZrO₂The Sb of powder, doping vario-property₂O₃Powder, titanium dioxide and triphenyl phosphate after mixing, pressurize in nitrogen atmosphere into Row esterification, moulding pressure 0.15MPa, the temperature of esterification is 260 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, mole of 2,3,3- tetra- fluoro- 1, 4- succinic acids Than for 1:1.5:0.04, the ZrO of doping vario-property₂The Sb of powder, doping vario-property₂O₃Powder, titanium dioxide and triphenyl phosphate plus Enter 0.055wt%, 0.015wt%, 0.25wt% and 0.05wt% that amount is respectively 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 modified poly ester that molecular weight distributing index is 2.1；

(2) modified poly ester POY are prepared；

Modified poly ester melt squeezes out through metering, spinneret, is cooling, oiling and obtaining modified poly ester POY after winding, POY The parameter of technique are as follows: 290 DEG C of spinning temperature, 18 DEG C of cooling temperature, winding speed 2800m/min；

(3) modified poly ester DTY are prepared；

Modified poly ester POY obtain modified poly ester DTY after seal wire, heating stretching, false twisting, thermal finalization and winding, i.e., Low elastic polyester filament semi-dull is obtained, the parameter of DTY technique are as follows: spinning speed 600m/min, overfeed rate of setting 3.5% wind overfeeding Rate 2.5%, the first 200 DEG C of heater temperature, the second 160 DEG C of heater temperature, draw ratio 1.6.

The filament number of low elastic polyester filament semi-dull obtained is 0.7dtex, breaking strength 3.7cN/dtex, and fracture stretches Long rate is 26%, crimp contraction 10%, and curling stability is 80%, and internet pricing is 95/m, and line density deviation ratio is 1.9%, breaking strength CV value be 7.5%, extension at break CV value be 7.6%, crimp contraction coefficient of variation CV value be≤ 9.0%, boiling water shrinkage 4.9%；

It is special after low elastic polyester filament semi-dull is placed 60 months under conditions of temperature is 25 DEG C and relative humidity is 65% Property viscosity decline 16.5%.

Embodiment 6

(1) modified poly ester is prepared；

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

(a) be by concentration 0.8mol% Mg (NO₃)₂Aqueous solution and Ca (NO₃)₂1:1 is mixed aqueous solution by volume To metal ion N^y+Aqueous solution, metal ion N^y+Aqueous solution and concentration be 8mol% Sb₂O₃Solution mixing it is equal It is even, Sb₂O₃The solvent of solution be oxalic acid, N in mixed liquor^y+With Sb³⁺Molar ratio be 2.5:100；

(b) pH value that ammonium hydroxide to mixed liquor that concentration is 2mol/L is added dropwise is 10 to obtain precipitated product, is then produced to precipitating Object is washed and is dried, and dry temperature is 105 DEG C, time 3h；

(c) 3h is kept the temperature after the product after drying being warming up to 400 DEG C first, 1.5h is kept the temperature after then heating to 900 DEG C, most It is crushed after cooling down in air afterwards and obtains the Sb for the doping vario-property that average grain diameter is 0.4 micron₂O₃Powder；

(1.2) ZrO of doping vario-property is prepared₂Powder；

(a) be by concentration 2wt% Mg (NO₃)₂Aqueous solution and Zn (NO₃)₂Aqueous solution 1:1 in mass ratio is mixed to get Metal ion M^x+Solution, by metal ion M^x+Solution and concentration be 20wt% ZrO₂Solution be uniformly mixed, ZrO₂The solvent of solution be nitric acid, metal ions M in mixed liquor^x+With Zr⁴⁺Molar ratio be 8:100；

(1.3) esterification；

By terephthalic acid (TPA), ethylene glycol and 2,2,3,3- tetra- fluoro- 1, 4- succinic acids are made into slurry, doping vario-property are added ZrO₂The 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 94% when be esterification terminal, terephthalic acid (TPA), ethylene glycol and 2, mole of 2,3,3- tetra- fluoro- 1, 4- succinic acids Than for 1:1.6:0.042, the ZrO of doping vario-property₂The Sb of powder, doping vario-property₂O₃Powder, titanium dioxide and triphenyl phosphate Additional amount is respectively 0.059wt%, 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 modified poly ester that molecular weight distributing index is 1.8；

(2) modified poly ester POY are prepared；

(3) modified poly ester DTY are prepared；

Modified poly ester POY obtain modified poly ester DTY after seal wire, heating stretching, false twisting, thermal finalization and winding, i.e., Obtain low elastic polyester filament semi-dull, the parameter of DTY technique are as follows: spinning speed 900m/min, overfeed rate of setting 5.5% wind overfeeding Rate 5.0%, the first 220 DEG C of heater temperature, the second 180 DEG C of heater temperature, draw ratio 1.8.

The filament number of low elastic polyester filament semi-dull obtained is 1.2dtex, breaking strength 3.6cN/dtex, and fracture stretches Long rate is 24%, crimp contraction 11%, and curling stability is 79%, and internet pricing is 95/m, and line density deviation ratio is 1.9%, breaking strength CV value is 7.6%, and extension at break CV value is 7.6%, and crimp contraction coefficient of variation CV value is 8.5%, Boiling water shrinkage is 5.1%；

It is special after low elastic polyester filament semi-dull is placed 60 months under conditions of temperature is 25 DEG C and relative humidity is 65% Property viscosity decline 17%.

Embodiment 7

(1) modified poly ester is prepared；

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

(a) be by concentration 0.5mol% Mg (NO₃)₂Aqueous solution, Ba (NO₃)₂Aqueous solution and Ca (NO₃)₂Aqueous solution is pressed Volume ratio 1:1:1 is mixed to get metal ion N^y+Aqueous solution, metal ion N^y+Aqueous solution and concentration be 10mol% Sb₂O₃Solution be uniformly mixed, Sb₂O₃The solvent of solution be oxalic acid, metal ion N in mixed liquor^y+With Sb³⁺Molar ratio For 2:100；

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

(c) 2.5h is kept the temperature after the product after drying being warming up to 400 DEG C first, 2h is kept the temperature after then heating to 900 DEG C, most It is crushed after cooling down in air afterwards and obtains the Sb for the doping vario-property that average grain diameter is 0.4 micron₂O₃Powder；

(1.2) ZrO of doping vario-property is prepared₂Powder；

(a) be by concentration 1wt% Mg (NO₃)₂Aqueous solution, LiNO₃Aqueous solution and Zn (NO₃)₂Aqueous solution is in mass ratio 1:1 is mixed to get metal ion M^x+Solution, by metal ion M^x+Solution and concentration be 24wt% ZrO₂Solution It is uniformly mixed, ZrO₂The solvent of solution be nitric acid, metal ions M in mixed liquor^x+With Zr⁴⁺Molar ratio be 6:100；

(b) pH value that ammonium hydroxide to the mixed liquor of concentration 2mol/L is added dropwise obtains precipitated product for 10, carries out to precipitated product Washing and drying, dry temperature are 110 DEG C, time 3h；

(c) 2h is kept the temperature after desciccate being warming up to 400 DEG C, 2h is kept the temperature after then heating to 700 DEG C, finally in air It is crushed after cooling and obtains the ZrO for the doping vario-property that partial size is 0.45 micron₂Powder；

(1.3) esterification；

By terephthalic acid (TPA), ethylene glycol and 2, fluoro- 1, the 3- malonic acid of 2- bis- is made into slurry, the ZrO of doping vario-property is added₂Powder The Sb of body, doping vario-property₂O₃Powder, titanium dioxide and triphenyl phosphate after mixing, pressurize in nitrogen atmosphere and are esterified Reaction, moulding pressure 0.2MPa, the temperature of esterification is 255 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 ratio of fluoro- 1, the 3- malonic acid of 2- bis- is 1:2.0: 0.045, the ZrO of doping vario-property₂The Sb of powder, doping vario-property₂O₃The additional amount of powder, titanium dioxide and triphenyl phosphate is distinguished For 0.064wt%, 0.012wt%, 0.20wt% 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 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 modified poly ester that molecular weight distributing index is 2.2；

(2) modified poly ester POY are prepared；

(3) modified poly ester DTY are prepared；

The filament number of low elastic polyester filament semi-dull obtained is 1.2dtex, breaking strength 3.6cN/dtex, and fracture stretches Long rate is 23%, crimp contraction 10.8%, and curling stability is 78%, and internet pricing is 95/m, and line density deviation ratio is 2.0%, breaking strength CV value is 7.9%, and extension at break CV value is 8.0%, and crimp contraction coefficient of variation CV value is 8.8%, Boiling water shrinkage is 5.4%；

Embodiment 8

(1) modified poly ester is prepared；

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

(1.2) ZrO of doping vario-property is prepared₂Powder；

(1.3) esterification；

By terephthalic acid (TPA), ethylene glycol and 2, fluoro- 1, the 3- malonic acid of 2- bis- is made into slurry, the ZrO of doping vario-property is added₂Powder 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 255 DEG C, when the water quantity of distillate in esterification reaches theoretical value 96% when be esterification terminal, terephthalic acid (TPA), ethylene glycol and 2, the molar ratio of fluoro- 1, the 3- malonic acid of 2- bis- is 1:2.0: 0.048, the ZrO of doping vario-property₂The Sb of powder, doping vario-property₂O₃The additional amount of powder, titanium dioxide and triphenyl phosphate is distinguished For 0.068wt%, 0.013wt%, 0.25wt% 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 50min Interior that absolute pressure 480Pa is steadily evacuated to by normal pressure, reaction temperature is 260 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 90min between seasonable, it is 29000 that number-average molecular weight, which is made, the modified poly ester that molecular weight distributing index is 2.1；

(2) modified poly ester POY are prepared；

Modified poly ester melt squeezes out through metering, spinneret, is cooling, oiling and obtaining modified poly ester POY after winding, POY The parameter of technique are as follows: 290 DEG C of spinning temperature, 20 DEG C of cooling temperature, winding speed 3200m/min；

(3) modified poly ester DTY are prepared；

Modified poly ester POY obtain modified poly ester DTY after seal wire, heating stretching, false twisting, thermal finalization and winding, i.e., Obtain low elastic polyester filament semi-dull, the parameter of DTY technique are as follows: spinning speed 800m/min, overfeed rate of setting 5%, winding overfeed rate 4.0%, the first 200 DEG C of heater temperature, the second 165 DEG C of heater temperature, draw ratio 1.7.

The filament number of low elastic polyester filament semi-dull obtained is 1.0dtex, breaking strength 3.5cN/dtex, and fracture stretches Long rate is 23%, crimp contraction 10%, and curling stability is 77%, and internet pricing is 90/m, and line density deviation ratio is 1.9%, breaking strength CV value is 8.0%, and extension at break CV value is 8.0%, and crimp contraction coefficient of variation CV value is 9.0%, Boiling water shrinkage is 5.5%；

It is special after low elastic polyester filament semi-dull is placed 60 months under conditions of temperature is 25 DEG C and relative humidity is 65% Property viscosity decline 18%.

Claims

1. the preparation method of low elastic polyester filament semi-dull, it is characterized in that: modified poly ester is made by modified poly ester melt by POY technique POY, then DTY technique is pressed by modified poly ester POY obtained modified poly ester DTY to get low elastic polyester filament semi-dull；

The modified poly ester the preparation method comprises the following steps: by terephthalic acid (TPA), ethylene glycol, fluorine-containing binary acid, delustering agent, doping vario-property ZrO₂The Sb of powder and doping vario-property₂O₃Powder successively carries out esterification and polycondensation reaction after mixing；

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 content of delustering agent is 0.20~0.25wt% in the modified poly ester；

ZrO₂The process of doping vario-property are as follows: first by metal ion M^x+Solution with contain Zr⁴⁺Solution be uniformly mixed, then drip The pH value for adding precipitating reagent to mixed liquor is 9~10, finally calcines precipitated product；

Metal ions M^x+For Mg²⁺、Li⁺And Zn²⁺One or more of；

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

Second heater temperature of the DTY technique is 160~180 DEG C.

2. the preparation method of low elastic polyester filament semi-dull according to claim 1, which is characterized in that ZrO₂It is doped When modified, the metal ion M^x+Solution concentration be 1~2wt%, solvent is water, the anion in solution be NO₃ ^-； It is described to contain Zr⁴⁺Solution be 20~25wt% of concentration ZrO₂Solution, solvent is nitric acid；The precipitating reagent is concentration 2mol/L Ammonium hydroxide；When precipitating starts, metal ions M in mixed liquor^x+With Zr⁴⁺Molar ratio be 5~8:100；To precipitating before the calcining Product is washed and is dried, and dry temperature is 105~110 DEG C, and the time is 2~3h；The process of the calcining are as follows: rise first Temperature keeps the temperature 1~2h, finally cools down in air to 2~3h of heat preservation after 400 DEG C after then heating to 700 DEG C；ZrO₂Change in doping It is crushed to obtain powder of the average grain diameter less than 0.5 micron after property.

3. the preparation method of low elastic polyester filament semi-dull according to claim 2, which is characterized in that Sb₂O₃It is doped When modified, the metal ion N^y+Solution concentration be 0.5~1.0mol%, solvent is water, and the anion in solution is NO₃ ^-；It is described to contain Sb³⁺Solution be 5~10mol% of concentration Sb₂O₃Solution, solvent is oxalic acid；The precipitating reagent is concentration The ammonium hydroxide of 2mol/L；When precipitating starts, metal ion N in mixed solution^y+With Sb³⁺Molar ratio be 1~3:100；The calcining Preceding that precipitated product is washed and dried, dry temperature is 105~110 DEG C, and the time is 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, is finally cooled down in air； Sb₂O₃It is crushed to obtain powder of the average grain diameter less than 0.5 micron after doping vario-property.

4. the preparation method of low elastic polyester filament semi-dull according to claim 3, which is characterized in that the modified poly ester Preparation step is as follows:

(1) esterification；

Terephthalic acid (TPA), ethylene glycol and fluorine-containing binary acid are made into slurry, the ZrO of doping vario-property is added₂Powder, doping vario-property Sb₂O₃After mixing, pressurization carries out esterification in nitrogen atmosphere, and moulding pressure is normal pressure for powder, delustering agent and stabilizer ~0.3MPa, the temperature of esterification are 250~260 DEG C, when the water quantity of distillate in esterification reach the 90% of theoretical value with It was esterification terminal when upper；

(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.

5. the preparation method of low elastic polyester filament semi-dull according to claim 4, which is characterized in that the terephthaldehyde The molar ratio of acid, ethylene glycol and fluorine-containing binary acid is 1:1.2~2.0:0.03~0.05, the ZrO of the doping vario-property₂Powder, The Sb of doping vario-property₂O₃The additional amount of powder, delustering agent and stabilizer be respectively terephthalic acid (TPA) additional amount 0.04~ 0.07wt%, 0.012~0.015wt%, 0.20~0.25wt% and 0.01~0.05wt%.

6. the preparation method of low elastic polyester filament semi-dull according to claim 5, which is characterized in that the delustering agent is two Titanium oxide, the stabilizer are triphenyl phosphate, trimethyl phosphate or Trimethyl phosphite.

7. the preparation method of low elastic polyester filament semi-dull according to claim 6, which is characterized in that the number of modified poly ester is equal Molecular weight is 25000~30000, and molecular weight distributing index is 1.8~2.2.

8. the preparation method of low elastic polyester filament semi-dull according to claim 1, which is characterized in that the POY technique Process are as follows: metering, spinneret squeeze out, are cooling, oiling and wind；

The parameter of the POY technique are as follows: 280~290 DEG C of spinning temperature, 18~22 DEG C of cooling temperature, winding speed 3200~ 3600m/min；

The parameter of the DTY technique are as follows: 600~900m/min of spinning speed, overfeed rate of setting 3.5~5.5%, winding overfeed rate 2.5~5.0%, the first 200~220 DEG C of heater temperature, draw ratio 1.6~1.8.

9. semi-dull made from the preparation method using low elastic polyester filament semi-dull as described in any one of claims 1 to 8 wash Synthetic fibre low stretch yarn, it is characterized in that: being modified poly ester DTY；

The ZrO of delustering agent, the doping vario-property is dispersed in the modified poly ester₂The Sb of powder and the doping vario-property₂O₃Powder Body, the content of delustering agent are 0.20~0.25wt%.

10. low elastic polyester filament semi-dull according to claim 9, which is characterized in that the monofilament of low elastic polyester filament semi-dull Fiber number is 0.5~1.5dtex, and breaking strength >=3.5cN/dtex, elongation at break is 25.0 ± 3.0%, and crimp contraction is 10.0 ± 1.0%, stability >=77% is crimped, internet pricing is 95 ± 5/m, line density deviation ratio≤2.0%, breaking strength CV Value≤8.0%, extension at break CV value≤8.0%, crimp contraction coefficient of variation CV value≤9.0%, boiling water shrinkage be 5.0 ± 0.5%；

After low elastic polyester filament semi-dull is placed 60 months under conditions of temperature is 25 DEG C and relative humidity is 65%, characteristic is viscous Degree decline 15~18%.