CN109722732A

CN109722732A - A kind of super fine denier polyester fiber and preparation method thereof

Info

Publication number: CN109722732A
Application number: CN201811614133.2A
Authority: CN
Inventors: 张元华; 康爱旗; 汤方明
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: 2019-05-07
Anticipated expiration: 2038-12-27
Also published as: CN109722732B

Abstract

The present invention relates to a kind of super fine denier polyester fibers and preparation method thereof, the preparation method comprises the following steps: being made modified poly ester FDY by modified poly ester melt by FDY technique to get super fine denier polyester fiber；Super fine denier polyester fiber obtained is modified poly ester FDY, the strand of modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment and the siliceous dihydric alcohol segment of main chain, the siliceous dihydric alcohol of main chain is Dimethylsilanediol, dimethyl diphenyl disiloxane glycol or tetramethyl disiloxane glycol, the solid heteropoly acid powder by high-temperature roasting is dispersed in modified poly ester, the temperature of 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.Preparation method of the present invention, simple process, can effectively improve polyester hydrolysis rate and dyeability and product mechanical property obtained it is excellent.

Description

A kind of super fine denier polyester fiber and preparation method thereof

Technical field

The invention belongs to polyester fiber technical field, it is related to a kind of super fine denier polyester fiber and preparation method thereof.

Background technique

Polyethylene terephthalate (PET) is a kind of polymer of function admirable, and PET is high with modulus, strong because of it The advantages that degree is high, conformality is good and barrier property is good is widely used in the fields such as fiber, bottle packaging, film and sheet material, yield Cumulative year after year, position in industry are obviously improved.With the production-scale expansion of polyester fiber, production technology has also obtained very big mention Height is gradually developed to production mode reforms such as high-tech, functionalization and fibres in differentiation by the production of the incipient product that routinizes, The application field of polyester fiber also gradually develops to the fields such as decoration, industry from initial fiber of taking.As fiber produces skill Art continuously improve and it is perfect, improve the surcharge of fiber, be chemical fibre development inexorable trend.Produce fibre in differentiation product There are mainly two types of approach: first is that manufacturing new high polymer using new monomer or synthetic method, another method is by existing Fiber be modified, so that it is obtained new performance, and have the advantages that small investment, quick thus wide using latter method General use, the major technique of this method have polymer modification technology, superfine fibre manufacturing technology, profiled filament manufacturing technology and Composite spinning technology etc..

Fine-denier, superfine Denier fibre are to develop a kind of very rapid fibre in differentiation in recent years, are a kind of high-quality, high skill The textile raw material of art is the Typical Representative for the shin-gosen that chemical fibre develops to high-tech, high summylation direction.About fine-denier and The definition of superfine Denier fibre, a unified standard received by everybody, most manufacturers are currently not yet with filament number Standard.Fine count fiber is defined as filament number < 1.2dtex by China, and superfine Denier fibre is defined as filament number < 0.56dtex. When filament number it is small to a certain extent when, it may appear that many strange performances.The small bending resistance of superfine Denier fibre diameter is small, yarn compared with It is soft；Large specific surface area, spreadability is big, more fluffy；Fabric surface has concaveconvex structure, increases powder sense.Superfine Denier fibre has Capillary core absorption, so as to improve the penetrability of fabric, the warmth retention property of packed density with higher, fabric is more preferable.

PET fiber has excellent physical mechanical property due to its regular molecular structure and higher crystallinity, but This also brings the difficulty of dyeing to PET fiber simultaneously.Lack the active group that can be bonded with dyestuff in molecular structure, only It can be dyed using disperse dyes.Disperse dyes belong to nonionic dye, and molecular dimension is larger, water-soluble very low, in addition PET fiber water imbibition is low, is not easy extruding in water, so the dispersion particle of dyestuff is difficult to from solution when being dyed with conventional method Into fiber.It is very low the dye-uptake under fluidized state.Generally use carrier dyeing process or high temperature and high pressure method, carrier dyeing It is expensive, and problem is brought at two aspects of technology and ecology；The internal plasticization of carrier is conducive to dyestuff in fibrous inside Diffusion, but remaining carrier can make the light resistance of dyestuff be deteriorated, and cause to pollute.The necessary special pressure resistance of high-temperature pressure dyeing Equipment, and it is unsuitable for the production of Large Scale and Continuous metaplasia, and it is big to consume energy, and produces dangerous.

In addition, with the fast development of PET industry, although PET will not directly cause damages to environment, due to its use Rear waste product huge amount and very strong to the repellence of atmosphere and microorganism reagent, PET waste oneself become global environment Organic Pollutants.Currently, the common processing method to PET waste has landfill, burning and recycling, though landfill and burning It is so simplest method, certain pollution will be also caused to environment, degradation recycling is that processing PET waste is effectively scientific Approach, but due to PET construction densification, crystallinity is high, and natural degradation time is very long, the ratio recycled at present also very little.Base Enhancing, resource-effective and sustainability demand in environmental consciousness, take polyester fiber natural degradation oneself become section, China Skilled worker author's problem in the urgent need to address.

Therefore, the great realistic meaning of super fine denier polyester fiber that a kind of dyeability is good and degradation rate is fast is studied.

Summary of the invention

The purpose of the present invention is overcoming to take the defect that dyeing polyester fibers are poor and degradation rate is slow in the prior art, mention For a kind of super fine denier polyester for improving polyester degradation rate and degradation effect and dyeability by being modified to polyester Fiber and preparation method thereof.

In order to achieve the above object, the present invention adopts the following technical scheme that:

Modified poly ester FDY is made by modified poly ester melt by FDY technique in a kind of preparation method of super fine denier polyester fiber Silk is to get super fine denier polyester fiber；

The modified poly ester the preparation method comprises the following steps: by the siliceous dihydric alcohol of terephthalic acid (TPA), ethylene glycol, main chain and through excessively high The solid heteropoly acid powder of temperature roasting successively carries out esterification and polycondensation reaction after mixing；

The siliceous dihydric alcohol of main chain is two silicon oxygen of Dimethylsilanediol, dimethyl diphenyl disiloxane glycol or tetramethyl Alkane glycol；The present invention on polyester molecule chain by introducing the siliceous dihydric alcohol of main chain, on the one hand, contains on high polymer main chain There is-Si-O-Si- key, silicon oxygen bond gap is larger, and inward turning Transactivation can be lower, is conducive to atom and rotates freely, and is conducive to improve high Strand is at a distance from the interaction force and chain and interchain of interchain, on the other hand, Si atom and-CH on high polymer main chain₃ Connection ,-CH₃- CH is led to due to Si-C key ratio C-C key bond distance perpendicular to the plane where Si-O-Si atom₃In three H be in Softened state ,-CH₃In three distracted H atoms can rotate freely and distance between adjacent Si-O molecule segment is made to become larger, The specification inertia methyl of this outside chain hinders high molecular close again, thus high molecular material is very submissive, and cavity is freely The high molecular material of the volume dihydric alcohol siliceous relative to main chain is not introduced into increases obvious.Disperse dyes are that molecule is smaller And exist in granular form mostly in structure without the dyestuff of water soluble group, partial size is in several hundred nanometers between one micron. When modified poly ester of the present invention starts dyeing, with the continuous improvement of temperature, due to containing-Si-O-Si- in polyester macromolecule chain Key, silicon oxygen bond is long compared with carbon-oxygen bond, and inward turning Transactivation can be lower, prior to the strand setting in motion containing carbon-oxygen bond, works as dye bath temperature 120~130 DEG C need to be increased to, the severe degree of the macromolecular chain movement containing silicon oxygen bond is greater than containing only carbon-oxygen bond strand, together When due to empty free volume it is bigger, graininess dyestuff is promoted significant to the diffusion rate of fibrous inside, contains silicon oxygen bond Macromolecular chain formed empty free volume it is more efficient than the free volume formed containing only carbon-oxygen bond strand, make water or its Its molecule such as dyestuff etc. is easier to penetrate into modified poly ester macromolecule internal, the shadow positive to generations such as the dyeing of modified poly ester It rings, dyeing temperature can be reduced, shorten the time of dyeing, reduce energy consumption, while also improving the dye-uptake of fiber.

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.

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.

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。

As a preferred technical scheme:

A kind of preparation method of super fine denier polyester fiber as described above, the time of high-temperature roasting are 2~4h；SiO₂- TiO₂、SiO₂-ZrO₂、B₂O₃-Al₂O₃、TiO₂- ZnO and SiO₂TiO in-CaO₂、ZrO₂、Al₂O₃, ZnO and CaO content difference For 30~50wt%, 30~50wt%, 20~40wt%, 20~40wt% and 20~50wt%；Solid heteropoly acid is roasted in high temperature It is crushed to obtain powder of the average grain diameter less than 0.5 micron after burning.

A kind of preparation method of super fine denier polyester fiber as described above, the preparation step of the modified poly ester are as follows:

(1) esterification；

Terephthalic acid (TPA), ethylene glycol and the siliceous dihydric alcohol of main chain are made into slurry, the solid Jing Guo high-temperature roasting is added After mixing, pressurization carries out esterification, pressurization in nitrogen atmosphere for heteropoly acid powder, catalyst, 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 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 270~280 DEG C, the reaction time is 50~90min.

A kind of preparation method of super fine denier polyester fiber as described above, the terephthalic acid (TPA), ethylene glycol and main chain contain The molar ratio of the dihydric alcohol of silicon is 1:1.2~2.0:0.03~0.05, and the solid heteropoly acid powder by high-temperature roasting is urged The additional amount of agent, delustering agent and stabilizer be respectively 0.03~0.05wt% of terephthalic acid (TPA) additional amount, 0.03~ 0.05wt%, 0.20~0.25wt% and 0.01~0.05wt%.The siliceous dihydric alcohol of main chain of the present invention and solid heteropoly acid 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 too big to the regularity destruction of polyester macromolecule structure greatly, it is excessive to the crystallinity and Effect on Mechanical Properties of fiber, it is unfavorable for The production and application of fiber, additive amount is too low, then dyeing effect and degradation effect are promoted unobvious；

A kind of preparation method of super fine denier polyester fiber as described above, the catalyst are antimony oxide, ethylene glycol Antimony or antimony acetate, the delustering agent are titanium dioxide, and the stabilizer is triphenyl phosphate, trimethyl phosphate or phosphorous acid front three Ester.

A kind of preparation method of super fine denier polyester fiber as described above, the number-average molecular weight of the modified poly ester are 25000~30000, molecular weight distributing index is 1.8~2.2.

A kind of preparation method of super fine denier polyester fiber as described above, the process of the FDY technique are as follows: metering, spinneret Plate squeezes out, cools down, oils, stretching, thermal finalization and winding；

The parameter of the FDY technique are as follows: 285~300 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 4200~4500m/min, two 115~135 DEG C of roll temperature, 4130~4415m/min of winding speed.

The present invention also provides ultra-fine using one kind made from a kind of preparation method of super fine denier polyester fiber as described above Denier polyester fiber is modified poly ester FDY；

The strand of the modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment and the siliceous dihydric alcohol chain of main chain Section；

The solid heteropoly acid powder by high-temperature roasting is dispersed in the modified poly ester；

The filament number of super fine denier polyester fiber is 0.28~0.35dtex.

As a preferred technical scheme:

A kind of super fine denier polyester fiber as described above, breaking strength >=3.7cN/dtex of super fine denier polyester fiber break Split elongation be 30.0 ± 4.0%, internet pricing be 14 ± 4/m, line density deviation ratio≤1.00%, breaking strength CV value≤ 5.00%, extension at break CV value≤8.0%, boiling water shrinkage is 7.0 ± 0.5%；The present invention by the siliceous dihydric alcohol of chain and Solid heteropoly acid is modified polyester, and the quality and quality of fiber obtained do not reduce compared with the prior art, modified Fiber still has good mechanical property and spinnability etc.；

Dye-uptake of super fine denier polyester fiber under the conditions of 120 DEG C of temperature is that 87.3~92.2%, K/S value is 22.06 ~25.34；In the identical situation of other test conditions, dye-uptake of comparative sample under the conditions of 130 DEG C of temperature is 84.8%, K/S value is 21.03, and the difference of comparative sample and super fine denier polyester fiber of the invention is only that its material is conventional polyester and does not add Add the solid heteropoly acid powder by high-temperature roasting；

After super fine denier polyester fiber is placed 60 months under conditions of temperature is 25 DEG C and relative humidity is 65%, characteristic Viscosity decline 13~18%；Under the same terms, the inherent viscosity of comparative sample decline 3.2%, comparative sample and super fine denier of the invention The difference of polyester fiber is only that its material is conventional polyester and is not added with solid heteropoly acid powder by high-temperature roasting.

Invention mechanism:

The present invention is modified polyester by the siliceous dihydric alcohol of main chain, increases modified poly ester cavity free volume, empty The increase of hole free volume can reduce dye molecule and penetrate into difficulty inside modified poly ester, make super fine denier polyester obtained Fiber dyeing performance is greatly promoted；In addition, the modification due to solid heteropoly acid to polyester again, can promote in hydrolytic process The progress of nucleophilic addition, and significantly improve degradation rate.

The siliceous dihydric alcohol of main chain is as follows to the specific mechanism of action for the dyeability that polyester modification improves polyester fiber:

The siliceous dihydric alcohol of main chain of the invention is Dimethylsilanediol, dimethyl diphenyl disiloxane glycol or tetramethyl Base disiloxane glycol, structural formula difference are as follows:

Macromolecule chain rigidity is decided by the size of Rotational Barriers in strand, and backbone structure is different, wherein bond angle and key Long not equal or bonded mode is different, and rigidity is also different, present invention introduces after the siliceous dihydric alcohol of main chain, on high polymer main chain Containing-Si-O-Si- key, silicon oxygen bond gap is larger, and inward turning Transactivation can be lower, is conducive to atom and rotates freely, while macromolecule Si atom and-CH on main chain₃Connection ,-CH₃Perpendicular to the plane where Si-O-Si atom, due to Si-C key ratio C-C key key It is long, lead to-CH₃In three H be in softened state ,-CH₃In three distracted H atoms can rotate freely and make adjacent Distance becomes larger between Si-O molecule segment, and the inertia methyl of this outside chain hinders high molecular close, thus high molecular material again Very submissive, the high molecular material of the empty free volume dihydric alcohol siliceous relative to main chain is not introduced into increases obvious；And when height When Si atom on molecular backbone is connect with chain substituent of drawing money on credit, what is mainly increased is slit free volume, and increase amplitude is smaller, Permeability and diffusible promotion effect to small molecule is limited, simultaneously because smaller, the strand of rigidity for chain substituent of drawing money on credit Between be easy to happen entanglement, be unfavorable for the increase of free volume, the introducing of the siliceous dihydric alcohol of main chain similarly makes modified poly- The empty free volume of ester increases.

The increase of empty free volume will make water or other molecules such as dyestuff etc. be easier to penetrate into modified poly ester macromolecular Inside generates active influence to dyeing of modified poly ester etc., can reduce dyeing temperature, shorten the time of dyeing, reduces energy consumption, The dye-uptake of fiber is also improved simultaneously.

Solid heteropoly acid is as follows to the specific mechanism of action for the degradation property that polyester modification improves polyester fiber:

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.It is fine although conventional polyester FDY fiber good mechanical performance The compact structure of dimension, crystallinity are high, and natural degradation time is very long, and difficulty is very in terms of recycling for the main application as clothes Greatly, the present invention is close by preparing the carbonylic carbon atom receiving that addition solid heteropoly acid in raw material significantly improves in polyester in polyester The ability of core reagent attack, and then the hydrolysis rate of polyester is improved, make super fine denier polyester fiber can within the limited time Natural degradation.

The utility model has the advantages that

(1) preparation method of a kind of super fine denier polyester fiber of the invention carries out polyester by addition solid heteropoly acid It is modified, the progress of nucleophilic addition in hydrolytic process is promoted, the degradation rate of polyester is improved, can be had for clothes weaving Effect solves the problems, such as that waste and old clothes recycle；

(2) preparation method of a kind of super fine denier polyester fiber of the invention, by the siliceous dihydric alcohol of main chain to polyester into Row is modified, and is increased the empty free volume of modified poly ester, is improved the dyeability of fiber；

(3) preparation method of a kind of super fine denier polyester fiber of the invention, it is simple process, low in cost, before great application Scape.

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 super fine denier polyester fiber, steps are as follows:

(1) solid heteropoly acid powder SiO is prepared₂-TiO₂；

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%；

(2) modified poly ester is prepared；

(1.1) esterification；

Terephthalic acid (TPA), ethylene glycol, Dimethylsilanediol are made into slurry, solid heteropoly acid powder SiO is added₂-TiO₂、 After mixing, pressurization carries out esterification, pressurization pressure in nitrogen atmosphere for antimony oxide, titanium dioxide and triphenyl phosphate Power is 0.3MPa, and the temperature of esterification is 250 DEG C, is esterification when the water quantity of distillate in esterification reaches the 95 of theoretical value Reaction end, wherein the molar ratio of phthalic acid and ethylene glycol is 1:1.2, and the additional amount of Dimethylsilanediol is terephthalic acid (TPA) The 3mol% of additional amount, solid heteropoly acid powder SiO₂-TiO₂, antimony oxide, titanium dioxide and triphenyl phosphate additional amount Respectively 0.03wt%, 0.03wt%, 0.22wt% and 0.02wt% of terephthalic acid (TPA) additional amount；

(1.2) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 30min The interior absolute pressure that is steadily evacuated to by normal pressure is 490Pa, and reaction temperature is 252 DEG C, reaction time 35min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 100Pa, reaction temperature 270 DEG C, reaction time 50min, the number-average molecular weight of modified poly ester obtained is 25000, molecular weight distributing index 1.8；

(3) super fine denier polyester fiber is prepared；

Modified poly ester melt is squeezed out through metering, spinneret, is cooled down, oiling, stretching, being made modified poly- after thermal finalization and winding Ester FDY to get super fine denier polyester fiber；The parameter of FDY technique are as follows: 290 DEG C of spinning temperature, 24 DEG C of cooling temperature, network pressure Power 0.25MPa, a roller speed 2400m/min, 80 DEG C of a roll temperature, two roller speed 4300m/min, two 120 DEG C of roll temperatures, winding Speed 4215m/min.

The filament number of final super fine denier polyester fiber obtained is 0.30dtex, breaking strength 4.1cN/dtex, is broken Splitting elongation is 34%, and internet pricing is 10/m, and line density deviation ratio is 0.8%, and breaking strength CV value is 4.4%, and fracture is stretched Long CV value is 7.2%, boiling water shrinkage 6.5%；

Dye-uptake of super fine denier polyester fiber under the conditions of 120 DEG C of temperature is that 87.3%, K/S value is 22.06；

After super fine denier polyester fiber is placed 60 months under conditions of temperature is 25 DEG C and relative humidity is 65%, characteristic Viscosity decline 13%.

Comparative example 1

A kind of preparation method of polyester fiber, step and embodiment 1 are almost the same, the difference is that in step (1.1) Dimethylsilanediol and solid heteropoly acid powder SiO are not added₂-TiO₂.Finally the filament number of polyester fiber obtained is 0.30dtex, breaking strength 4.1cN/dtex, elongation at break 36%, internet pricing are 10/m, and line density deviation ratio is 1.0%, breaking strength CV value is 4.5%, and extension at break CV value is 7.2%, boiling water shrinkage 6.5%；With embodiment 1 its In the identical situation of his test condition, dye-uptake of polyester fiber under the conditions of 130 DEG C of temperature is that 84.8%, K/S value is 21.03, after being placed 60 months under conditions of temperature is 25 DEG C and relative humidity is 65%, inherent viscosity decline 3.2%.It will Embodiment 1 compares with comparative example 1 it is found that the present invention substantially increases the dyeing of polyester fiber by being modified to polyester Performance and natural degradation performance and mechanical property is unaffected.

Comparative example 2

A kind of preparation method of polyester fiber, preparation step and embodiment 1 are almost the same, the difference is that, step (1.1) Dimethylsilanediol is substituted using 1,6- hexylene glycol in, in situation identical with other test conditions of embodiment 1, is gathered Dye-uptake of ester fiber under the conditions of 130 DEG C of temperature is that 85.7%, K/S value is 20.36, with embodiment 1 comparison it can be found that The siliceous dihydric alcohol of main chain introduces so that contain-Si-O-Si- key on high polymer main chain, so that silicon oxygen bond gap is larger, interior rotation Activation energy is lower, is conducive to atom and rotates freely, so that empty free volume is increased, it is more advantageous relative to chain substituent of drawing money on credit In the dyeability for promoting fiber.

Embodiment 2

(1) solid heteropoly acid powder SiO is prepared₂-ZrO₂；

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%；

(2) modified poly ester is prepared；

(2.1) esterification；

Terephthalic acid (TPA), ethylene glycol, dimethyl diphenyl disiloxane glycol are made into slurry, solid heteropoly acid powder is added Body SiO₂-ZrO₂, antimony oxide, titanium dioxide and trimethyl phosphate after mixing, pressurize and be esterified in nitrogen atmosphere Reaction, moulding pressure 0.2MPa, the temperature of esterification is 252 DEG C, when the water quantity of distillate in esterification reaches theoretical value 90% when be esterification terminal, wherein the molar ratio of phthalic acid and ethylene glycol be 1:1.5, two silicon oxygen of dimethyl diphenyl The additional amount of alkane glycol is the 3.2mol%, solid heteropoly acid powder SiO of terephthalic acid (TPA) additional amount₂-ZrO₂, antimony oxide, The additional amount of titanium dioxide and trimethyl phosphate be respectively terephthalic acid (TPA) additional amount 0.032wt%, 0.04wt%, 0.20wt% and 0.04wt%；

(2.2) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 35min The interior absolute pressure that is steadily evacuated to by normal pressure is 420Pa, and reaction temperature is 255 DEG C, reaction time 40min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 95Pa, reaction temperature 271 DEG C, reaction time 55min, the number-average molecular weight of modified poly ester obtained is 26300, molecular weight distributing index 2.2；

(3) super fine denier polyester fiber is prepared；

Modified poly ester melt is squeezed out through metering, spinneret, is cooled down, oiling, stretching, being made modified poly- after thermal finalization and winding Ester FDY to get super fine denier polyester fiber；；The parameter of FDY technique are as follows: 290 DEG C of spinning temperature, 24 DEG C of cooling temperature, network pressure Power 0.25MPa, a roller speed 2400m/min, 80 DEG C of a roll temperature, two roller speed 4300m/min, two 120 DEG C of roll temperatures, winding Speed 4215m/min.

The filament number of final super fine denier polyester fiber obtained is 0.28dtex, breaking strength 3.9cN/dtex, is broken Splitting elongation is 33%, and internet pricing is 10/m, and line density deviation ratio is 0.8%, and breaking strength CV value is 4.5%, and fracture is stretched Long CV value is 7.2%, boiling water shrinkage 6.6%；

Dye-uptake of super fine denier polyester fiber under the conditions of 120 DEG C of temperature is that 87.5%, K/S value is 22.36；

Embodiment 3

(1) solid heteropoly acid powder B is prepared₂O₃-Al₂O₃；

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%；

(2) modified poly ester is prepared；

(2.1) esterification；

Terephthalic acid (TPA), ethylene glycol, tetramethyl disiloxane glycol are made into slurry, solid heteropoly acid powder B is added₂O₃- Al₂O₃, antimony glycol, titanium dioxide and Trimethyl phosphite after mixing, pressurization carries out esterification in nitrogen atmosphere, Moulding pressure is 0.1MPa, and the temperature of esterification is 255 DEG C, when the water quantity of distillate in esterification reaches the 92% of theoretical value When be esterification terminal, wherein the molar ratio of phthalic acid and ethylene glycol be 1:1.3, the addition of tetramethyl disiloxane glycol Amount is the 3.4mol%, solid heteropoly acid powder B of terephthalic acid (TPA) additional amount₂O₃-Al₂O₃, antimony glycol, titanium dioxide and Asia The additional amount of trimethyl phosphate be respectively terephthalic acid (TPA) additional amount 0.034wt%, 0.05wt%, 0.24wt% and 0.01wt%；

(2.2) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 45min The interior absolute pressure that is steadily evacuated to by normal pressure is 500Pa, and reaction temperature is 256 DEG C, reaction time 30min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 96Pa, reaction temperature 273 DEG C, reaction time 60min, the number-average molecular weight of modified poly ester obtained is 25800, molecular weight distributing index 2.0；

(3) super fine denier polyester fiber is prepared；

The filament number of final super fine denier polyester fiber obtained is 0.35dtex, breaking strength 4.0cN/dtex, is broken Splitting elongation is 33%, and internet pricing is 10/m, and line density deviation ratio is 0.8%, and breaking strength CV value is 4.8%, and fracture is stretched Long CV value is 7.5%, boiling water shrinkage 6.6%；

Dye-uptake of super fine denier polyester fiber under the conditions of 120 DEG C of temperature is that 87.9%, K/S value is 22.9；

Embodiment 4

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

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；

(2) modified poly ester is prepared；

(2.1) esterification；

Terephthalic acid (TPA), ethylene glycol, Dimethylsilanediol are made into slurry, solid heteropoly acid powder TiO is added₂-ZnO、 After mixing, pressurization carries out esterification, moulding pressure in nitrogen atmosphere for antimony glycol, titanium dioxide and triphenyl phosphate For 0.1MPa, the temperature of esterification is 250 DEG C, is esterification when the water quantity of distillate in esterification reaches the 95% of theoretical value Reaction end, wherein the molar ratio of phthalic acid and ethylene glycol is 1:1.6, and the additional amount of Dimethylsilanediol is terephthalic acid (TPA) The 3.6mol% of additional amount, solid heteropoly acid powder TiO₂The additional amount of-ZnO, antimony glycol, titanium dioxide and triphenyl phosphate Respectively 0.036wt%, 0.04wt%, 0.25wt% and 0.03wt% of terephthalic acid (TPA) additional amount；

(2.2) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 40min The interior absolute pressure that is steadily evacuated to by normal pressure is 440Pa, and reaction temperature is 260 DEG C, reaction time 40min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 99Pa, reaction temperature 273 DEG C, reaction time 75min, the number-average molecular weight of modified poly ester obtained is 27000, molecular weight distributing index 1.9；

(3) super fine denier polyester fiber is prepared；

The filament number of final super fine denier polyester fiber obtained is 0.30dtex, breaking strength 4.0cN/dtex, is broken Splitting elongation is 33%, and internet pricing is 15/m, and line density deviation ratio is 0.8%, and breaking strength CV value is 4.6%, and fracture is stretched Long CV value is 7.5%, boiling water shrinkage 6.7%；

Dye-uptake of super fine denier polyester fiber under the conditions of 120 DEG C of temperature is that 88.3%, K/S value is 23.06；

After super fine denier polyester fiber is placed 60 months under conditions of temperature is 25 DEG C and relative humidity is 65%, characteristic Viscosity decline 14%.

Embodiment 5

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

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%；

(2) modified poly ester is prepared；

(2.1) esterification；

Terephthalic acid (TPA), ethylene glycol, dimethyl diphenyl disiloxane glycol are made into slurry, solid heteropoly acid powder is added Body SiO₂After mixing, pressurization be esterified anti-in nitrogen atmosphere for-CaO, antimony acetate, titanium dioxide and trimethyl phosphate It answers, moulding pressure is 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 91%, wherein the molar ratio of phthalic acid and ethylene glycol is 1:1.8, dimethyl diphenyl disiloxane The additional amount of glycol is the 3.8mol%, solid heteropoly acid powder SiO of terephthalic acid (TPA) additional amount₂- CaO, antimony acetate, titanium dioxide The additional amount of titanium and trimethyl phosphate be respectively terephthalic acid (TPA) additional amount 0.038wt%, 0.03wt%, 0.25wt% and 0.01wt%；

(2.2) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 50min The interior absolute pressure that is steadily evacuated to by normal pressure is 490Pa, and reaction temperature is 258 DEG C, reaction time 35min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 100Pa, reaction temperature 274 DEG C, reaction time 80min, the number-average molecular weight of modified poly ester obtained is 28000, molecular weight distributing index 2.1；

(3) super fine denier polyester fiber is prepared；

The filament number of final super fine denier polyester fiber obtained is 0.3dtex, breaking strength 4.0cN/dtex, fracture Elongation is 32%, and internet pricing is 15/m, and line density deviation ratio is 0.8%, and breaking strength CV value is 4.5%, extension at break CV value is 7.6%, boiling water shrinkage 6.7%；

Dye-uptake of super fine denier polyester fiber under the conditions of 120 DEG C of temperature is that 88.8%, K/S value is 23.36；

Embodiment 6

(1) 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%；

(2) modified poly ester is prepared；

(2.1) esterification；

Terephthalic acid (TPA), ethylene glycol, tetramethyl disiloxane glycol are made into slurry, solid heteropoly acid powder, vinegar is added After mixing, pressurization carries out esterification in nitrogen atmosphere for sour antimony, titanium dioxide and Trimethyl phosphite, and moulding pressure is Normal pressure, the temperature of esterification are 254 DEG C, are esterification when the water quantity of distillate in esterification reaches the 94% of theoretical value Terminal, wherein the molar ratio of phthalic acid and ethylene glycol is 1:2.0, and the additional amount of tetramethyl disiloxane glycol is terephthaldehyde The 4.0mol% of sour additional amount, solid heteropoly acid powder, antimony acetate, titanium dioxide and Trimethyl phosphite additional amount be respectively 0.04wt%, 0.04wt%, 0.20wt% and 0.05wt% of terephthalic acid (TPA) additional amount；

(2.2) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 35min The interior absolute pressure that is steadily evacuated to by normal pressure is 450Pa, and reaction temperature is 250 DEG C, reaction time 50min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 100Pa, reaction temperature 275 DEG C, reaction time 85min, the number-average molecular weight of modified poly ester obtained is 29000, molecular weight distributing index 1.9；

(3) super fine denier polyester fiber is prepared；

The filament number of final super fine denier polyester fiber obtained is 0.3dtex, breaking strength 4.0cN/dtex, fracture Elongation is 30%, and internet pricing is 10/m, and line density deviation ratio is 0.8%, and breaking strength CV value is 4.5%, extension at break CV value is 7.4%, boiling water shrinkage 6.8%；

Dye-uptake of super fine denier polyester fiber under the conditions of 120 DEG C of temperature is that 89.3%, K/S value is 23.34；

Embodiment 7

(1) 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%；

(2) modified poly ester is prepared；

(2.1) esterification；

Terephthalic acid (TPA), ethylene glycol, tetramethyl disiloxane glycol are made into slurry, solid heteropoly acid powder, three is added Aoxidize two antimony, titanium dioxide and trimethyl phosphate after mixing, pressurization carries out esterification, moulding pressure in nitrogen atmosphere For 0.3MPa, the temperature of esterification is 260 DEG C, is esterification when the water quantity of distillate in esterification reaches the 99% of theoretical value Reaction end, wherein the molar ratio of phthalic acid and ethylene glycol is 1:1.3, and the additional amount of tetramethyl disiloxane glycol is to benzene The 4.2mol% of dioctyl phthalate additional amount, the additional amount of solid heteropoly acid powder, antimony oxide, titanium dioxide and trimethyl phosphate Respectively 0.042wt%, 0.04wt%, 0.21wt% and 0.01wt% of terephthalic acid (TPA) additional amount；

(2.2) polycondensation reaction；

After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 45min The interior absolute pressure that is steadily evacuated to by normal pressure is 500Pa, and reaction temperature is 250 DEG C, reaction time 50min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 90Pa, reaction temperature 280 DEG C, reaction time 90min, the number-average molecular weight of modified poly ester obtained is 30000, molecular weight distributing index 1.8；

(3) super fine denier polyester fiber is prepared；

Modified poly ester melt is squeezed out through metering, spinneret, is cooled down, oiling, stretching, being made modified poly- after thermal finalization and winding Ester FDY to get super fine denier polyester fiber；The parameter of FDY technique are as follows: 285 DEG C of spinning temperature, 25 DEG C of cooling temperature, network pressure Power 0.20MPa, a roller speed 2200m/min, 75 DEG C of a roll temperature, two roller speed 4200m/min, two 115 DEG C of roll temperatures, winding Speed 4130m/min.

The filament number of final super fine denier polyester fiber obtained is 0.3dtex, breaking strength 4.1cN/dtex, fracture Elongation is 30%, and internet pricing is 10/m, and line density deviation ratio is 0.8%, and breaking strength CV value is 4.5%, extension at break CV value is 7.5%, boiling water shrinkage 6.9%；

Dye-uptake of super fine denier polyester fiber under the conditions of 120 DEG C of temperature is that 89.6%, K/S value is 23.71；

Embodiment 8

(1) modified poly ester is prepared；

(1.1) esterification；

Terephthalic acid (TPA), ethylene glycol, Dimethylsilanediol are made into slurry, solid heteropoly acid powder B is added₂O₃-Al₂O₃、 After mixing, pressurization carries out esterification, pressurization pressure in nitrogen atmosphere for antimony oxide, titanium dioxide and triphenyl phosphate Power is 0.3MPa, and the temperature of esterification is 250 DEG C, is esterification when the water quantity of distillate in esterification reaches the 95 of theoretical value Reaction end, wherein the molar ratio of phthalic acid and ethylene glycol is 1:1.2, and the additional amount of Dimethylsilanediol is terephthalic acid (TPA) The 4.3mol% of additional amount, solid heteropoly acid powder B₂O₃-Al₂O₃, antimony oxide, titanium dioxide and triphenyl phosphate plus Enter 0.043wt%, 0.03wt%, 0.22wt% and 0.02wt% that amount is respectively terephthalic acid (TPA) additional amount, solid heteropoly acid Powder B₂O₃-Al₂O₃Average grain diameter be 0.4 micron, B₂O₃-Al₂O₃Middle Al₂O₃Content be respectively 40wt%；；

(1.2) polycondensation reaction；

(2) super fine denier polyester fiber is prepared；

The filament number of final super fine denier polyester fiber obtained is 0.3dtex, breaking strength 4.0cN/dtex, fracture Elongation is 30%, and internet pricing is 15/m, and line density deviation ratio is 0.8%, and breaking strength CV value is 4.6%, extension at break CV value is 7.6%, boiling water shrinkage 6.9%；

Dye-uptake of super fine denier polyester fiber under the conditions of 120 DEG C of temperature is that 89.9%, K/S value is 24.24；

Embodiment 9

(1) modified poly ester is prepared；

(1.1) esterification；

Terephthalic acid (TPA), ethylene glycol, dimethyl diphenyl disiloxane glycol are made into slurry, solid heteropoly acid powder is added Body TiO₂- ZnO, antimony oxide, titanium dioxide and trimethyl phosphate after mixing, pressurize in nitrogen atmosphere and are esterified Reaction, moulding pressure 0.2MPa, the temperature of esterification is 252 DEG C, when the water quantity of distillate in esterification reaches theoretical value 90% when be esterification terminal, wherein the molar ratio of phthalic acid and ethylene glycol be 1:1.5, two silicon oxygen of dimethyl diphenyl The additional amount of alkane glycol is the 4.4mol%, solid heteropoly acid powder TiO of terephthalic acid (TPA) additional amount₂- ZnO, antimony oxide, The additional amount of titanium dioxide and trimethyl phosphate be respectively terephthalic acid (TPA) additional amount 0.045wt%, 0.04wt%, 0.20wt% and 0.04wt%, solid heteropoly acid powder TiO₂The average grain diameter of-ZnO is 0.4 micron, TiO₂ZnO's contains in-ZnO Amount is 20wt%；

(1.2) polycondensation reaction；

(2) super fine denier polyester fiber is prepared；

Modified poly ester melt is squeezed out through metering, spinneret, is cooled down, oiling, stretching, being made modified poly- after thermal finalization and winding Ester FDY to get super fine denier polyester fiber；The parameter of FDY technique are as follows: 300 DEG C of spinning temperature, 25 DEG C of cooling temperature, network pressure Power 0.30MPa, a roller speed 2600m/min, 90 DEG C of a roll temperature, two roller speed 4500m/min, two 135 DEG C of roll temperatures, winding Speed 4415m/min.

The filament number of final super fine denier polyester fiber obtained is 0.32dtex, breaking strength 3.9cN/dtex, is broken Splitting elongation is 28%, and internet pricing is 10/m, and line density deviation ratio is 0.7%, and breaking strength CV value is 4.7%, and fracture is stretched Long CV value is 7.5%, boiling water shrinkage 7.0%；

Dye-uptake of super fine denier polyester fiber under the conditions of 120 DEG C of temperature is that 90.2%, K/S value is 23.84；

After super fine denier polyester fiber is placed 60 months under conditions of temperature is 25 DEG C and relative humidity is 65%, characteristic Viscosity decline 15%.

Embodiment 10

(1) modified poly ester is prepared；

(1.1) esterification；

Terephthalic acid (TPA), ethylene glycol, tetramethyl disiloxane glycol are made into slurry, solid heteropoly acid powder is added TiO₂After mixing, pressurization be esterified anti-in nitrogen atmosphere for-ZnO, antimony glycol, titanium dioxide and Trimethyl phosphite It answers, moulding pressure 0.1MPa, the temperature of esterification is 255 DEG C, when the water quantity of distillate in esterification reaches theoretical value It is esterification terminal when 92%, wherein the molar ratio of phthalic acid and ethylene glycol is 1:1.3, tetramethyl disiloxane glycol Additional amount is the 4.5mol%, solid heteropoly acid powder TiO of terephthalic acid (TPA) additional amount₂- ZnO, antimony glycol, titanium dioxide and The additional amount of Trimethyl phosphite be respectively terephthalic acid (TPA) additional amount 0.045wt%, 0.05wt%, 0.24wt% and 0.01wt%, solid heteropoly acid powder TiO₂The average grain diameter of-ZnO is 0.4 micron, TiO₂The content of ZnO is in-ZnO 40wt%；

(1.2) polycondensation reaction；

(2) super fine denier polyester fiber is prepared；

The filament number of final super fine denier polyester fiber obtained is 0.3dtex, breaking strength 4.0cN/dtex, fracture Elongation is 28%, and internet pricing is 15/m, and line density deviation ratio is 0.8%, and breaking strength CV value is 4.5%, extension at break CV value is 7.6%, boiling water shrinkage 7.2%；

Dye-uptake of super fine denier polyester fiber under the conditions of 120 DEG C of temperature is that 91.2%, K/S value is 24.88；

After super fine denier polyester fiber is placed 60 months under conditions of temperature is 25 DEG C and relative humidity is 65%, characteristic Viscosity decline 16%.

Embodiment 11

(1) modified poly ester is prepared；

(1.1) esterification；

Terephthalic acid (TPA), ethylene glycol, Dimethylsilanediol are made into slurry, solid heteropoly acid powder SiO is added₂-CaO、 After mixing, pressurization carries out esterification, moulding pressure in nitrogen atmosphere for antimony glycol, titanium dioxide and triphenyl phosphate For 0.1MPa, the temperature of esterification is 250 DEG C, is esterification when the water quantity of distillate in esterification reaches the 95% of theoretical value Reaction end, wherein the molar ratio of phthalic acid and ethylene glycol is 1:1.6, and the additional amount of Dimethylsilanediol is terephthalic acid (TPA) The 4.7mol% of additional amount, solid heteropoly acid powder SiO₂The additional amount of-CaO, antimony glycol, titanium dioxide and triphenyl phosphate Respectively 0.048wt%, 0.04wt%, 0.25wt% and 0.03wt% of terephthalic acid (TPA) additional amount, solid heteropoly acid powder SiO₂The average grain diameter of-CaO is 0.4 micron, SiO₂The content of CaO is 20wt% in-CaO；

(1.2) polycondensation reaction；

(2) super fine denier polyester fiber is prepared；

The filament number of final super fine denier polyester fiber obtained is 0.3dtex, breaking strength 4.0cN/dtex, fracture Elongation is 28%, and internet pricing is 10/m, and line density deviation ratio is 0.8%, and breaking strength CV value is 5.00%, extension at break CV value is 8.0%, boiling water shrinkage 7.4%；

Dye-uptake of super fine denier polyester fiber under the conditions of 120 DEG C of temperature is that 91.7%, K/S value is 24.99；

After super fine denier polyester fiber is placed 60 months under conditions of temperature is 25 DEG C and relative humidity is 65%, characteristic Viscosity decline 17%.

Embodiment 12

(1) modified poly ester is prepared；

(1.1) esterification；

Terephthalic acid (TPA), ethylene glycol, Dimethylsilanediol are made into slurry, solid heteropoly acid powder SiO is added₂-CaO、 After mixing, pressurization carries out esterification, moulding pressure in nitrogen atmosphere for antimony glycol, titanium dioxide and triphenyl phosphate For 0.1MPa, the temperature of esterification is 250 DEG C, is esterification when the water quantity of distillate in esterification reaches the 95% of theoretical value Reaction end, wherein the molar ratio of phthalic acid and ethylene glycol is 1:1.6, and the additional amount of Dimethylsilanediol is terephthalic acid (TPA) The 4.9mol% of additional amount, solid heteropoly acid powder SiO₂The additional amount of-CaO, antimony glycol, titanium dioxide and triphenyl phosphate Respectively 0.048wt%, 0.04wt%, 0.25wt% and 0.03wt% of terephthalic acid (TPA) additional amount, solid heteropoly acid powder SiO₂The average grain diameter of-CaO is 0.4 micron, SiO₂The content of CaO is 50wt% in-CaO；

(1.2) polycondensation reaction；

(2) super fine denier polyester fiber is prepared；

The filament number of final super fine denier polyester fiber obtained is 0.3dtex, breaking strength 3.7cN/dtex, fracture Elongation is 26%, and internet pricing is 10/m, and line density deviation ratio is 1.00%, and breaking strength CV value is 4.8%, extension at break CV value is 7.8%, boiling water shrinkage 7.5%；

Dye-uptake of super fine denier polyester fiber under the conditions of 120 DEG C of temperature is that 92.2%, K/S value is 25.34；

After super fine denier polyester fiber is placed 60 months under conditions of temperature is 25 DEG C and relative humidity is 65%, characteristic Viscosity decline 18%.

Claims

1. a kind of preparation method of super fine denier polyester fiber, it is characterized in that: being made modified poly- by modified poly ester melt by FDY technique Ester FDY to get super fine denier polyester fiber；

The modified poly ester the preparation method comprises the following steps: by the siliceous dihydric alcohol of terephthalic acid (TPA), ethylene glycol, main chain and by high temperature roast The solid heteropoly acid powder of burning successively carries out esterification and polycondensation reaction after mixing；

The siliceous dihydric alcohol of main chain is Dimethylsilanediol, dimethyl diphenyl disiloxane glycol or tetramethyl disiloxane two Alcohol；

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.

2. a kind of preparation method of super fine denier polyester fiber according to claim 1, which is characterized in that high-temperature roasting when Between be 2~4h；SiO₂-TiO₂、SiO₂-ZrO₂、B₂O₃-Al₂O₃、TiO₂- ZnO and SiO₂TiO in-CaO₂、ZrO₂、Al₂O₃, ZnO and The content of CaO is respectively 30~50wt%, 30~50wt%, 20~40wt%, 20~40wt% and 20~50wt%；Solid is miscellaneous Polyacid is crushed to obtain powder of the average grain diameter less than 0.5 micron after high-temperature roasting.

3. a kind of preparation method of super fine denier polyester fiber according to claim 2, which is characterized in that the modified poly ester Preparation step it is as follows:

(1) esterification；

Terephthalic acid (TPA), ethylene glycol and the siliceous dihydric alcohol of main chain are made into slurry, the solid being added Jing Guo high-temperature roasting is miscellaneous more After mixing, pressurization carries out esterification, moulding pressure in nitrogen atmosphere for sour powder, catalyst, delustering agent and stabilizer For 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 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 270~280 DEG C, and the reaction time is 50~90min.

4. a kind of preparation method of super fine denier polyester fiber according to claim 3, which is characterized in that the terephthaldehyde The molar ratio of acid, ethylene glycol and the siliceous dihydric alcohol of main chain is 1:1.2~2.0:0.03~0.05, described by high-temperature roasting Solid heteropoly acid powder, catalyst, delustering agent and stabilizer additional amount be respectively terephthalic acid (TPA) additional amount 0.03~ 0.05wt%, 0.03~0.05wt%, 0.20~0.25wt% and 0.01~0.05wt%.

5. a kind of preparation method of super fine denier polyester fiber according to claim 4, which is characterized in that the catalyst is Antimony oxide, antimony glycol or antimony acetate, the delustering agent are titanium dioxide, and the stabilizer is triphenyl phosphate, phosphoric acid Trimethyl or Trimethyl phosphite.

6. a kind of preparation method of super fine denier polyester fiber according to claim 5, which is characterized in that the modified poly ester Number-average molecular weight be 25000~30000, molecular weight distributing index be 1.8~2.2.

7. a kind of preparation method of super fine denier polyester fiber according to claim 6, which is characterized in that the FDY technique Process are as follows: metering, spinneret squeeze out, cool down, oil, stretching, thermal finalization and winding；

The parameter of the FDY technique are as follows: 285~300 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 4200~4500m/min of roller speed, two rollers 115~135 DEG C of temperature, 4130~4415m/min of winding speed.

8. using one kind made from a kind of preparation method of super fine denier polyester fiber as described in any one of claims 1 to 7 super Microdenier polyester fibers, it is characterized in that: being modified poly ester FDY；

The strand of the modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment and the siliceous dihydric alcohol segment of main chain；

The filament number of super fine denier polyester fiber is 0.28~0.35dtex.

9. a kind of super fine denier polyester fiber according to claim 8, which is characterized in that the fracture of super fine denier polyester fiber is strong Degree >=3.7cN/dtex, elongation at break be 30.0 ± 4.0%, internet pricing be 14 ± 4/m, line density deviation ratio≤ 1.00%, breaking strength CV value≤5.00%, extension at break CV value≤8.0%, boiling water shrinkage is 7.0 ± 0.5%.

10. a kind of super fine denier polyester fiber according to claim 8, which is characterized in that super fine denier polyester fiber is at 120 DEG C Temperature under the conditions of dye-uptake be 87.3~92.2%, K/S value be 22.06~25.34；Super fine denier polyester fiber is in temperature After 25 DEG C and relative humidity are placed 60 months under conditions of being 65%, inherent viscosity declines 13~18%.