CN109722737A - A kind of modified polyester fiber and preparation method thereof containing solid base catalyst - Google Patents

Abstract

The present invention relates to a kind of modified polyester fiber and preparation method thereof containing solid base catalyst, after preparation method is is made modified poly ester POY by modified poly ester melt by POY technique, then it is carried out to process by DTY technique, the modified polyester fiber containing solid base catalyst is made；The strand of modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment and 2,5,6,6- tetramethyl -2,5- heptandiol segment；The structural formula of 2,5,6,6- tetramethyl -2,5- heptandiol is as follows:The Sb of the solid base catalyst powder and doping vario-property by high-temperature roasting is dispersed in modified poly ester₂O₃Powder.After obtained product is placed 60 months under conditions of temperature is 25 DEG C and relative humidity is 65%, inherent viscosity decline 18~24%.Preparation method of the invention, low in cost, simple process；Product is made, natural degradation rate is fast, great application prospect.

Description

A kind of modified polyester fiber and preparation method thereof containing solid base catalyst

Technical field

The invention belongs to modified fibre technical field, be related to a kind of modified polyester fiber containing solid base catalyst and its Preparation method.

Background technique

Polyester (PET) is due to at low cost, tensile strength is good, chemical stability is good, the transparency is good, easy to process and hot Many advantages, such as stability is good has been widely used in numerous areas since the forties in 19th century, early stage was by invention.At present its It is mainly used for weaving, the 60% of worldwide production amount is for weaving.Transparency as having with category of glass it, at present more More to become the packaging material of the main material of food packaging, especially carbonated beverage.In addition to this, PET is also used for Manufacture daily necessities, automobile product, illuminating product and sports goods etc..

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, PET waste has become global environmental pollution Organic matter.Currently, the common processing method to PET waste has landfill, burning and recycling, although landfill and burning are Simplest method will also cause certain pollution to environment, and degradation recycling is to handle PET waste effectively and the way of science Diameter, the ratio recycled at present also very little, a maximum of about of 13%, although in recent years China have in terms of PET recycling compared with Big speedup, but its rate of recovery is still very low, and less than 10%, this is because PET construction is fine and close, crystallinity is high, chemical stability Good, natural degradation time is very long (degradation cycle of conventional polyester fiber was up to 16~48 years).

The method for mostly using chemical degradation for the degradation of PET in practical applications, chemical decomposition method mainly have Hydrolyze method And alcoholysis method, in addition there are ammonolysis, aminolysis and pyrolysis etc..But chemical degradation method used at present still remains degradation rate Slowly, the problems such as degradation effect is poor, the degradation that still can not solve a large amount of PET waste recycle.To polyester The means that modification is change polyester properties relatively conventional at present are learned, the performance in terms of polyester can be significantly changed.

In addition, synthetic method used in PET polyester material production at present is broadly divided into ester-interchange method (DMT method) and straight contracting (PTA method), the catalyst used in process of polyester synthesizing is mainly antimony-based catalyst.Common antimony-based catalyst on the market at present Such as Sb₂O₃Additive amount in process of polyester synthesizing is larger, and metallic antimony can all bring harm, the catalysis of antimony system to man and nature The larger influence generated to environment of the additive amount of agent is also larger, is unfavorable for the environmental protection production of polyester.

Therefore, it studies and a kind of improve polyester degradation rate and degradation effect by being modified to polyester reduction is urged simultaneously The method of agent dosage and using the modified poly ester come the great realistic meaning of the excellent polyester fiber of processability.

Summary of the invention

The purpose of the present invention is prior art degradation rate is slow and the biggish defect of catalyst amount, provides and a kind of drop naturally Solve that rate is fast and lesser polyester fiber of catalyst amount and preparation method thereof.

In order to achieve the above object, present invention employs the following technical solutions:

A kind of preparation method of the modified polyester fiber containing solid base catalyst, by POY technique by modified poly ester melt After being made modified poly ester POY, then processing is carried out to it by DTY technique, the modified poly ester fibre containing solid base catalyst is made Dimension；

The modified poly ester the preparation method comprises the following steps: by terephthalic acid (TPA), ethylene glycol, 2,5,6,6- tetramethyl -2,5- heptan two The Sb of alcohol, solid base catalyst powder and doping vario-property by high-temperature roasting₂O₃Powder successively carries out being esterified after mixing anti- Should and polycondensation reaction；

The structural formula of 2,5,6,6- tetramethyl -2,5- heptandiol is as follows:

The temperature of solid base catalyst high-temperature roasting is 400~700 DEG C, solid base catalyst MgO, BaO and SiO₂- One or more of BaO；

High-temperature roasting can remove volatile component and retain certain chemical composition, in addition during high-temperature roasting Since solid-state reaction, available certain crystal form, crystallite dimension, pore structure and specific surface, the temperature of high-temperature roasting occurs Can be adjusted in the appropriate range, but be not easy it is too high or too low, it is excessively high that active principle is easy to cause to volatilize, it is too low to be easy to lead It causes crystal transfer not reach requirement, while being difficult to remove volatile components；

Sb₂O₃The process of doping vario-property are as follows: first by metal ion M^x+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 and crushes；

Metal ions M^x+For Mg²⁺、Ca²⁺、Ba²⁺And Zn²⁺One or more of.

Solid base catalyst has many advantages, such as that corrosion-free, selectivity is high, catalytic activity is high and product easily decomposes.The present invention makes Polyester is modified with 2,5,6,6- tetramethyl -2,5- heptandiols, 2,5,6,6- tetramethyl -2,5- heptandiols can significantly increase The space free volume of big modified poly ester, the presence of tert-butyl can cause in especially 2,5,6,6- tetramethyl -2,5- heptandiols The variation of main chain activity, thus the interaction force between changing chain element, phase can also occur for the distance between molecule chain element The change answered increases modified poly ester cavity free volume.Empty free volume is more conducive to empty gas and water compared to slit free volume Equimolal diffusion can reduce the molecules such as sky gas and water and penetrate into difficulty inside modified poly ester, to a certain degree to fibrous inside The upper natural degradation performance for improving modified poly ester.

The present invention enhances the attack ability of nucleopilic reagent, improves poly- by introducing solid base catalyst in the polyester The degradation rate of ester.Solid base selected by the present invention is MgO, BaO or SiO by high-temperature roasting₂- BaO, MgO or BaO exist Predominantly weakly alkaline hydroxyl when low temperature, but after high-temperature roasting, surface can generate the lattice defects such as point, line, surface, crystal table The oxygen in face can be enriched at tip, and when solid base catalyst charges, charge density of the distribution of charges at its surface, tip is most Greatly, it so that the surface MgO or BaO has different strong basicity positions, is easier to ionize out OH when combined with water^-, OH^-Relative to H₂O With stronger nucleophilie nucleus ability, thus in the polyester after introducing solid base catalyst, the difficulty that nucleophilic addition occurs is reduced Degree, and then improve the degradation rate of polyester.In addition, SiO₂- BaO is carrier loaded alkali metal, is also added relative to BaO Carrier S iO₂, carrier S iO₂Skeleton as active component plays a part of dispersing BaO and increases BaO intensity, additionally it is possible to change The crystal structure of BaO, forms defect and cavity, specific surface area and the aperture for increasing BaO enhance to increase the alkalinity of BaO Reinforcing effect of the BaO to the attack ability of nucleopilic reagent.

Present invention introduces 2,5,6,6- tetramethyl -2,5- heptandiols and solid base catalyst can also play synergistic effect, Solid base catalyst enhances the attack ability of nucleopilic reagent, promotes natural degradation reaction, 2,5,6,6- tetramethyls -2,5- Heptandiol increases the empty free volume of polyester, is conducive to the infiltration of oxygen and water, improves the concentration of oxygen atom inside polyester, Natural degradation reaction is further promoted, improves degradation rate significantly.

The present invention is also modified antimony oxide, improves the activity of antimony oxide, and attenuating prepares PET Process The additive amount of middle antimony oxide.The present invention is by by metal ion M^x+Solution with contain Sb³⁺Solution first be uniformly mixed again The last calcining of precipitating is to realize the doping and blending of metal oxide and antimony oxide with certain catalytic activity, metal Oxide is one or more of MgO, CaO, BaO and ZnO, after metal oxide of the invention and antimony oxide adulterate, gold Belong to oxide by inhibition antimony oxide crystallization and cubic crystal antimony oxide crystal grain grow up and same order elements antimony Into the lattice position of antimony, antimony oxide crystal is made to generate defect, crystal habit generates variation, and crystallite dimension becomes smaller, improves The specific surface area S of antimony oxide catalyst_g, while metal can also be enriched in part antimony oxide plane of crystal, make three oxygen Change the active r in two antimony per surface areas_sIncrease, specific surface area S_gWith the active r in per surface area_sBigger, catalyst is urged It is higher to change activity, therefore the present invention can be in low Sb₂O₃Realize that polyester catalyzes and synthesizes under additive amount, be good for the environment production and Guarantee the quality of synthesis polyester.

As a preferred option:

A kind of preparation method of the modified polyester fiber containing solid base catalyst as described above, described 2,5,6,6- tetra- The synthesis step of methyl -2,5- heptandiol is as follows:

(1) by 1~1.2:1:1.2~1.3:2.0~3.0 molar ratio by KOH powder, 3- methyl -3- hydroxyl butine, 3, 3- dimethyl-2-butanone and isopropyl ether mixing, react 2~4h under condition of ice bath, carry out crystallisation by cooling, centrifugation after reaction Separate, wash, refine and be dried to obtain octyne glycol；

(2) octyne glycol, ethyl alcohol and palladium catalyst are mixed by the weight ratio of 2~3:10:0.01~0.03,40~50 DEG C temperature under the conditions of react 50~60min, be continually fed into hydrogen in reaction process, separated and purified after reaction To 2,5,6,6- tetramethyl -2,5- heptandiol.

A kind of preparation method of the modified polyester fiber containing solid base catalyst as described above, SiO₂BaO in-BaO Content be 40~80wt%；The process of high-temperature roasting are as follows: keep the temperature 2~3h after being warming up to 400 DEG C first, then heat to 700 1~2h is kept the temperature after DEG C, is finally cooled down in air；Solid base catalyst is crushed to obtain average grain diameter after high-temperature roasting small In 0.5 micron of powder.

A kind of preparation method of the modified polyester fiber containing solid base catalyst as described above, to Sb₂O₃It is doped When modified, the metal ion M^x+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 ions M in mixed solution^x+With Sb³⁺Molar ratio be 1~3:100, Sb₂O₃It is mesh The preceding highest polyester catalyst of cost performance, the present invention is by penetrating into metal oxide (i.e. M₂O_X) inhibit antimony oxide (Sb₂O₃) Crystallization and cubic crystal antimony oxide crystal grain grow up, while metal ions M^x+The lattice position that antimony and entrance antimony can be replaced, makes It obtains antimony oxide crystal and generates defect, to improve the catalytic activity of antimony oxide.It (rubs as blended metal oxide amount is very few You are than too low), relatively low on the influence of antimony oxide crystal grain, excessive (molar ratio is excessively high) can make the main body Sb of catalyst³⁺Decline Amplitude is bigger than normal, unfavorable to antimony oxide catalytic activity is improved；Precipitated product is washed and dried before the calcining, is done 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, 1~2h is kept the temperature after then heating to 900 DEG C, is finally cooled down in air, and the present invention calcines preceding to precipitated product after precipitating Treatment process includes but are not limited to this, as long as can guarantee the OH for sufficiently removing precipitated product surface^-With moisture therein, energy Impurity and hydrone is enough avoided to be suitable for the present invention to the dysgenic treatment process of calcining；Sb₂O₃It is laggard in doping vario-property Row crushes and obtains powder of the average grain diameter less than 0.5 micron, and calcination process of the invention includes but are not limited to this, other can It realizes the doping of metal oxide (MgO, CaO, BaO and ZnO) and antimony oxide, realizes to Sb₂O₃Doping vario-property calcining Technique is suitable for the present invention.

A kind of preparation method of the modified polyester fiber containing solid base catalyst as described above, the modified poly ester Preparation step is as follows:

(1) esterification；

By terephthalic acid (TPA), ethylene glycol and 2,5,6,6- tetramethyl -2,5- heptandiols are made into slurry, are added and roast by high temperature The Sb of the solid base catalyst powder of burning, doping vario-property₂O₃Powder, delustering agent and stabilizer after mixing, in nitrogen atmosphere Pressurization carries out esterification, and moulding pressure is normal pressure~0.3MPa, and the temperature of esterification is 250~260 DEG C, works as esterification In water quantity of distillate be esterification terminal when reaching 90% of theoretical value 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 270~275 DEG C, the reaction time is 50~90min.

A kind of preparation method of the modified polyester fiber containing solid base catalyst as described above, the terephthaldehyde Acid, ethylene glycol and 2, the molar ratios of 5,6,6- tetramethyl -2,5- heptandiols are 1:1.2~2.0:0.03~0.05,2,5,6,6- The additive amount of tetramethyl -2,5- heptandiol is excessive (such as larger than 0.1), too big to the regularity destruction of polyester macromolecule structure, right Crystallinity and mechanical property (rigidity) influence of fiber are excessive, are unfavorable for the production and application of fiber；Additive amount is very few (such as small It is unobvious to the increase of polyester cavity free volume, it is difficult to be obviously improved the natural degradation performance of polyester, the warp in 0.01) Cross the solid base catalyst powder of high-temperature roasting, the Sb of doping vario-property₂O₃The additional amount of powder, delustering agent and stabilizer is respectively 0.20~0.25wt% of terephthalic acid (TPA) additional amount, 0.012~0.015wt%, 0.20~0.25wt% and 0.01~ 0.05wt%；Solid base catalyst is a long-term process to the degradation catalysis of polyester, and the height of additive amount mainly considers Time and the time limit of degradation that influence and fibrous mechanical property to polyester fiber technical indicator are kept etc., solid base catalyst Additional amount can be adjusted according to practical application, but adjust amplitude should not be too large, by the solid base catalyst of high-temperature roasting The additional amount of powder is excessive, can the performance (mechanical property) to fiber have an impact, the application of fiber is influenced, by high-temperature roasting Solid base catalyst powder additional amount it is too small, the degradation property of fiber is influenced too small, it is difficult to be obviously improved fiber from Right degradation rate；Sb in process of polyester synthesizing in the prior art₂O₃Additional amount be usually terephthalic acid (TPA) additional amount 0.02~ The additional amount of 0.04wt%, antimony-based catalyst are high, and this is mainly due to undoped Sb₂O₃Active r in per surface area_sIt is low And specific surface area S_gIt is small, therefore Sb₂O₃Whole catalytic activity is lower, and the present invention passes through to Sb₂O₃It is doped modification, is improved Sb₂O₃Activity, therefore significantly reduce Sb in process of polyester synthesizing₂O₃Additive amount；The delustering agent is titanium dioxide, institute Stating stabilizer is triphenyl phosphate, trimethyl phosphate or Trimethyl phosphite.

A kind of preparation method of the modified polyester fiber containing solid base catalyst as described above, the number of modified poly ester are equal Molecular weight is 25000~30000, and molecular weight distributing index is 1.8~2.2.

A kind of preparation method of the modified polyester fiber containing solid base catalyst as described above, 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 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: 400~800m/min of spinning speed, overfeed rate of setting 3.5~5.5%, winding are super Feed rate 2.5~5.0%, the first 180~220 DEG C of heater temperature, the second 150~180 DEG C of heater temperature, draw ratio 1.6~1.8.

The design parameter of POY and DTY technique of the invention is not limited to that, only provides a feasible technique ginseng herein Number.

The present invention also provides a kind of using a kind of modified polyester fiber containing solid base catalyst as described above A kind of modified polyester fiber containing solid base catalyst made from preparation method is DTY fiber, the strand packet of modified poly ester Include terephthalic acid (TPA) segment, ethylene glycol segment and 2,5,6,6- tetramethyl -2,5- heptandiol segment；

The solid base catalyst powder and the doping vario-property by high-temperature roasting is dispersed in the modified poly ester Sb₂O₃Powder.

As a preferred option:

A kind of modified polyester fiber containing solid base catalyst as described above, the modification containing solid base catalyst are poly- The filament number of ester fiber is 1.0~2.0tex, and breaking strength >=3.0cN/dtex, elongation at break is 25.0 ± 3.0%, volume Bent shrinking percentage be 10.0 ± 1.0%, crimp stability >=77%, internet pricing be 95 ± 5/m, line density deviation ratio≤1.5%, Breaking strength CV value≤8.0%, extension at break CV value≤8.0%, crimp contraction coefficient of variation CV value≤9.0%, boiling water are received Shrinkage is smaller for the additive amount of 5.0 ± 0.5%, of the invention 2,5,6,6- tetramethyl -2,5- heptandiols and solid base catalyst, It is smaller to the processing of polyester fiber and the influence of mechanical performance, the modified polyester fiber of the invention containing solid base catalyst Processing performance and mechanical performance (be not added with 2,5,6,6- tetramethyl -2,5- heptandiol with conventional polyester fiber and solid base urged Agent) quite；

Modified polyester fiber containing solid base catalyst is put under conditions of temperature is 25 DEG C and relative humidity is 65% After setting 60 months, inherent viscosity decline 18~24%；Under the same terms, comparative sample inherent viscosity decline 4.0%, comparative sample with The difference of modified polyester fiber containing solid base catalyst of the invention be its material be conventional polyester and be not added with by The solid base catalyst powder of high-temperature roasting, the modified polyester fiber of the invention containing solid base catalyst is compared to routine PET fiber natural degradation rate dramatically increases, and 2,5,6,6- tetramethyl -2,5- heptandiols and solid base catalyst can be mentioned significantly Rise the natural degradation rate of fiber.

Invention mechanism:

Macromolecular chain in polymer is not closely to pile up completely, always with the presence of gap between macromolecular chain, this Portion void volume is free volume.It penetrates into small molecule inside macromolecule, to have foot in macromolecule or between macromolecule Enough big gaps, so pore size (the i.e. ruler of free volume in the permeability and diffusivity of small molecule and macromolecular structure It is very little) it is related, in a certain range, the size of free volume is bigger, and the permeability of small molecule is higher, and diffusivity is better.Free body Product is divided into empty free volume and slit free volume again, and empty free body has bigger bulk compared with slit free volume, Promotion for the permeability of small molecule, empty free volume are more obvious compared with slit free volume effect.

The size and type of free volume depend primarily on the structure of polymer, and the principal element for influencing polymer architecture is Steric hindrance, side group size, side group structure etc..When position a certain on main polymer chain is replaced by side group, necessarily cause main chain The variation of activity, to change the interaction force of chain and interchain, chain can also occur to change accordingly at a distance from interchain, As a result lead to the variation of cohesive energy and free volume, polarity, size, length of the substituent group on polymer side chain etc. are to strand Rigid, intermolecular interaction so that the fractional free volume of polymer architecture all have a certain impact, therefore, substituent group The effect that difference generates is different, and the permeability and separation performance for often leading to polymer is also different.

For the dihydric alcohols straight chain molecule such as ethylene glycol, butanediol, the C atom on main chain is arranged in indention one on the other Column, when two H atoms on main chain on some methylene are by methyl (- CH₃) when replacing, C atom and master in the two side groups Chain C atom not in the same plane, then, four sp3 hybridized orbits on the C of center respectively with the sky on four C atoms around Orbital Overlap forms four identical σ keys, arranges in positive tetrahedron, and four carbon atom is located at the four of positive tetrahedron At this moment a vertex is equivalent to tert-butyl substitution when three hydrogen of methyl are further replaced by methyl, formed one bigger Tetrahedral structure, the strand that this strand in the arrangement of positive tetrahedron shape is arranged relative to indention, empty free body Product significantly increases very much, can significantly improve the permeability and diffusivity of small molecule；And work as on main chain on some methylene Two H atoms are drawn money on credit chain substituent when replacing, and what is mainly increased is slit free volume, and it is smaller to increase amplitude, to small molecule Permeability and diffusible promotion effect it is limited, simultaneously because chain substituent of drawing money on credit rigidity it is smaller, between strand be easy It tangles, is unfavorable for the increase of free volume.

The present invention has been obviously improved modified gather by introducing 2,5,6,6- tetramethyl -2,5- heptandiol in polyester molecule chain The structural formula of the natural degradation performance of ester fiber, 2,5,6,6- tetramethyl -2,5- heptandiols is as follows:

The presence of tert-butyl can cause the variation of main chain activity in 2,5,6,6- tetramethyl -2,5- heptandiols, to change The interaction force between chain element is become, the distance between molecule chain element can also occur to change accordingly, lead to modified poly ester Empty free volume increases.Compared with short-chain branch substituent group (such as methyl, ethyl group), tert-butyl occupies biggish space Position will obtain bigger free volume in the mode of strand arrangement；Compared with chain substituent of drawing money on credit, one side tert-butyl What is increased is empty free volume, and draw money on credit chain substituent increase is slit free volume, the rigidity of another aspect tert-butyl Greater than chain substituent of drawing money on credit, reduce the entanglement between strand, thus tert-butyl relatively draws money on credit chain substituent in strand arrangement Mode on have more free volumes.Since for molecules such as empty gas and waters, to for the diffusion of fibrous inside, cavity is freely More preferably, the present invention is by increasing empty free volume for the raising of volume ratio slit free volume, so that water or other molecules are such as empty Gas etc. is easier to penetrate into modified poly ester macromolecule internal, generates active influence to natural degradation performance of modified poly ester etc..

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 It is mainly H that a slower major reason of rate, which is nucleopilic reagent,₂O, H₂O to the C atom attack ability of ester carbonyl group RCOOR` compared with It is weak, it is not susceptible to nucleophilic addition, is hardly formed tetrahedral intermediate, therefore the degradation rate of polyester is slower.

The present invention enhances the attack ability of nucleopilic reagent, improves poly- by introducing solid base catalyst in the polyester The degradation rate of ester.Solid base selected by the present invention is MgO, BaO or SiO by high-temperature roasting₂- BaO, MgO or BaO exist Predominantly weakly alkaline hydroxyl when low temperature, but after high-temperature roasting, surface can generate the lattice defects such as point, line, surface, crystal table The oxygen in face can be enriched at tip, and when solid base catalyst charges, charge density of the distribution of charges at its surface, tip is most Greatly, it so that the surface MgO or BaO has different strong basicity positions, is easier to ionize out OH when combined with water^-, OH^-Relative to H₂O With stronger nucleophilie nucleus ability, thus in the polyester after introducing solid base catalyst, the difficulty that nucleophilic addition occurs is reduced Degree, and then improve the degradation rate of polyester.In addition, SiO₂- BaO is carrier loaded alkali metal, is also added relative to BaO Carrier S iO₂, carrier S iO₂Skeleton as active component plays a part of dispersing BaO and increases BaO intensity, additionally it is possible to change The crystal structure of BaO, forms defect and cavity, specific surface area and the aperture for increasing BaO enhance to increase the alkalinity of BaO Reinforcing effect of the BaO to the attack ability of nucleopilic reagent.

Present invention introduces 2,5,6,6- tetramethyl -2,5- heptandiols and solid base catalyst can also play synergistic effect, Solid base catalyst enhances the attack ability of nucleopilic reagent, promotes natural degradation reaction, 2,5,6,6- tetramethyls -2,5- Heptandiol increases the empty free volume of polyester, is conducive to the infiltration of oxygen and water, improves the concentration of oxygen atom inside polyester, Natural degradation reaction is further promoted, improves degradation rate significantly.

The present invention is also modified antimony oxide, improves the activity of antimony oxide, and attenuating prepares PET Process The additive amount of middle antimony oxide.

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

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 the modified polyester fiber of the invention containing solid base catalyst, by introducing in the polyester Modified component --- 2,5,6,6- tetramethyl -2,5- heptandiols increase empty free volume, improve nature drop to a certain extent Solve rate；

(2) preparation method of the modified polyester fiber of the invention containing solid base catalyst, by introducing in the polyester Component --- solid base catalyst significantly improves the natural degradation rate of modified polyester fiber；

(3) preparation method of the modified polyester fiber of the invention containing solid base catalyst, by having certain catalysis Active metal oxide improves antimony oxide specific surface area S to the doping vario-property of antimony oxide_gAnd per surface area On active r_s, to improve the catalytic activity of antimony oxide, improve polymerization efficiency；And then polyester life can met The additive amount for producing antimony-based catalyst when reducing synthesis polyester while needs effectively reduces the antimony discharge that fiber is made thereafter, It is advantageously implemented environmentally friendly production；

(4) preparation method of the modified polyester fiber of the invention containing solid base catalyst, low in cost, technique letter It is single, great application prospect；

(5) modified polyester fiber of the invention containing solid base catalyst, natural degradation rate is fast, good mechanical property, It has a extensive future.

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 the modified polyester fiber containing solid base catalyst, steps are as follows:

(1) modified poly ester is prepared；

(1.1) synthesis step of 2,5,6,6- tetramethyl -2,5- heptandiol is as follows:

(a) by the molar ratio of 1:1:1.2:2.0 by KOH powder, 3- methyl -3- hydroxyl butine, 3,3- dimethyl-2-butanone It is mixed with isopropyl ether, 2h is reacted under condition of ice bath, carry out crystallisation by cooling, centrifuge separation, washing, purification after reaction and done It is dry to obtain octyne glycol；

(b) octyne glycol, ethyl alcohol and palladium catalyst are mixed by the weight ratio of 2:10:0.01, in 40 DEG C of temperature condition Lower reaction 50min is continually fed into hydrogen in reaction process, carries out separation after reaction and purification obtains 2,5,6,6- tetramethyls Base -2,5- heptandiol, shown in the structural formula such as formula (I) of 2,5,6,6- tetramethyl -2,5- heptandiols；

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

Mg (the NO that concentration is 0.8mol% by (1.2.1)₃)₂The Sb that aqueous solution and concentration are 8mol%₂O₃Solution mixing Uniformly, Sb₂O₃The solvent of solution be oxalic acid, Mg in mixed liquor²⁺With Sb³⁺Molar ratio be 2:100；

The pH value that ammonium hydroxide to mixed liquor that concentration is 2mol/L is added dropwise in (1.2.2) is 9 to obtain precipitated product, then to precipitating Product is washed and is dried, and dry temperature is 105 DEG C, time 2.5h；

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

(1.3) MgO powder is prepared；

2h is kept the temperature after heating MgO to 400 DEG C first, 1h is kept the temperature after then heating to 700 DEG C, then cool down in air, most It is crushed to obtain the MgO powder that average grain diameter is 0.49 micron afterwards；

(1.4) esterification；

By terephthalic acid (TPA), ethylene glycol and 2,5,6,6- tetramethyl -2,5- heptandiols are made into slurry, are added and roast by high temperature The Sb of the MgO powder of burning, doping vario-property₂O₃Powder, titanium dioxide and Trimethyl phosphite after mixing, in nitrogen atmosphere Pressurization carries out esterification, and moulding pressure 0.3MPa, the temperature of esterification is 260 DEG C, when the water in esterification distillates Amount is esterification terminal when reaching the 92% of theoretical value, wherein terephthalic acid (TPA), ethylene glycol and 2,5,6,6- tetramethyls -2,5- The molar ratio of heptandiol is 1:1.5:0.04, the Sb of MgO powder, doping vario-property by high-temperature roasting₂O₃Powder, titanium dioxide Additional amount with Trimethyl phosphite be respectively terephthalic acid (TPA) additional amount 0.20wt%, 0.015wt%, 0.20wt% and 0.04wt%；

(1.5) 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 400Pa, and reaction temperature is 250 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 80Pa, reaction temperature 272 DEG C, reaction time 65min, the number-average molecular weight of modified poly ester obtained is 27900, molecular weight distributing index 1.8；

(2) modified poly ester POY are prepared；

Modified poly ester melt is squeezed out through metering, spinneret, is cooling, oiling and winding is made modified poly ester POY, POY The parameter of technique are as follows: 280 DEG C of spinning temperature, 20 DEG C of cooling temperature, winding speed 3600m/min；

(3) modified polyester fiber containing solid base catalyst is prepared；

Modified poly ester POY are made through seal wire, heating stretching, false twisting, thermal finalization and winding and contain solid base catalyst Modified polyester fiber, the parameter of DTY technique are as follows: spinning speed 400m/min, overfeed rate of setting 3.5%, winding overfeed rate 3.5%, the first 220 DEG C of heater temperature, the second 160 DEG C of heater temperature, draw ratio 1.6.

The final obtained modified polyester fiber containing solid base catalyst is DTY fiber, filament number 1.0tex, Breaking strength is 3.0cN/dtex, and elongation at break 25.0%, crimp contraction 11.0%, curling stability is 78%, Internet pricing is 90/m, and line density deviation ratio is 1.5%, and breaking strength CV value is 7.8%, and extension at break CV value is 7.2%, volume Bent shrinking percentage coefficient of variation CV value is 9.0%, boiling water shrinkage 5.0%；

Modified polyester fiber containing solid base catalyst is put under conditions of temperature is 25 DEG C and relative humidity is 65% After setting 60 months, inherent viscosity decline 18%.

Comparative example 1

A kind of preparation method of polyester fiber, preparation step is substantially the same manner as Example 1, the difference is that, it does not add The Sb of 2,5,6,6- tetramethyl -2,5- heptandiol, MgO powder and doping vario-property by high-temperature roasting₂O₃Powder, i.e., it is not right Polyester is modified, and the filament number of polyester fiber obtained is 1.0tex, breaking strength 3.2cN/dtex, elongation at break It is 24.0%, crimp contraction 10.2%, curling stability is 77%, and internet pricing is 90/m, and line density deviation ratio is 1.5%, breaking strength CV value is 7.5%, and extension at break CV value is 7.2%, and crimp contraction coefficient of variation CV value is 9.0%, Boiling water shrinkage is 4.8%；Under the same conditions, the inherent viscosity decline 4.0% of comparative sample, comparative sample contains with of the invention The difference of the modified polyester fiber of solid base catalyst is that its material is conventional polyester and is not added with consolidating by high-temperature roasting The Sb of body base catalyst powder and doping vario-property₂O₃Powder.Modified polyester fiber containing solid base catalyst of the invention is compared It is dramatically increased in conventional polyester fiber natural degradation rate, 2,5,6,6- tetramethyl -2,5- heptandiols and solid base catalyst powder The addition of body can be obviously improved the natural degradation rate of fiber, and mechanical property is unaffected.

Comparative example 2

A kind of preparation method of polyester fiber, preparation step is substantially the same manner as Example 1, the difference is that, preparation changes Property polyester during using using 1,2 dodecanediols substitute 2,5,6,6- tetramethyl -2,5- heptandiols, polyester obtained The filament number of fiber is 1.0tex, and breaking strength 3.1cN/dtex, elongation at break 26.0%, crimp contraction is 11.2%, curling stability is 77%, and internet pricing is 90/m, and line density deviation ratio is 1.5%, and breaking strength CV value is 7.8%, extension at break CV value is 7.2%, and crimp contraction coefficient of variation CV value is 9.0%, boiling water shrinkage 5.2%；? Under the same terms, the inherent viscosity decline 11.3% of comparative sample.

With the comparison of embodiment 1 it can be found that 2,5,6,6- tetramethyl -2,5- heptandiols are relative to containing chain substituent of drawing money on credit 1,2 dodecanediol is more advantageous to the degradation property for promoting fiber, this is primarily due on the one hand 2,5,6,6- tetramethyl -2, The free volume that tert-butyl in 5- heptandiol increases is more empty free volume, and the length in 1,2 dodecanediol The free volume that branched alkyl substituent increases is more slit free volume, on the other hand 2,5,6,6- tetramethyl -2,5- heptan two The rigidity of tert-butyl in alcohol is greater than the chain substituent of drawing money on credit in 1,2 dodecanediols, reduces the entanglement between strand, Thus 2,5,6,6- tetramethyl -2,5- heptandiol has more in the mode that polyester molecule chain arranges compared with 1,2 dodecanediols More free volumes, and then be more advantageous to and act synergistically with solid base catalyst, nucleophilic is enhanced in solid base catalyst The attack ability of reagent, on the basis of promoting natural degradation reaction, 2,5,6,6- tetramethyl -2,5- heptandiols are further increased The empty free volume of polyester, is conducive to the infiltration of oxygen and water, improves the concentration of oxygen atom inside polyester, further promotes Natural degradation reaction, improves degradation rate significantly.

Embodiment 2

A kind of preparation method of the modified polyester fiber containing solid base catalyst, steps are as follows:

(1) modified poly ester is prepared；

(1.1) synthesis step of 2,5,6,6- tetramethyl -2,5- heptandiol is as follows:

(a) by the molar ratio of 1.1:1:1.2:2.3 by KOH powder, 3- methyl -3- hydroxyl butine, 3,3- dimethyl -2- fourth Ketone and isopropyl ether mixing, 2h is reacted under condition of ice bath, after reaction carry out crystallisation by cooling, centrifuge separation, washing, purification and It is dried to obtain octyne glycol；

(b) octyne glycol, ethyl alcohol and palladium catalyst are mixed by the weight ratio of 2:10:0.01, in 45 DEG C of temperature condition Lower reaction 50min is continually fed into hydrogen in reaction process, carries out separation after reaction and purification obtains 2,5,6,6- tetramethyls Base -2,5- heptandiol, shown in the structural formula such as formula (I) of 2,5,6,6- tetramethyl -2,5- heptandiols；

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

Ca (the NO that concentration is 0.5mol% by (1.2.1)₃)₂The Sb that aqueous solution and concentration are 5mol%₂O₃Solution mixing Uniformly, Sb₂O₃The solvent of solution be oxalic acid, Ca in mixed liquor²⁺With Sb³⁺Molar ratio be 1:100；

The pH value that ammonium hydroxide to mixed liquor that concentration is 2mol/L is added dropwise in (1.2.2) is 10 to obtain precipitated product, then to heavy Shallow lake product is washed and is dried, and dry temperature is 110 DEG C, time 2h；

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

(1.3) BaO powder is prepared；

3h is kept the temperature after heating BaO to 400 DEG C first, 2h is kept the temperature after then heating to 700 DEG C, then cool down in air, most It is crushed to obtain the BaO powder that average grain diameter is 0.45 micron afterwards；

(1.4) esterification；

By terephthalic acid (TPA), ethylene glycol and 2,5,6,6- tetramethyl -2,5- heptandiols are made into slurry, are added and roast by high temperature The Sb of the BaO powder of burning, doping vario-property₂O₃Powder, titanium dioxide and Trimethyl phosphite after mixing, in nitrogen atmosphere Pressurization carries out esterification, and moulding pressure 0.3MPa, the temperature of esterification is 260 DEG C, when the water in esterification distillates Amount is esterification terminal when reaching the 92% of theoretical value, wherein terephthalic acid (TPA), ethylene glycol and 2,5,6,6- tetramethyls -2,5- The molar ratio of heptandiol is 1:1.5:0.05, the Sb of BaO powder, doping vario-property by high-temperature roasting₂O₃Powder, titanium dioxide Additional amount with Trimethyl phosphite be respectively terephthalic acid (TPA) additional amount 0.22wt%, 0.0135wt%, 0.25wt% and 0.01wt%；

(1.5) 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 400Pa, and reaction temperature is 250 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 80Pa, reaction temperature 270 DEG C, reaction time 50min, the number-average molecular weight of modified poly ester obtained is 29000, molecular weight distributing index 2.2；

(2) modified poly ester POY are prepared；

Modified poly ester melt is squeezed out through metering, spinneret, is cooling, oiling and winding is made modified poly ester POY, POY The parameter of technique are as follows: 280 DEG C of spinning temperature, 21 DEG C of cooling temperature, winding speed 3500m/min；

(3) modified polyester fiber containing solid base catalyst is prepared；

Modified poly ester POY are made through seal wire, heating stretching, false twisting, thermal finalization and winding and contain solid base catalyst Modified polyester fiber, the parameter of DTY technique are as follows: spinning speed 400m/min, overfeed rate of setting 5.5%, winding overfeed rate 2.5%, the first 200 DEG C of heater temperature, the second 170 DEG C of heater temperature, draw ratio 1.8.

The final obtained modified polyester fiber containing solid base catalyst is DTY fiber, filament number 1.5tex, Breaking strength is 3.2cN/dtex, and elongation at break 22.0%, crimp contraction 10.0%, curling stability is 77%, Internet pricing is 100/m, and line density deviation ratio is 1.46%, and breaking strength CV value is 7.9%, and extension at break CV value is 8.0%, Crimp contraction coefficient of variation CV value is 8.8%, boiling water shrinkage 4.5%；

Modified polyester fiber containing solid base catalyst is put under conditions of temperature is 25 DEG C and relative humidity is 65% After setting 60 months, inherent viscosity decline 18%.

Embodiment 3

A kind of preparation method of the modified polyester fiber containing solid base catalyst, steps are as follows:

(1) modified poly ester is prepared；

(1.1) synthesis step of 2,5,6,6- tetramethyl -2,5- heptandiol is as follows:

(a) by the molar ratio of 1.2:1:1.25:2.0 by KOH powder, 3- methyl -3- hydroxyl butine, 3,3- dimethyl -2- Butanone and isopropyl ether mixing, 3h is reacted under condition of ice bath, carries out crystallisation by cooling, centrifuge separation, washing, purification after reaction Be dried to obtain octyne glycol；

(b) octyne glycol, ethyl alcohol and palladium catalyst are mixed by the weight ratio of 3:10:0.03, in 40 DEG C of temperature condition Lower reaction 50min is continually fed into hydrogen in reaction process, carries out separation after reaction and purification obtains 2,5,6,6- tetramethyls Base -2,5- heptandiol, shown in the structural formula such as formula (I) of 2,5,6,6- tetramethyl -2,5- heptandiols；

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

Ba (the NO that concentration is 1.0mol% by (1.2.1)₃)₂The Sb that aqueous solution and concentration are 10mol%₂O₃Solution it is mixed It closes uniformly, Sb₂O₃The solvent of solution be oxalic acid, Ba in mixed liquor²⁺With Sb³⁺Molar ratio be 3:100；

The pH value that ammonium hydroxide to mixed liquor that concentration is 2mol/L is added dropwise in (1.2.2) is 9.5 to obtain precipitated product, then to heavy Shallow lake product is washed and is dried, and dry temperature is 105 DEG C, time 3h；

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

(1.3) SiO is prepared₂- BaO powder；

SiO is heated first₂2.5h is kept the temperature after-BaO to 400 DEG C, 1.5h is kept the temperature after then heating to 700 DEG C, then in air Middle cooling is finally crushed to obtain the SiO that average grain diameter is 0.48 micron₂- BaO powder, SiO₂The content of BaO is in-BaO 40wt%；

(1.4) esterification；

By terephthalic acid (TPA), ethylene glycol and 2,5,6,6- tetramethyl -2,5- heptandiols are made into slurry, are added and roast by high temperature The B of burning₂O₃-Al₂O₃The Sb of powder, doping vario-property₂O₃Powder, titanium dioxide and triphenyl phosphate after mixing, in nitrogen atmosphere It encloses middle pressurization and carries out esterification, moulding pressure 0.2MPa, the temperature of esterification is 255 DEG C, when the water in esterification Quantity of distillate is esterification terminal when reaching the 90% of theoretical value, wherein terephthalic acid (TPA), ethylene glycol and 2,5,6,6- tetramethyls- The molar ratio of 2,5- heptandiols is 1:2.0:0.053, by the SiO of high-temperature roasting₂The Sb of-BaO powder, doping vario-property₂O₃Powder The additional amount of body, titanium dioxide and triphenyl phosphate be respectively terephthalic acid (TPA) additional amount 0.24wt%, 0.012wt%, 0.21wt% and 0.03wt%；

(1.5) 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 450Pa, and reaction temperature is 256 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 60min, the number-average molecular weight of modified poly ester obtained is 30000, molecular weight distributing index 1.9；

(2) modified poly ester POY are prepared；

Modified poly ester melt is squeezed out through metering, spinneret, is cooling, oiling and winding is made modified poly ester POY, POY The parameter of technique are as follows: 285 DEG C of spinning temperature, 22 DEG C of cooling temperature, winding speed 3300m/min；

(3) modified polyester fiber containing solid base catalyst is prepared；

Modified poly ester POY are made through seal wire, heating stretching, false twisting, thermal finalization and winding and contain solid base catalyst Modified polyester fiber, the parameter of DTY technique are as follows: spinning speed 600m/min, overfeed rate of setting 3.5%, winding overfeed rate 2.5%, the first 180 DEG C of heater temperature, the second 180 DEG C of heater temperature, draw ratio 1.7.

The final obtained modified polyester fiber containing solid base catalyst is DTY fiber, filament number 1.5tex, Breaking strength is 3.1cN/dtex, and elongation at break 22.0%, crimp contraction 11.0%, curling stability is 77%, Internet pricing is 100/m, and line density deviation ratio is 1.46%, and breaking strength CV value is 7.8%, and extension at break CV value is 8.0%, Crimp contraction coefficient of variation CV value is 9.0%, boiling water shrinkage 5.5%；

Modified polyester fiber containing solid base catalyst is put under conditions of temperature is 25 DEG C and relative humidity is 65% After setting 60 months, inherent viscosity decline 20%.

Embodiment 4

A kind of preparation method of the modified polyester fiber containing solid base catalyst, steps are as follows:

(1) modified poly ester is prepared；

(1.1) synthesis step of 2,5,6,6- tetramethyl -2,5- heptandiol is as follows:

(a) by the molar ratio of 1.2:1:1.3:2.5 by KOH powder, 3- methyl -3- hydroxyl butine, 3,3- dimethyl -2- fourth Ketone and isopropyl ether mixing, 3h is reacted under condition of ice bath, after reaction carry out crystallisation by cooling, centrifuge separation, washing, purification and It is dried to obtain octyne glycol；

(b) octyne glycol, ethyl alcohol and palladium catalyst are mixed by the weight ratio of 2.5:10:0.02, in 45 DEG C of temperature strip 60min is reacted under part, hydrogen is continually fed into reaction process, carries out separation after reaction and purification obtains 2,5,6,6- tetramethyls Base -2,5- heptandiol, shown in the structural formula such as formula (I) of 2,5,6,6- tetramethyl -2,5- heptandiols；

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

Zn (the NO that concentration is 0.6mol% by (1.2.1)₃)₂The Sb that aqueous solution and concentration are 6mol%₂O₃Solution mixing Uniformly, Sb₂O₃The solvent of solution be oxalic acid, Zn in mixed liquor²⁺With Sb³⁺Molar ratio be 1.2:100；

The pH value that ammonium hydroxide to mixed liquor that concentration is 2mol/L is added dropwise in (1.2.2) is 10 to obtain precipitated product, then to heavy Shallow lake product is washed and is dried, and dry temperature is 110 DEG C, time 2.5h；

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

(1.3) MgO/BaO powder is prepared；

2h is kept the temperature after heating MgO/BaO (mixture that mass ratio is 1:1) to 400 DEG C first, after then heating to 700 DEG C 2h is kept the temperature, then is cooled down in air, is finally crushed to obtain the MgO/BaO powder that average grain diameter is 0.47 micron；

(1.4) esterification；

By terephthalic acid (TPA), ethylene glycol and 2,5,6,6- tetramethyl -2,5- heptandiols are made into slurry, are added and roast by high temperature The Sb of the MgO/BaO powder of burning, doping vario-property₂O₃Powder, titanium dioxide and Trimethyl phosphite after mixing, in nitrogen atmosphere It encloses middle pressurization and carries out esterification, moulding pressure 0.1MPa, the temperature of esterification is 250 DEG C, when the water in esterification Quantity of distillate is esterification terminal when reaching the 90% of theoretical value, wherein terephthalic acid (TPA), ethylene glycol and 2,5,6,6- tetramethyls- The molar ratio of 2,5- heptandiols is 1:1.5:0.07, the Sb of MgO/BaO powder, doping vario-property by high-temperature roasting₂O₃Powder, The additional amount of titanium dioxide and Trimethyl phosphite be respectively terephthalic acid (TPA) additional amount 0.23wt%, 0.012wt%, 0.20wt% and 0.02wt%；

(1.5) 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 420Pa, and reaction temperature is 260 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 85Pa, reaction temperature 270 DEG C, reaction time 90min, the number-average molecular weight of modified poly ester obtained is 25000, molecular weight distributing index 2.0；

(2) modified poly ester POY are prepared；

Modified poly ester melt is squeezed out through metering, spinneret, is cooling, oiling and winding is made modified poly ester POY, POY The parameter of technique are as follows: 283 DEG C of spinning temperature, 20 DEG C of cooling temperature, winding speed 3500m/min；

(3) modified polyester fiber containing solid base catalyst is prepared；

Modified poly ester POY are made through seal wire, heating stretching, false twisting, thermal finalization and winding and contain solid base catalyst Modified polyester fiber, the parameter of DTY technique are as follows: spinning speed 500m/min, overfeed rate of setting 4.0%, winding overfeed rate 5.0%, the first 180 DEG C of heater temperature, the second 150 DEG C of heater temperature, draw ratio 1.62.

The final obtained modified polyester fiber containing solid base catalyst is DTY fiber, filament number 2.0tex, Breaking strength is 3.2cN/dtex, and elongation at break 25.0%, crimp contraction 11.0%, curling stability is 78%, Internet pricing is 90/m, and line density deviation ratio is 1.4%, and breaking strength CV value is 7.9%, and extension at break CV value is 7.9%, volume Bent shrinking percentage coefficient of variation CV value is 8.92%, boiling water shrinkage 5.5%；

Modified polyester fiber containing solid base catalyst is put under conditions of temperature is 25 DEG C and relative humidity is 65% After setting 60 months, inherent viscosity decline 21%.

Embodiment 5

A kind of preparation method of the modified polyester fiber containing solid base catalyst, steps are as follows:

(1) modified poly ester is prepared；

(1.1) synthesis step of 2,5,6,6- tetramethyl -2,5- heptandiol is as follows:

(a) by the molar ratio of 1:1:1.3:3.0 by KOH powder, 3- methyl -3- hydroxyl butine, 3,3- dimethyl-2-butanone It is mixed with isopropyl ether, 4h is reacted under condition of ice bath, carry out crystallisation by cooling, centrifuge separation, washing, purification after reaction and done It is dry to obtain octyne glycol；

(b) octyne glycol, ethyl alcohol and palladium catalyst are mixed by the weight ratio of 2.5:10:0.02, in 50 DEG C of temperature strip 55min is reacted under part, hydrogen is continually fed into reaction process, carries out separation after reaction and purification obtains 2,5,6,6- tetramethyls Base -2,5- heptandiol, shown in the structural formula such as formula (I) of 2,5,6,6- tetramethyl -2,5- heptandiols；

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

Mg (the NO that concentration is 0.7mol% by (1.2.1)₃)₂The Sb that aqueous solution and concentration are 8mol%₂O₃Solution mixing Uniformly, Sb₂O₃The solvent of solution be oxalic acid, Mg in mixed liquor²⁺With Sb³⁺Molar ratio be 2:100；

The pH value that ammonium hydroxide to mixed liquor that concentration is 2mol/L is added dropwise in (1.2.2) is 10 to obtain precipitated product, then to heavy Shallow lake product is washed and is dried, and dry temperature is 110 DEG C, time 2.5h；

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

(1.3) MgO/SiO is prepared₂- BaO powder；

MgO/SiO is heated first₂2h is kept the temperature after-BaO (mixture of mass ratio 1:2) to 400 DEG C, then heats to 700 2h is kept the temperature after DEG C, then is cooled down in air, is finally crushed to obtain the MgO/SiO that average grain diameter is 0.48 micron₂- BaO powder Body, SiO₂The content of BaO is 80wt% in-BaO；

(1.4) esterification；

By terephthalic acid (TPA), ethylene glycol and 2,5,6,6- tetramethyl -2,5- heptandiols are made into slurry, are added and roast by high temperature The MgO/SiO of burning₂The Sb of-BaO powder, doping vario-property₂O₃Powder, titanium dioxide and trimethyl phosphate after mixing, in nitrogen Pressurization carries out esterification in atmosphere, and moulding pressure 0.3MPa, the temperature of esterification is 252 DEG C, when in esterification Water quantity of distillate is esterification terminal when reaching the 90% of theoretical value, wherein terephthalic acid (TPA), ethylene glycol and 2,5,6,6- tetramethyls The molar ratio of base -2,5- heptandiol is 1:1.6:0.064, by the MgO/SiO of high-temperature roasting₂- BaO powder, doping vario-property Sb₂O₃The additional amount of powder, titanium dioxide and trimethyl phosphate be respectively terephthalic acid (TPA) additional amount 0.25wt%, 0.015wt%, 0.24wt% and 0.01wt%；

(1.5) 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 500Pa, and reaction temperature is 256 DEG C, reaction time 45min, 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 88Pa, reaction temperature 271 DEG C, reaction time 75min, the number-average molecular weight of modified poly ester obtained is 25000, molecular weight distributing index 1.8；

(2) modified poly ester POY are prepared；

Modified poly ester melt is squeezed out through metering, spinneret, is cooling, oiling and winding is made modified poly ester POY, POY The parameter of technique are as follows: 288 DEG C of spinning temperature, 18 DEG C of cooling temperature, winding speed 3200m/min；

(3) modified polyester fiber containing solid base catalyst is prepared；

Modified poly ester POY are made through seal wire, heating stretching, false twisting, thermal finalization and winding and contain solid base catalyst Modified polyester fiber, the parameter of DTY technique are as follows: spinning speed 800m/min, overfeed rate of setting 4.5%, winding overfeed rate 4.0%, the first 220 DEG C of heater temperature, the second 150 DEG C of heater temperature, draw ratio 1.6.

The final obtained modified polyester fiber containing solid base catalyst is DTY fiber, filament number 2.0tex, Breaking strength is 3.22cN/dtex, and elongation at break 22.0%, crimp contraction 9.0%, curling stability is 79%, Internet pricing is 95/m, and line density deviation ratio is 1.5%, and breaking strength CV value is 8.0%, and extension at break CV value is 7.9%, volume Bent shrinking percentage coefficient of variation CV value is 8.83%, boiling water shrinkage 5.2%；

Modified polyester fiber containing solid base catalyst is put under conditions of temperature is 25 DEG C and relative humidity is 65% After setting 60 months, inherent viscosity decline 24%.

Embodiment 6

A kind of preparation method of the modified polyester fiber containing solid base catalyst, steps are as follows:

(1) modified poly ester is prepared；

(1.1) synthesis step of 2,5,6,6- tetramethyl -2,5- heptandiol is as follows:

(a) by the molar ratio of 1.1:1:1.2:3.0 by KOH powder, 3- methyl -3- hydroxyl butine, 3,3- dimethyl -2- fourth Ketone and isopropyl ether mixing, 4h is reacted under condition of ice bath, after reaction carry out crystallisation by cooling, centrifuge separation, washing, purification and It is dried to obtain octyne glycol；

(b) octyne glycol, ethyl alcohol and palladium catalyst are mixed by the weight ratio of 3:10:0.03, in 50 DEG C of temperature condition Lower reaction 60min is continually fed into hydrogen in reaction process, carries out separation after reaction and purification obtains 2,5,6,6- tetramethyls Base -2,5- heptandiol, shown in the structural formula such as formula (I) of 2,5,6,6- tetramethyl -2,5- heptandiols；

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

Concentration is the Mg (NO of 0.8mol% by (1.2.1)₃)₂Aqueous solution and Ca (NO₃)₂1:1 is mixed by volume for aqueous solution Conjunction obtains metal ion M^x+Aqueous solution, metal ion M^x+Aqueous solution and concentration be 8mol% Sb₂O₃Solution it is mixed It closes uniformly, Sb₂O₃The solvent of solution be oxalic acid, M in mixed liquor^x+With Sb³⁺Molar ratio be 2.5:100；

The pH value that ammonium hydroxide to mixed liquor that concentration is 2mol/L is added dropwise in (1.2.2) is 10 to obtain precipitated product, then to heavy Shallow lake product is washed and is dried, and dry temperature is 105 DEG C, time 3h；

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

(1.3) BaO/SiO is prepared₂- BaO powder；

BaO/SiO is heated first₂3h is kept the temperature after-BaO (mixture that mass ratio is 1:3) to 400 DEG C, is then heated to 1h is kept the temperature after 700 DEG C, then is cooled down in air, is finally crushed to obtain the BaO/SiO that average grain diameter is 0.44 micron₂-BaO Powder, SiO₂The content of BaO is 60wt% in-BaO；

(1.4) esterification；

By terephthalic acid (TPA), ethylene glycol and 2,5,6,6- tetramethyl -2,5- heptandiols are made into slurry, are added and roast by high temperature The BaO/SiO of burning₂The Sb of-BaO powder, doping vario-property₂O₃Powder, titanium dioxide and triphenyl phosphate after mixing, in nitrogen Pressurization carries out esterification in atmosphere, and moulding pressure is normal pressure, and the temperature of esterification is 260 DEG C, when the water in esterification Quantity of distillate is esterification terminal when reaching the 95% of theoretical value, wherein terephthalic acid (TPA), ethylene glycol and 2,2,3,4,5,5- six The molar ratio of methyl -3,4- hexylene glycol is 1:1.8:0.06, by the BaO/SiO of high-temperature roasting₂- BaO powder, doping vario-property Sb₂O₃The additional amount of powder, titanium dioxide and triphenyl phosphate be respectively terephthalic acid (TPA) additional amount 0.20wt%, 0.014wt%, 0.21wt% and 0.05wt%；

(1.5) 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 260 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 275 DEG C, reaction time 50min, the number-average molecular weight of modified poly ester obtained is 25000, molecular weight distributing index 1.8；

(2) modified poly ester POY are prepared；

Modified poly ester melt is squeezed out through metering, spinneret, is cooling, oiling and winding is made modified poly ester POY, POY The parameter of technique are as follows: 290 DEG C of spinning temperature, 19 DEG C of cooling temperature, winding speed 3400m/min；

(3) modified polyester fiber containing solid base catalyst is prepared；

Modified poly ester POY are made through seal wire, heating stretching, false twisting, thermal finalization and winding and contain solid base catalyst Modified polyester fiber, the parameter of DTY technique are as follows: spinning speed 800m/min, overfeed rate of setting 5.5%, winding overfeed rate 5.0%, the first 210 DEG C of heater temperature, the second 150 DEG C of heater temperature, draw ratio 1.6.

The final obtained modified polyester fiber containing solid base catalyst is DTY fiber, filament number 1.3tex, Breaking strength is 3.2cN/dtex, and elongation at break 24.0%, crimp contraction 11.0%, curling stability is 77%, Internet pricing is 90/m, and line density deviation ratio is 1.5%, and breaking strength CV value is 7.8%, and extension at break CV value is 8.0%, volume Bent shrinking percentage coefficient of variation CV value is 8.7%, boiling water shrinkage 5.5%；

Modified polyester fiber containing solid base catalyst is put under conditions of temperature is 25 DEG C and relative humidity is 65% After setting 60 months, inherent viscosity decline 18%.

Embodiment 7

A kind of preparation method of the modified polyester fiber containing solid base catalyst, steps are as follows:

(1) modified poly ester is prepared；

(1.1) synthesis step of 2,5,6,6- tetramethyl -2,5- heptandiol is as follows:

(a) by the molar ratio of 1.2:1:1.2:3.0 by KOH powder, 3- methyl -3- hydroxyl butine, 3,3- dimethyl -2- fourth Ketone and isopropyl ether mixing, 3h is reacted under condition of ice bath, after reaction carry out crystallisation by cooling, centrifuge separation, washing, purification and It is dried to obtain octyne glycol；

(b) octyne glycol, ethyl alcohol and palladium catalyst are mixed by the weight ratio of 3:10:0.02, in 42 DEG C of temperature condition Lower reaction 55min is continually fed into hydrogen in reaction process, carries out separation after reaction and purification obtains 2,5,6,6- tetramethyls Base -2,5- heptandiol, shown in the structural formula such as formula (I) of 2,5,6,6- tetramethyl -2,5- heptandiols；

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

Concentration is the Mg (NO of 0.5mol% by (1.2.1)₃)₂Aqueous solution, Ba (NO₃)₂Aqueous solution and Ca (NO₃)₂It is water-soluble 1:1:1 is mixed to get metal ion M to liquid by volume^x+Aqueous solution, metal ion M^x+Aqueous solution be with concentration The Sb of 10mol%₂O₃Solution be uniformly mixed, Sb₂O₃The solvent of solution be oxalic acid, metal ions M in mixed liquor^x+With Sb³⁺'s Molar ratio is 2:100；

The pH value that ammonium hydroxide to mixed liquor that concentration is 2mol/L is added dropwise in (1.2.2) is 9 to obtain precipitated product, then to precipitating Product is washed and is dried, and dry temperature is 108 DEG C, time 2.5h；

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

(1.3) MgO powder is prepared；

2h is kept the temperature after heating MgO to 400 DEG C first, 1.2h is kept the temperature after then heating to 700 DEG C, then cool down in air, It is finally crushed to obtain the MgO powder that average grain diameter is 0.48 micron；

(1.4) esterification；

By terephthalic acid (TPA), ethylene glycol and 2,5,6,6- tetramethyl -2,5- heptandiols are made into slurry, are added and roast by high temperature The Sb of the MgO powder of burning, doping vario-property₂O₃Powder, titanium dioxide and Trimethyl phosphite after mixing, in nitrogen atmosphere Pressurization carries out esterification, and moulding pressure 0.2MPa, the temperature of esterification is 250 DEG C, when the water in esterification distillates Amount is esterification terminal when reaching the 92% of theoretical value, wherein terephthalic acid (TPA), ethylene glycol and 2,2,3,4,5,5- hexamethyls- The molar ratio of 3,4- hexylene glycols is 1:1.2:0.05, the Sb of MgO powder, doping vario-property by high-temperature roasting₂O₃Powder, dioxy The additional amount of change titanium and Trimethyl phosphite is respectively 0.25wt%, 0.015wt%, 0.25wt% of terephthalic acid (TPA) additional amount And 0.03wt%；

(1.5) 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 95Pa, reaction temperature 274 DEG C, reaction time 70min, the number-average molecular weight of modified poly ester obtained is 30000, molecular weight distributing index 2.2；

(2) modified poly ester POY are prepared；

Modified poly ester melt is squeezed out through metering, spinneret, is cooling, oiling and winding is made modified poly ester POY, POY The parameter of technique are as follows: 280 DEG C of spinning temperature, 20 DEG C of cooling temperature, winding speed 3600m/min；

(3) modified polyester fiber containing solid base catalyst is prepared；

Modified poly ester POY are made through seal wire, heating stretching, false twisting, thermal finalization and winding and contain solid base catalyst Modified polyester fiber, the parameter of DTY technique are as follows: spinning speed 600m/min, overfeed rate of setting 3.5%, winding overfeed rate 3.0%, the first 210 DEG C of heater temperature, the second 180 DEG C of heater temperature, draw ratio 1.8.

The final obtained modified polyester fiber containing solid base catalyst is DTY fiber, filament number 1.0tex, Breaking strength is 3.0cN/dtex, and elongation at break 28.0, crimp contraction 10.0%, curling stability is 78.5%, Internet pricing is 96/m, and line density deviation ratio is 1.44%, and breaking strength CV value is 7.6%, and extension at break CV value is 7.8%, Crimp contraction coefficient of variation CV value is 8.2%, boiling water shrinkage 4.5%；

Modified polyester fiber containing solid base catalyst is put under conditions of temperature is 25 DEG C and relative humidity is 65% After setting 60 months, inherent viscosity decline 22%.

Claims (10)

1. a kind of preparation method of the modified polyester fiber containing solid base catalyst, it is characterized in that: poly- by being modified by POY technique After ester melt is made modified poly ester POY, then the obtained modification containing solid base catalyst of processing is carried out to it by DTY technique and is gathered Ester fiber；

The modified poly ester the preparation method comprises the following steps: by terephthalic acid (TPA), ethylene glycol, 2,5,6,6- tetramethyl -2,5- heptandiol, warp Cross the solid base catalyst powder of high-temperature roasting and the Sb of doping vario-property₂O₃Powder after mixing successively carry out esterification and Polycondensation reaction；

The structural formula of 2,5,6,6- tetramethyl -2,5- heptandiol is as follows:

The temperature of solid base catalyst high-temperature roasting is 400~700 DEG C, solid base catalyst MgO, BaO and SiO₂In-BaO More than one；

Sb₂O₃The process of doping vario-property are as follows: first by metal ion M^x+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 and crushes；

Metal ions M^x+For Mg²⁺、Ca²⁺、Ba²⁺And Zn²⁺One or more of.

2. a kind of preparation method of modified polyester fiber containing solid base catalyst according to claim 1, feature It is, described 2, the synthesis step of 5,6,6- tetramethyl -2,5- heptandiols is as follows:

(1) 1~1.2:1:1.2~1.3:2.0~3.0 molar ratio is pressed by KOH powder, 3- methyl -3- hydroxyl butine, 3,3- bis- Methyl -2- butanone and isopropyl ether mixing, react 2~4h under condition of ice bath, carry out crystallisation by cooling, centrifugation point after reaction From, wash, refine and be dried to obtain octyne glycol；

(2) octyne glycol, ethyl alcohol and palladium catalyst are mixed by the weight ratio of 2~3:10:0.01~0.03, at 40~50 DEG C 50~60min is reacted under the conditions of temperature, is continually fed into hydrogen in reaction process, carries out separation after reaction and purification obtains 2, 5,6,6- tetramethyl -2,5- heptandiol.

3. a kind of preparation method of modified polyester fiber containing solid base catalyst according to claim 2, feature It is, SiO₂The content of BaO is 40~80wt% in-BaO；The process of high-temperature roasting are as follows: keep the temperature 2 after being warming up to 400 DEG C first ~3h keeps the temperature 1~2h, finally cools down in air after then heating to 700 DEG C；Solid base catalyst carries out after high-temperature roasting Crushing obtains powder of the average grain diameter less than 0.5 micron.

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

5. a kind of preparation method of modified polyester fiber containing solid base catalyst according to claim 4, feature It is, the preparation step of the modified poly ester is as follows:

(1) esterification；

By terephthalic acid (TPA), ethylene glycol and 2,5,6,6- tetramethyl -2,5- heptandiols are made into slurry, are added by high-temperature roasting The Sb of solid base catalyst powder, doping vario-property₂O₃Powder, delustering agent and stabilizer after mixing, pressurize in nitrogen atmosphere Esterification is carried out, moulding pressure is normal pressure~0.3MPa, and the temperature of esterification is 250~260 DEG C, when in esterification Water quantity of distillate is esterification terminal when reaching 90% of theoretical value 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 270~275 DEG C, and the reaction time is 50~90min.

6. a kind of preparation method of modified polyester fiber containing solid base catalyst according to claim 5, feature It is, the terephthalic acid (TPA), ethylene glycol and 2, the molar ratio of 5,6,6- tetramethyl -2,5- heptandiols is 1:1.2~2.0: 0.03~0.05, the Sb of the solid base catalyst powder by high-temperature roasting, doping vario-property₂O₃Powder, delustering agent and stabilization The additional amount of agent be respectively 0.20~0.25wt% of terephthalic acid (TPA) additional amount, 0.012~0.015wt%, 0.20~ 0.25wt% and 0.01~0.05wt%；The delustering agent is titanium dioxide, and the stabilizer is triphenyl phosphate, tripotassium phosphate Ester or Trimethyl phosphite.

7. a kind of preparation method of modified polyester fiber containing solid base catalyst according to claim 6, feature It is, the number-average molecular weight of modified poly ester is 25000~30000, and molecular weight distributing index is 1.8~2.2.

8. a kind of preparation method of modified polyester fiber containing solid base catalyst according to claim 1, feature It is, the process of the POY technique 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 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: 400~800m/min of spinning speed, overfeed rate of setting 3.5~5.5%, winding overfeed rate 2.5~5.0%, the first 180~220 DEG C of heater temperature, the second 150~180 DEG C of heater temperature, draw ratio 1.6~1.8.

9. using a kind of preparation of the modified polyester fiber containing solid base catalyst as described in any one of claims 1 to 8 A kind of modified polyester fiber containing solid base catalyst made from method, it is characterized in that: being DTY fiber, point of modified poly ester Subchain includes terephthalic acid (TPA) segment, ethylene glycol segment and 2,5,6,6- tetramethyl -2,5- heptandiol segment；

The solid base catalyst powder by high-temperature roasting and the doping vario-property are dispersed in the modified poly ester Sb₂O₃Powder.

10. a kind of modified polyester fiber containing solid base catalyst according to claim 9, which is characterized in that contain The filament number of the modified polyester fiber of solid base catalyst is 1.0~2.0tex, and breaking strength >=3.0cN/dtex, fracture stretches Long rate is 25.0 ± 3.0%, and crimp contraction is 10.0 ± 1.0%, crimps stability >=77%, and internet pricing is 95 ± 5/m, Line density deviation ratio≤1.5%, breaking strength CV value≤8.0%, extension at break CV value≤8.0%, crimp contraction variation lines Number CV value≤9.0%, boiling water shrinkage are 5.0 ± 0.5%；Modified polyester fiber containing solid base catalyst is 25 in temperature DEG C and relative humidity be 65% under conditions of places 60 months after, inherent viscosity decline 18~24%.