CN106283264A - A kind of porous surpasses flexible polyester fiber POY silk and preparation method thereof - Google Patents

A kind of porous surpasses flexible polyester fiber POY silk and preparation method thereof Download PDF

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Publication number
CN106283264A
CN106283264A CN201610788733.5A CN201610788733A CN106283264A CN 106283264 A CN106283264 A CN 106283264A CN 201610788733 A CN201610788733 A CN 201610788733A CN 106283264 A CN106283264 A CN 106283264A
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phthalic acid
preparation
esterification
porous
ethylene glycol
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CN106283264B (en
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范红卫
汤方明
王力军
孙晓华
温浩
熊克
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Jiangsu Hengli Chemical Fiber Co Ltd
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Jiangsu Hengli Chemical Fiber Co Ltd
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The present invention relates to a kind of porous and surpass flexible polyester fiber POY silk and preparation method thereof, modified poly ester uses porous spinneret spinning prepare porous and surpasses flexible polyester fiber POY silk；On porous spinneret, the arrangement mode of spinneret orifice is that the hole of oval shaped arrangements, i.e. spinneret orifice is centrally located on concentration ellipse, and concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear.Porous surpasses flexible polyester fiber POY silk and is obtained Modified polyester chips by modified poly ester through pelletizing, Modified polyester chips is prepared through measuring, extrude, cool down, oil and winding, the preparation method of modified poly ester is: p-phthalic acid and glycol reaction prepare ethylene glycol terephthalate, add p-phthalic acid and react, with the hexanediol containing side chain, the p-phthalic acid binary alcohol esters prepared, continue reaction and obtain modified poly ester.The fibre property that the present invention prepares is excellent, line density deviation ratio≤0.2%, fracture strength CV value≤2.5%, extension at break CV value≤5.0%.

Description

A kind of porous surpasses flexible polyester fiber POY silk and preparation method thereof
Technical field
The invention belongs to field of polyester fiber, relate to a kind of porous and surpass flexible polyester fiber POY silk and preparation method thereof.
Background technology
Polyethylene terephthalate (PET or polyester fiber) fiber from come out since, have fracture strength and Elastic modelling quantity is high, and resilience is moderate, and thermal finalization is excellent, and heat-resisting light resistance is good and acid-fast alkali-proof corrosion resistance etc. is a series of excellent Performance, and fabric has wash and wear, the advantages such as stiffness is good, is widely used in the field such as clothing, home textile.
But owing to the degree of crystallinity of PET is high, the functional group that compact structure, and strand do not combine with dyestuff, cause Dye molecule hardly enters fibrous inside, dyeing difficulty.People cannot be met to bright-coloured beautiful, the fabric demand of unique style.
The reason causing PET dyeing difficulty is that PET belongs to symmetric straight chain macromolecular, and strand does not contains side chain radical Group, regularity is the best, and its main chain contains the phenyl ring of rigidity and flexible alkyl, and the ester group being directly connected with phenyl ring and Phenyl ring constitutes again the conjugated system of rigidity, thus constrains rotating freely of its soft segment.Such a structure increases molecule The wall ridge of sub-chain motion, the glass transition temperature causing PET is higher, needs to promote dye molecule under the highest temperature conditions To the diffusion of fibrous inside, complete staining procedure.It addition, the strand of PET is regular, good crystallinity, strand arrangement is tight, and And the polar group not having an effect with dye molecule on strand, the colouring making PET is more difficult.
Therefore, under the general High Temperature High Pressure of dyeing of common PET, select disperse dyeing, when temperature reaches PET When fiber obtains more than vitrification point, between PET polymer molecule, space increases, but the degree that its free volume increases is little, Dyeing rate is the highest, but the energy consumption brought of high temperature and high pressure method and dye-uptake low be the subject matter faced now.It addition, PET melt viscosity is higher, is unfavorable for processing.
The method of preparation PET is a lot, the one that wherein melt spinning method is more in being the application of current commercial production.Molten Melting and have many parameters in spinning process, these parameters determine the course of fiberizing and spin structure and the performance of fiber, produce On be through the fiber that controls these parameters to prepare desired properties.Mainly spin according to what technical process can control in producing Silk summary of parameters.An is melting condition, spinning conditions, condition of cure, wrapping wire condition etc., and wherein strand cooling and solidifying condition is to fiber Structure and performance have conclusive impact, for controlling rate of cooling and the uniformity thereof of polyester fondant thread, generally adopt in production Take cooling blowing.Cooling blowing can accelerate the rate of cooling of melt stream, is conducive to improving spinning speed；Strengthen around strand empty The convection current of gas, makes the cooling of ectonexine strand uniformly, for using porous spinneret to create condition；Cooling blowing can make as-spun fibre Quality advance, tensile property improves, the beneficially production capacity of raising equipment.
Experimental branch line all uses cross air blasting as the type of cooling for a long time, and energy resource consumption accounts for long filament production cost very Major part, along with chemical fibre performance and quality requirements are improved by people day by day, the exploitation of chemical-fibres filaments new product is to high added value Fibre in differentiation direction is developed, it is desirable to higher cooling blowing condition, then proposes ring blowing device.Ring blowing device is not only Possess every uniform advantage of synnema wind-engaging, and energy consumption is compared relatively low, effectively solve cross air blasting owing to blowing area is big The wind energy loss problem caused.
In spinning process, although ring blowing has an obvious advantage, but still existing problems: due to spun silk from After circular jetting filament plate extrusion, by ring quenching, owing to the circular jetting filament plate number of turns is more so that ring blowing hardly enters interior Layer, causes the silk at outermost silk innermost layer the most after cooling may be the most uncolled, thus the silk of gained occurs that fiber number is irregular, The problems such as intensity is irregular, uneven dyeing, cause and follow-up silk are processed further difficulty occur.
Summary of the invention
It is an object of the invention to overcome the problems such as existing dyeing polyester fibers is irregular, mechanical property is poor, it is achieved extensive The production spinning changed, it is provided that a kind of porous surpasses flexible polyester fiber POY silk and preparation method thereof.The polyester fiber of the present invention former Material for modified poly ester, introduces the hexanediol segment containing side chain in the strand of modified poly ester, be modified porous prepared by polyester and surpass Flexible polyester fiber POY silk, under the conditions of uniform temperature, porous surpasses between the space of flexible polyester fiber POY silk interior molecules interchain The increasing degree of gap is far longer than at equal temperature the molecules such as unbranched conventional polyester fiber, beneficially stain and enters Internal degree, improves dyeing rate；Porous surpasses the melt viscosity of flexible polyester fiber POY silk and reduces, and reduces processing temperature, subtracts Few degradation rate, is conducive to processing；Additionally the hexanediol segment containing side chain surpasses the structure rule of flexible polyester fiber POY silk to porous Whole property does not has big destruction, maintains the premium properties of polyester fiber.Spinning process of the present invention uses spinneret orifice ellipse row The spinneret of row, beneficially uniform, sufficiently cool in spinning process of fiber, performance and structure between fiber differ relatively Little, improve dyeing uniformity and the mechanical property of fiber.
For reaching above-mentioned purpose, the technical solution used in the present invention is:
A kind of porous surpasses flexible polyester fiber POY silk, and the material that described porous surpasses flexible polyester fiber POY silk is poly-for modification Ester, described modified poly ester is made up of p-phthalic acid segment, ethylene glycol segment and the hexanediol segment containing side chain, described containing side chain Hexanediol segment refer on the non-end group carbon that side chain is positioned in hexanediol segment and side chain is for containing 5-10 carbon atom The hexanediol segment of linear carbon chain；
It is 0.3～2.0dtex that described porous surpasses the filament number of flexible polyester fiber POY silk, initial modulus≤60cN/ Dtex, fracture strength >=2.6cN/dtex, elongation at break is 100.0 ± 10.0%；Described porous surpasses flexible polyester fiber POY Silk is at temperature is 80～130 DEG C, and the spatial joint clearance of fibrous inside molecule interchain increases 10～30v/v%, at 260～290 DEG C Under, melt viscosity declines 10～20%；Described porous surpasses line density deviation ratio≤0.2% of flexible polyester fiber POY silk, fracture Intensity CV value≤2.5%, extension at break CV value≤5.0%.
Present invention also offers a kind of porous and surpass the preparation method of flexible polyester fiber POY silk, modified poly ester is used many Hole spinneret spinning prepares porous and surpasses flexible polyester fiber POY silk；On described porous spinneret, the arrangement mode of spinneret orifice is ellipse Circular arrangement, described oval shaped arrangements refers to that the hole of spinneret orifice is centrally located on concentration ellipse, and described concentration ellipse is that series is ellipse Circle, the major axis conllinear of all ellipses, and short axle conllinear；
Described porous surpasses the preparation method of flexible polyester fiber POY silk: modified poly ester obtains modified poly ester through pelletizing and cuts Sheet, Modified polyester chips is through measuring, extrude, cool down, oil and wind prepared modified poly ester POY silk；
The preparation process of described modified poly ester is:
(1) preparation of p-phthalic acid binary alcohol esters；
After p-phthalic acid is made into slurry with the hexanediol containing side chain, under the catalytic action of concentrated sulphuric acid, it is esterified Reaction obtains p-phthalic acid binary alcohol esters；The described hexanediol containing side chain refer to one that side chain is positioned in hexanediol segment non- On end group carbon and dihydroxylic alcohols that side chain is the linear carbon chain containing 5-10 carbon atom；
For the hexanediol containing side chain, its side chain is alkyl, is electron withdraw group, in the existence of side chain, makes strand Spatial volume increases, and solvation diminishes, and in dihydroxylic alcohols, proton is difficult to dissociation so that the hexanediol containing side chain and terephthaldehyde The reactivity of acid is less than ethylene glycol, according to the mixing of same ethylene glycol and terephthaldehyde's acid reaction, can cause containing side chain oneself two Alcohol reaction is imperfect, thus the ratio that the hexanediol that impact is containing side chain is in polyester macromolecule, and then affect the performance of polyester.This Invention uses and first with p-phthalic acid, the hexanediol containing side chain is carried out esterification under the catalytic action of sulphuric acid, and its product exists Ethylene glycol and p phthalic acid esterification add after terminating, it is ensured that the stability of the hexanediol proportioning containing side chain；
(2) preparation of ethylene glycol terephthalate；
After p-phthalic acid and ethylene glycol are made into slurry, carry out esterification, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester；
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), stir Mix mixing, under the effect of catalyst and stabilizer, under conditions of negative pressure, carry out successively the coarse vacuum stage polycondensation reaction and The polycondensation reaction of high vacuum stage of Fig, prepares modified poly ester.
As preferred technical scheme:
A kind of porous as above surpasses the preparation method of flexible polyester fiber POY silk, the concrete system of described modified poly ester Standby step is:
(1) preparation of p-phthalic acid binary alcohol esters；
P-phthalic acid is made into slurry with the hexanediol containing side chain, under the catalytic action of concentrated sulphuric acid, carries out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is normal pressure～0.3MPa, and temperature is 180～240 DEG C, works as ester Change reaction in water quantity of distillate reach theoretical value more than 90% time be esterification terminal, obtain p-phthalic acid dihydroxylic alcohols Ester；
(2) preparation of ethylene glycol terephthalate；
After p-phthalic acid and ethylene glycol are made into slurry, carrying out esterification, esterification is pressurizeed in nitrogen atmosphere Reaction, moulding pressure is normal pressure～0.3MPa, and temperature is 250～260 DEG C, when the water quantity of distillate in esterification reaches theoretical value More than 90% time be esterification terminal, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester；
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), stir Mixing mixing 15-20 minute, under the effect of catalyst and stabilizer, the polycondensation starting the coarse vacuum stage under conditions of negative pressure is anti- Should, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, and temperature controls at 260～270 DEG C, and the response time is 30～50 minutes；Then proceed to evacuation, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure and be less than 100Pa, reaction temperature controls at 275～280 DEG C, response time 50～90 minutes, prepares modified poly ester；
Described porous surpasses the main spinning technology parameter of flexible polyester fiber POY silk:
The temperature of extrusion: 280～290 DEG C；
The pathogenic wind-warm of cooling: 20～25 DEG C；
The speed of winding: 2500～3000m/min.
A kind of porous as above surpasses the preparation method of flexible polyester fiber POY silk, in step (1), and p-phthalic acid It is 1:1.3-1.5 with the mol ratio of the hexanediol containing side chain；Concentrated sulphuric acid addition is the 0.3-0.5% of p-phthalic acid weight； The concentration of described concentrated sulphuric acid is 50-60wt%；
In step (2), p-phthalic acid is 1:1.2～2.0 with the mol ratio of ethylene glycol；
In step (3), described p-phthalic acid binary alcohol esters is 2 with the Mole percent ratio of ethylene glycol terephthalate ～5%；Described catalyst is antimony oxide, antimony glycol or antimony acetate, and catalyst charge is p-phthalic acid gross weight 0.01%～0.05%；Described stabilizer is triphenyl phosphate, trimethyl phosphate or NSC 6513, stabilizer addition For described p-phthalic acid gross weight 0.01%～0.05%；
The number-average molecular weight of described modified poly ester is 15000～30000.
A kind of porous as above surpasses the preparation method of flexible polyester fiber POY silk, and the described hexanediol containing side chain is 2-amyl group-1,6 hexanediol, 2-hexyl-1,6 hexanediol, 2-heptyl-1,6 hexanediol, 2-octyl group-1,6 hexanediol, 2-nonyl-1, More than one in 6 hexanediol or 2-decyl-1,6 hexanediol.
A kind of porous as above surpasses the preparation method of flexible polyester fiber POY silk, and being arranged as of described spinneret orifice is long Axle and/or short axial symmetry.
A kind of porous as above surpasses the preparation method of flexible polyester fiber POY silk, oval major axis and minor axis length Ratio be 1.3～1.8；The spacing of adjacent spinneret orifice adds 1.5mm more than or equal to the guide hole diameter of spinneret orifice.When spinneret Effective area phase is simultaneously as the girth of ellipse is more than circular girth, and the number of plies of spinneret orifice oval shaped arrangements is less than circle The number of plies of arrangement, the hole count of spinneret orifice oval shaped arrangements is more than the hole count of circular arrangement, and therefore, spinneret orifice oval shaped arrangements is favourable In the cooling of ring blowing, improving the cooling effectiveness of ring blowing, the fibre property of preparation is the most more excellent.Major axis and minor axis length Ratio is closer to 1, and ellipse is more similar to circle, and the difference of cooling effectiveness and cooling effect is little；Major axis and the ratio of minor axis length When value is 1.3, cooling effect significantly improves, and individual pen hole count increases by 16% accordingly；When the ratio of major axis and minor axis length is 1.8, Cooling effect improves relatively big, and individual pen hole count increases by 33% accordingly, and in the case of identical hole count, the oval shaped arrangements of the present invention is than routine The number of turns of concentric arrays reduces, it is easy to cooling wind is saturating, makes the fiber cooling condition of Internal and external cycle evenly；Major axis and short axial length When the ratio of degree is more than 1.8, ellipse is partial to form flat shape, is difficult to punching, and cooling no longer raises.Cause This, the oval major axis of series is 1.3～1.8 with the ratio of minor axis length, it is possible to reach higher cooling effectiveness and the coldest But effect.
A kind of porous as above surpasses the preparation method of flexible polyester fiber POY silk, and described spinneret is circular spray webbing Plate or elliptical spinneret plate；The difference of the long axis length that the diameter of described circular jetting filament plate is maximum with series ellipse is more than 10mm, The difference of the long axis length that described elliptical spinneret plate is maximum with series ellipse is more than 10mm.
A kind of porous as above surpasses the preparation method of flexible polyester fiber POY silk, the guide hole diameter of described spinneret orifice It is 1.5～2.5mm；The spray webbing hole count of described spinneret is more than or equal to 192.
A kind of porous as above surpasses the preparation method of flexible polyester fiber POY silk, the spinneret orifice of described spinneret Shape of cross section be circle, square, rhombus, yi word pattern, triangular form, trilobal cross, hollow type or platypelloid type.
The principle of the present invention is:
For unbranched polyester fiber, its molecular chain structure is the linear macromolecule containing benzene ring structure, on strand Functional group's marshalling, regularity is good, flexible poor；When temperature raises, its free volume increments is little, and these characteristics hinder Hinder dyestuff to enter inside polyester fiber, thus dyeability is poor.
The raw material of the polyester fiber of the present invention is modified poly ester, the hexanediol containing side chain contained in modified poly ester macromole Segment, when temperature is higher than vitrification point, side chain, prior to backbone motion, makes the increasing degree of free volume be far longer than without propping up The characteristic of the polyester macromolecule chain of chain, the increase of free volume improves molecule and enters the degree within polyester, is modified The free volume of polyester fiber prepared by polyester is far longer than unbranched polyester fiber at equal temperature, increases the diffusion of dyestuff Degree, improves the dyeability of polyester fiber.Meanwhile, polyester fiber prepared by modified poly ester advantageously reduces melt viscosity, has It is beneficial to improve its processing characteristics.The introducing of the hexanediol segment containing side chain does not has big destruction to polyester fiber structures regularity, Maintain the premium properties of polyester fiber.
When the effective area phase of spinneret is simultaneously as the girth of ellipse is more than circular girth, and spinneret orifice is oval The number of plies of arrangement is less than the number of plies of circular arrangement, and the hole count of spinneret orifice oval shaped arrangements, more than the hole count of circular arrangement, uses spray The spinneret of silk hole oval shaped arrangements enables to fiber quickly, uniformly cool down, and between fiber, the difference of structure and performance is less, Be conducive to improving even dyeing rate and the performance of fiber of fiber.
Beneficial effect:
1) on the spinneret of the present invention, the arrangement mode of spinneret orifice is oval shaped arrangements, and the effective area of spinneret is identical Time, the number of plies of spinneret orifice oval shaped arrangements is easier to blow through dynamic analysis of spinning, dynamic analysis of spinning less than the number of plies of circular arrangement, ring blowing Cooling effect more preferable, the fibre property of preparation is the most more excellent.
2) on the spinneret of the present invention, the arrangement mode of spinneret orifice is oval shaped arrangements, and the effective area of spinneret is identical Time, the hole count of spinneret orifice oval shaped arrangements is more than the hole count of circular arrangement, and oval shaped arrangements is capable of cooling down greatly, Significantly improve cooling effectiveness.
3) porous that the present invention prepares surpasses the material of flexible polyester fiber POY silk is modified poly ester, modified poly ester macromole In the hexanediol segment containing side chain that contains, when temperature is higher than vitrification point, side chain, prior to backbone motion, makes free volume Increasing degree be far longer than the characteristic of unbranched polyester macromolecule chain, the increase of free volume improves molecule and enters Degree within polyester, is added the free volume diffusion with increase dyestuff of polyester fiber, improves polyester by side chain The dyeability of fiber.
4) porous that the present invention prepares surpasses flexible polyester fiber POY silk, and the increase of polyester fiber free volume is conducive to fall Low melt viscosity, is conducive to improving its processing characteristics.
5) porous that the present invention prepares surpasses flexible polyester fiber POY silk, the hexanediol segment containing side chain introduce to poly- The structural regularity of ester fiber does not has big destruction, maintains the premium properties of polyester fiber.
6) porous that the present invention prepares surpasses flexible polyester fiber POY silk dyeability and good mechanical performance, initial modulus ≤ 60cN/dtex, porous surpasses line density deviation ratio≤0.2% of flexible polyester fiber POY silk, fracture strength CV value≤2.5%, Extension at break CV value≤5.0%.
Accompanying drawing explanation
Fig. 1 is the oval shaped arrangements figure of 374 spinneret orifices, and the aperture of spinneret orifice is 2.0mm, transverse and the length of short axle Degree ratio is 1.3；
Fig. 2 is the circular arrangement figure of 370 spinneret orifices, and the aperture of spinneret orifice is 2.0mm；
Fig. 3 is the oval shaped arrangements figure of 382 spinneret orifices, and the aperture of spinneret orifice is 2.0mm, transverse and the length of short axle Degree ratio is 1.6.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate this Bright rather than limit the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, art technology The present invention can be made various changes or modifications by personnel, and these equivalent form of values fall within the application appended claims equally and limited Fixed scope.
Embodiment 1
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.3 and 2-amyl group-1,6 hexanediol are made into slurry and add in reactor, Concentration is 50wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.3% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is normal pressure, and temperature is 180 DEG C, when the water in esterification distillates Amount reach theoretical value 90% time be esterification terminal, obtain p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.2 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is normal pressure, and temperature is 250 DEG C, when the water in esterification distillates Amount reach theoretical value 90% time be esterification terminal, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 2% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 15 minutes, is adding The catalytic antimony trioxide of 0.01% that amount is p-phthalic acid weight and addition is p-phthalic acid weight 0.01% Stabilizer triphenyl phosphate effect under, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure Steadily being evacuated to absolute pressure by normal pressure is 500Pa, and temperature controls at 260 DEG C, and the response time is 30 minutes；Then proceed to take out very Sky, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 100Pa, and reaction temperature controls 275 DEG C, in 50 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 15000, by p-phthalic acid segment, ethylene glycol segment and 2-penta Base-1,6 hexanediol segment compositions, 2-amyl group-1,6 hexanediol segments are 2% with the Mole percent ratio of ethylene glycol segment.
Embodiment 2
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.38 and 2-hexyl-1,6 hexanediol are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.32% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.13MPa, and temperature is 181 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 91% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.3 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.12MPa, and temperature is 251 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 91% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 2.1% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 16 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.011% are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.02%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and temperature controls at 262 DEG C, and the response time is 31 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 99Pa, and reaction temperature controls at 276 DEG C, In 51 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 16000, own by p-phthalic acid segment, ethylene glycol segment and 2- Base-1,6 hexanediol segment compositions, 2-hexyl-1,6 hexanediol segments are 2.1% with the Mole percent ratio of ethylene glycol segment.
Embodiment 3
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.33 and 2-heptyl-1,6 hexanediol are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.33% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.12MPa, and temperature is 183 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.31 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.31MPa, and temperature is 252 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 2.2% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 16 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.03% are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.02%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 498Pa by normal pressure, and temperature controls at 263 DEG C, and the response time is 32 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 80Pa, and reaction temperature controls at 277 DEG C, In 57 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester prepared is 15900, by p-phthalic acid segment, ethylene glycol segment and 2-heptan Base-1,6 hexanediol segment compositions, 2-heptyl-1,6 hexanediol segments are 2.2% with the Mole percent ratio of ethylene glycol segment.
Embodiment 4
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.34 and 2-octyl group-1,6 hexanediol are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.34% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.13MPa, and temperature is 184 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 93% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.32 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.33MPa, and temperature is 253 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 93% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 2.3% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 17 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.033% are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.023%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank It is 497Pa that section pressure is steadily evacuated to absolute pressure by normal pressure, and temperature controls at 264 DEG C, and the response time is 33 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 80Pa, and reaction temperature controls 278 DEG C, in 58 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 15800, pungent by p-phthalic acid segment, ethylene glycol segment and 2- Base-1,6 hexanediol segment compositions, 2-octyl group-1,6 hexanediol segments are 2.3% with the Mole percent ratio of ethylene glycol segment.
Embodiment 5
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.35 and 2-nonyl-1,6 hexanediol are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.36% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.14MPa, and temperature is 185 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 93.2% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.33 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.14MPa, and temperature is 254 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 93.2% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 2.4% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 17 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.034% are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.024%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 34 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 70Pa, and reaction temperature controls 277 DEG C, in 59 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 15900, by p-phthalic acid segment, ethylene glycol segment and 2-nonyl Base-1,6 hexanediol segment compositions, 2-nonyl-1,6 hexanediol segments are 2.4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 6
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.36 and 2-decyl-1,6 hexanediol are made into slurry and add in reactor, Concentration is 50wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.37% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.15MPa, and temperature is 186 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 93.3% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.34 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.15MPa, and temperature is 255 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 93.3% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 2.5% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.035% are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.025%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and temperature controls at 266 DEG C, and the response time is 35 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 70Pa, and reaction temperature controls 278 DEG C, in 60 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester prepared is 16000, by p-phthalic acid segment, ethylene glycol segment and 2-last of the ten Heavenly stems Base-1,6 hexanediol segment compositions, 2-decyl-1,6 hexanediol segments are 2.5% with the Mole percent ratio of ethylene glycol segment.
Embodiment 7
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.37 and 2-amyl group-1,6 hexanediol are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.38% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.16MPa, and temperature is 187 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 93.4% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.36 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.16MPa, and temperature is 256 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 93.4% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 2.6% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 19 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.036% are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.025%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and temperature controls at 267 DEG C, and the response time is 36 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 70Pa, and reaction temperature controls 278 DEG C, in 61 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 16000, by p-phthalic acid segment, ethylene glycol segment and 2-penta Base-1,6 hexanediol segment compositions, 2-amyl group-1,6 hexanediol segments are 2.6% with the Mole percent ratio of ethylene glycol segment.
Embodiment 8
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.38 and 2-hexyl-1,6 hexanediol are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.39% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.17MPa, and temperature is 188 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 93.5% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.37 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.17MPa, and temperature is 257 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 93.5% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 2.7% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 19 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.036% are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.025%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and temperature controls at 267 DEG C, and the response time is 36 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 60Pa, and reaction temperature controls 278 DEG C, in 61 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 17000, own by p-phthalic acid segment, ethylene glycol segment and 2- Base-1,6 hexanediol segment compositions, 2-hexyl-1,6 hexanediol segments are 2.7% with the Mole percent ratio of ethylene glycol segment.
Embodiment 9
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.39 and 2-heptyl-1,6 hexanediol are made into slurry and add in reactor, Concentration is 50wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.4% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.17MPa, and temperature is 188 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 93.5% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.37 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.17MPa, and temperature is 257 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 93.5% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 2.8% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 16 minutes, is adding Enter the catalyst glycol antimony of amount is p-phthalic acid weight 0.04% and addition is p-phthalic acid weight 0.026% Stabilizer trimethyl phosphate effect under, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure Steadily be evacuated to absolute pressure 497Pa by normal pressure, temperature controls at 268 DEG C, and the response time is 38 minutes；Then proceed to evacuation, Carrying out the polycondensation reaction of high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 50Pa, and reaction temperature controls at 279 DEG C, instead Between Ying Shi 62 minutes, prepare modified poly ester.
The number-average molecular weight of modified poly ester prepared is 18000, by p-phthalic acid segment, ethylene glycol segment and 2-heptan Base-1,6 hexanediol segment compositions, 2-heptyl-1,6 hexanediol segments are 2.8% with the Mole percent ratio of ethylene glycol segment.
Embodiment 10
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.4 and 2-octyl group-1,6 hexanediol are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.4% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.17MPa, and temperature is 188 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 93.5% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.38 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.18MPa, and temperature is 257.8 DEG C, when in esterification Water quantity of distillate reach theoretical value 93.6% time be esterification terminal, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 3% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 17 minutes, is adding The catalyst glycol antimony of 0.03% that amount is p-phthalic acid weight and addition is p-phthalic acid weight 0.027% Under the effect of stabilizer trimethyl phosphate, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure by Normal pressure is steadily evacuated to absolute pressure 498Pa, and temperature controls at 269 DEG C, and the response time is 39 minutes；Then proceed to evacuation, enter The polycondensation reaction of row high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 50Pa, and reaction temperature controls at 278 DEG C, reaction 64 minutes time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 19000, pungent by p-phthalic acid segment, ethylene glycol segment and 2- Base-1,6 hexanediol segment compositions, 2-octyl group-1,6 hexanediol segments are 3% with the Mole percent ratio of ethylene glycol segment.
Embodiment 11
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.4 and 2-nonyl-1,6 hexanediol are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.4% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.18MPa, and temperature is 189 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 93.6% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.39 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.19MPa, and temperature is 258.8 DEG C, when in esterification Water quantity of distillate reach theoretical value 94% time be esterification terminal, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, is adding The catalyst glycol antimony of 0.04% that amount is p-phthalic acid weight and addition is p-phthalic acid weight 0.03% Under the effect of stabilizer trimethyl phosphate, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure by Normal pressure is steadily evacuated to absolute pressure 497Pa, and temperature controls at 260 DEG C, and the response time is 40 minutes；Then proceed to evacuation, enter The polycondensation reaction of row high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 40Pa, and reaction temperature controls at 277 DEG C, reaction 63 minutes time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 20000, by p-phthalic acid segment, ethylene glycol segment and 2-nonyl Base-1,6 hexanediol segment compositions, 2-nonyl-1,6 hexanediol segments are 4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 12
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.4 and 2-nonyl-1,6 hexanediol are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.4% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.2MPa, and temperature is 200 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 94% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.6 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.2MPa, and temperature is 256 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 94% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.5% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, is adding Enter the catalyst acetic acid antimony of amount is p-phthalic acid weight 0.038% and addition is p-phthalic acid weight 0.03% Under the effect of stabilizer NSC 6513, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, this staged pressure Steadily be evacuated to absolute pressure 497Pa by normal pressure, temperature controls at 265 DEG C, and the response time is 42 minutes；Then proceed to evacuation, Carrying out the polycondensation reaction of high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 40Pa, and reaction temperature controls at 277 DEG C, instead Between Ying Shi 70 minutes, prepare modified poly ester.
The number-average molecular weight of modified poly ester prepared is 26000, by p-phthalic acid segment, ethylene glycol segment and 2-last of the ten Heavenly stems Base-1,6 hexanediol segment compositions, 2-decyl-1,6 hexanediol segments are 4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 13
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.5 and 2-decyl-1,6 hexanediol are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.5% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.3MPa, and temperature is 240 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:2.0 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.3MPa, and temperature is 260 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 5% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 20 minutes, is adding The catalyst acetic acid antimony of 0.05% that amount is p-phthalic acid weight and addition is p-phthalic acid weight 0.05% steady Determine under the effect of agent NSC 6513, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure by It is 450Pa that normal pressure is steadily evacuated to absolute pressure, and temperature controls at 270 DEG C, and the response time is 50 minutes；Then proceed to evacuation, Carrying out the polycondensation reaction of high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 30Pa, and reaction temperature controls at 280 DEG C, instead Between Ying Shi 90 minutes, prepare modified poly ester.
The number-average molecular weight of modified poly ester prepared is 30000, by p-phthalic acid segment, ethylene glycol segment and 2-last of the ten Heavenly stems Base-1,6 hexanediol segment compositions, 2-decyl-1,6 hexanediol segments are 5% with the Mole percent ratio of ethylene glycol segment.
Embodiment 14
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.47 and 2-nonyl-1,6 hexanediol are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.47% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 220 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.8 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.27MPa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, is adding The catalyst glycol antimony of 0.04% that amount is p-phthalic acid weight and addition is p-phthalic acid weight 0.04% Under the effect of stabilizer trimethyl phosphate, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure by Normal pressure is steadily evacuated to absolute pressure 460Pa, and temperature controls at 263 DEG C, and the response time is 47 minutes；Then proceed to evacuation, enter The polycondensation reaction of row high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 278 DEG C, during reaction Between 85 minutes, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 28000, by p-phthalic acid segment, ethylene glycol segment and 2-nonyl Base-1,6 hexanediol segment compositions, 2-nonyl-1,6 hexanediol segments are 4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 15
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.46 and 2-octyl group-1,6 hexanediol are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.49% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 233 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.8 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 259 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.5% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 19 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.044% are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.046%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and temperature controls at 269 DEG C, and the response time is 48 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 279 DEG C, In 87 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 29000, pungent by p-phthalic acid segment, ethylene glycol segment and 2- Base-1,6 hexanediol segment compositions, 2-octyl group-1,6 hexanediol segments are 4.5% with the Mole percent ratio of ethylene glycol segment.
Embodiment 16
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.49 and 2-heptyl-1,6 hexanediol are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.48% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 230 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.8 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.7% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 19 minutes, is adding The catalyst glycol antimony and the addition that enter amount is p-phthalic acid weight 0.048% are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.047%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 460Pa by normal pressure, and temperature controls at 267 DEG C, and the response time is 48 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 279 DEG C, In 83 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester prepared is 27000, by p-phthalic acid segment, ethylene glycol segment and 2-heptan Base-1,6 hexanediol segment compositions, 2-heptyl-1,6 hexanediol segments are 4.7% with the Mole percent ratio of ethylene glycol segment.
Embodiment 17
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.467 and 2-hexyl-1,6 hexanediol are made into slurry and add in reactor, Being 60wt% in concentration, addition is under the catalytic action of the concentrated sulphuric acid of the 0.47% of p-phthalic acid weight, carries out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.27MPa, and temperature is 236 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.89 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 258 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.3% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.04% are p-phthalic acid weight Under the effect of the stabilizer NSC 6513 of 0.041%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and temperature controls at 268 DEG C, and the response time is 48 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls 278 DEG C, in 85 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 29000, own by p-phthalic acid segment, ethylene glycol segment and 2- Base-1,6 hexanediol segment compositions, 2-hexyl-1,6 hexanediol segments are 4.3% with the Mole percent ratio of ethylene glycol segment.
Embodiment 18
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.48 and 2-amyl group-1,6 hexanediol are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.46% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 230 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.88 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 256 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.7% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.047% are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.047%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 480Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 47 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 279 DEG C, In 85 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 28000, by p-phthalic acid segment, ethylene glycol segment and 2-penta Base-1,6 hexanediol segment compositions, 2-amyl group-1,6 hexanediol segments are 4.7% with the Mole percent ratio of ethylene glycol segment.
Embodiment 19
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.46 and 2-decyl-1,6 hexanediol are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.47% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 238 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.9 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 259 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches more than the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.7% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 19 minutes, is adding Enter the catalyst acetic acid antimony of amount is p-phthalic acid weight 0.046% and addition is p-phthalic acid weight 0.048% Stabilizer NSC 6513 effect under, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this stage press It is 446Pa that power is steadily evacuated to absolute pressure by normal pressure, and temperature controls at 267 DEG C, and the response time is 49 minutes；Then proceed to take out very Sky, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 40Pa, and reaction temperature controls at 278 DEG C, In 87 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester prepared is 29000, by p-phthalic acid segment, ethylene glycol segment and 2-last of the ten Heavenly stems Base-1,6 hexanediol segment compositions, 2-decyl-1,6 hexanediol segments are 4.7% with the Mole percent ratio of ethylene glycol segment.
Embodiment 20
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.46 and 2-nonyl-1,6 hexanediol are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.46% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.26MPa, and temperature is 221 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.89 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.25MPa, and temperature is 259 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.1% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, is adding The catalyst glycol antimony and the addition that enter amount is p-phthalic acid weight 0.041% are p-phthalic acid weight Under the effect of the stabilizer trimethyl phosphate of 0.042%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 460Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 47 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 278 DEG C, In 85 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 28000, by p-phthalic acid segment, ethylene glycol segment and 2-nonyl Base-1,6 hexanediol segment compositions, 2-nonyl-1,6 hexanediol segments are 4.1% with the Mole percent ratio of ethylene glycol segment.
Embodiment 21
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.43 and 2-octyl group-1,6 hexanediol are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.47% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.27MPa, and temperature is 235 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.78 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.26MPa, and temperature is 255 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.3% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 17 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.043% are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.049%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and temperature controls at 268 DEG C, and the response time is 46 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 275 DEG C, In 85 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 28000, pungent by p-phthalic acid segment, ethylene glycol segment and 2- Base-1,6 hexanediol segment compositions, 2-octyl group-1,6 hexanediol segments are 4.3% with the Mole percent ratio of ethylene glycol segment.
Embodiment 22
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.43 and 2-heptyl-1,6 hexanediol are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.45% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.29MPa, and temperature is 235 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.87 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.27MPa, and temperature is 255 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.6% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, is adding Enter the catalyst glycol antimony of amount is p-phthalic acid weight 0.047% and addition is p-phthalic acid weight 0.04% Stabilizer triphenyl phosphate effect under, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure Steadily be evacuated to absolute pressure 470Pa by normal pressure, temperature controls at 268 DEG C, and the response time is 45 minutes；Then proceed to evacuation, Carrying out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 40Pa, reaction temperature controls at 279 DEG C, reaction 83 minutes time, prepare modified poly ester.
The number-average molecular weight of modified poly ester prepared is 29000, by p-phthalic acid segment, ethylene glycol segment and 2-heptan Base-1,6 hexanediol segment compositions, 2-heptyl-1,6 hexanediol segments are 4.6% with the Mole percent ratio of ethylene glycol segment.
Embodiment 23
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.457 and 2-hexyl-1,6 hexanediol are made into slurry and add in reactor, Being 55% in concentration, addition is under the catalytic action of the concentrated sulphuric acid of the 0.46% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 239 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.81 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.27MPa, and temperature is 255 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.41% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 19 minutes, Addition is the catalytic antimony trioxide of the 0.042% of p-phthalic acid weight and addition is p-phthalic acid weight Under the effect of the stabilizer NSC 6513 of 0.048%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 45 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50Pa, and reaction temperature controls 275 DEG C, in 85 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 28000, own by p-phthalic acid segment, ethylene glycol segment and 2- Base-1,6 hexanediol segment compositions, 2-hexyl-1,6 hexanediol segments are 4.41% with the Mole percent ratio of ethylene glycol segment.
Embodiment 24
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.47 and 2-amyl group-1,6 hexanediol are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.48% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.27MPa, and temperature is 245 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.81 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.27MPa, and temperature is 259 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.67% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 19 minutes, Addition is the catalytic antimony trioxide of the 0.041% of p-phthalic acid weight and addition is p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.042%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 485Pa by normal pressure, and temperature controls at 268 DEG C, and the response time is 46 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50Pa, and reaction temperature controls at 275 DEG C, In 89 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 29000, by p-phthalic acid segment, ethylene glycol segment and 2-penta Base-1,6 hexanediol segment compositions, 2-amyl group-1,6 hexanediol segments are 4.67% with the Mole percent ratio of ethylene glycol segment.
Embodiment 25
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
Mixed by p-phthalic acid that mol ratio is 1:1.45 and 2-hexyl-1,6 hexanediol and 2-amyl group-1,6 hexanediol Compound is made into slurry and adds in reactor, wherein 2-hexyl-1,6 hexanediol and 2-amyl group-1, and the mol ratio of 6 hexanediol is 3:1, Being 55% in concentration, addition is under the catalytic action of the concentrated sulphuric acid of the 0.49% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.26MPa, and temperature is 236 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.8 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.4% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.042% are p-phthalic acid weight Under the effect of the stabilizer NSC 6513 of 0.047%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 49 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50Pa, and reaction temperature controls 278 DEG C, in 88 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester prepared is 29000, by p-phthalic acid segment, ethylene glycol segment, 2-hexyl- 1,6 hexanediol segment and 2-amyl group-1,6 hexanediol segments compositions, 2-hexyl-1,6 hexanediol segments and 2-amyl group-1,6 oneself two The summation of alcohol segment is 4.4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 26
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By 2-octyl group-1,6 hexanediol of p-phthalic acid sum that mol ratio is 1:1.45 and 2-amyl group-1,6 hexanediol Mixture is made into slurry and adds in reactor, wherein 2-octyl group-1,6 hexanediol and 2-amyl group-1, and the mol ratio of 6 hexanediol is 3: 2, it is 60% in concentration, addition is under the catalytic action of the concentrated sulphuric acid of the 0.45% of p-phthalic acid weight, carries out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 239 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.84 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.29MPa, and temperature is 255 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.6% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.0423% are p-phthalic acid weight Under the effect of the stabilizer NSC 6513 of 0.045%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 45 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50Pa, and reaction temperature controls 278 DEG C, in 85 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester prepared is 28000, by p-phthalic acid segment, ethylene glycol segment, 2-octyl group- 1,6 hexanediol segment and 2-amyl group-1,6 hexanediol segments composition, 2-octyl group-1,6 hexanediol segments and 2-amyl group-1,6 oneself two Alcohol segment is 4.6% with the Mole percent ratio of ethylene glycol segment.
Embodiment 27
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
Mixed by p-phthalic acid that mol ratio is 1:1.45 and 2-hexyl-1,6 hexanediol and 2-amyl group-1,6 hexanediol Compound is made into slurry and adds in reactor, wherein 2-hexyl-1,6 hexanediol and 2-amyl group-1, and the mol ratio of 6 hexanediol is 3:1, Being 55% in concentration, addition is under the catalytic action of the concentrated sulphuric acid of the 0.49% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.26MPa, and temperature is 236 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 96% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.8 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.4% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.042% are p-phthalic acid weight Under the effect of the stabilizer NSC 6513 of 0.047%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 49 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50Pa, and reaction temperature controls 278 DEG C, in 88 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester prepared is 29000, by p-phthalic acid segment, ethylene glycol segment, 2-hexyl- 1,6 hexanediol segment and 2-amyl group-Isosorbide-5-Nitrae butanediol segment composition, 2-hexyl-1,6 hexanediol segments and 2-amyl group-Isosorbide-5-Nitrae fourth two The summation of alcohol segment is 4.4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 28
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.45 and 2-octyl group-1,6 hexanediol, 2-amyl group-1,6 hexanediol and 2-oneself Base-1, the mixture of 6 hexanediol is made into slurry and adds in reactor, wherein 2-octyl group-1,3 propylene glycol, 2-amyl group-Isosorbide-5-Nitrae fourth two Alcohol and 2-hexyl-1, the mol ratio of 6 hexanediol is 3:2:1, is 60% in concentration, and addition is p-phthalic acid weight Under the catalytic action of the concentrated sulphuric acid of 0.47%, carrying out esterification, esterification is compressive reaction in nitrogen atmosphere, moulding pressure For 0.29MPa, temperature is 235 DEG C, is esterification terminal when the water quantity of distillate in esterification reaches the 92% of theoretical value, Obtain p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.8 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.27MPa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.71% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, Addition is the catalytic antimony trioxide of the 0.04% of p-phthalic acid weight and addition is p-phthalic acid weight Under the effect of the stabilizer NSC 6513 of 0.041%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and temperature controls at 268 DEG C, and the response time is 49 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50Pa, and reaction temperature controls 277 DEG C, in 84 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 29000, by p-phthalic acid segment, ethylene glycol segment, band side chain Glycol segment composition, the most branched glycol segment is 2-octyl group-1,6 hexanediol segments, 2-amyl group-1,6 hexanediol chains Section and 2-hexyl-1,6 hexanediol segment compositions, branched glycol segment with the Mole percent ratio of ethylene glycol segment is 4.71%.
Embodiment 29
A kind of porous surpasses the preparation method of flexible polyester fiber POY silk, and porous surpasses flexible polyester fiber POY silk and uses porous Spinneret prepares, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to the center, hole of spinneret orifice Being positioned on concentration ellipse, concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear.
As it is shown in figure 1, the ratio of the major axis of ellipse and minor axis length is 1.3, the spacing of adjacent spinneret orifice is equal to spinneret orifice Guide hole diameter plus 1.5mm, spinneret is circular jetting filament plate, the long axial length that the diameter of circular jetting filament plate is maximum with series ellipse The difference of degree is 11mm, and a diameter of 2.0mm of guide hole of spinneret orifice, the spray webbing hole count of spinneret is 374, the spinneret orifice of spinneret Shape of cross section be circular.
Modified poly ester embodiment 1 prepared, obtains Modified polyester chips through pelletizing；Again through measuring, extrude, cooling down, on Oil and winding, prepare POY silk, and the temperature of the extrusion of POY silk is 285 DEG C, and the pathogenic wind-warm of cooling is 25 DEG C, and the speed of winding is 2500m/min；
It is 1.4dtex that the porous prepared surpasses the filament number of flexible polyester fiber POY silk, initial modulus 58cN/dtex, disconnected Resistance to spalling is 4.7cN/dtex, and elongation at break is 105.6%；Porous surpasses flexible polyester fiber POY silk at temperature is 80 DEG C, The spatial joint clearance of fibrous inside molecule interchain increases 15v/v%, and at 289 DEG C, melt viscosity declines 16%；Porous is super soft poly- The line density deviation ratio of ester fiber POY silk is 0.13%, and fracture strength CV value is 2.2%, and extension at break CV value is 3.9%.
Embodiment 30
A kind of porous surpasses the preparation method of flexible polyester fiber POY silk, and porous surpasses flexible polyester fiber POY silk and uses porous Spinneret prepares, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to the center, hole of spinneret orifice Being positioned on concentration ellipse, concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear.
As it is shown on figure 3, the ratio of the major axis of ellipse and minor axis length is 1.6, the spacing of adjacent spinneret orifice is equal to spinneret orifice Guide hole diameter plus 1.5mm, spinneret is circular jetting filament plate, the long axial length that the diameter of circular jetting filament plate is maximum with series ellipse The difference of degree is 11mm, and a diameter of 2.0mm of guide hole of spinneret orifice, the spray webbing hole count of spinneret is 382, the spinneret orifice of spinneret Shape of cross section be circular.
Modified poly ester embodiment 1 prepared, obtains Modified polyester chips through pelletizing；Again through measuring, extrude, cooling down, on Oil and winding, prepare POY silk, and the temperature of the extrusion of POY silk is 285 DEG C, and the pathogenic wind-warm of cooling is 25 DEG C, and the speed of winding is 2500m/min；
It is 1.7dtex that the porous prepared surpasses the filament number of flexible polyester fiber POY silk, initial modulus 60cN/dtex, disconnected Resistance to spalling is 5.6N/dtex, and elongation at break is 109.6%；Porous surpasses flexible polyester fiber POY silk at temperature is 80 DEG C, The spatial joint clearance of fibrous inside molecule interchain increases 15v/v%, and at 289 DEG C, melt viscosity declines 16%；Porous is super soft poly- The line density deviation ratio of ester fiber POY silk is 0.11%, and fracture strength CV value is 2.1%, and extension at break CV value is 3.6%.
Comparative example 1
A kind of porous surpasses the preparation method of flexible polyester fiber POY silk, and porous surpasses flexible polyester fiber POY silk and uses porous Spinneret prepares, and on spinneret, the arrangement mode of spinneret orifice is circular arrangement, and circular arrangement refers to that the hole of spinneret orifice is centrally located at On concentric circular, concentric circular is that series is circular.As in figure 2 it is shown, the spacing of adjacent spinneret orifice adds equal to the guide hole diameter of spinneret orifice 1.5mm, spinneret is circular jetting filament plate, and the difference of the diameter that the diameter of circular jetting filament plate is maximum with series circle is 11mm, spray The a diameter of 2.0mm of guide hole in silk hole, the spray webbing hole count of spinneret is 370, and the shape of cross section of the spinneret orifice of spinneret is circle Shape.
Modified poly ester embodiment 1 prepared, obtains Modified polyester chips through pelletizing；Again through measuring, extrude, cooling down, on Oil and winding, prepare POY silk, and the temperature of the extrusion of POY silk is 285 DEG C, and the pathogenic wind-warm of cooling is 25 DEG C, and the speed of winding is 2500m/min；
It is 1.0dtex that the porous prepared surpasses the filament number of flexible polyester fiber POY silk, initial modulus 55cN/dtex, disconnected Resistance to spalling is 2.7cN/dtex, and elongation at break is 108.6%；Porous surpasses flexible polyester fiber POY silk at temperature is 80 DEG C, The spatial joint clearance of fibrous inside molecule interchain increases 15v/v%, and at 289 DEG C, melt viscosity declines 16%；Porous is super soft poly- The line density deviation ratio of ester fiber POY silk is 0.23%, and fracture strength CV value is 2.7%, and extension at break CV value is 5.9%.
When contrasting it can be seen that the effective area of spinneret is identical with embodiment 29, (circular arrangement when spray webbing hole count is close Spray webbing hole count is 370, and oval shaped arrangements spray webbing hole count is 374), the spinneret orifice number of plies of oval shaped arrangements is 6, less than circular arrangement The spinneret orifice number of plies 8, cooling effect is more preferable；When contrasting it can be seen that the effective area of spinneret is identical with embodiment 30, oval The spinneret orifice number of plies of shape arrangement is 5, and less than the spinneret orifice number of plies 8 of circular arrangement, cooling effect is more preferable, the spray webbing of oval shaped arrangements The hole count 382 in hole is more than the hole count 370 of the spinneret orifice of circular arrangement, and cooling effectiveness is higher.The comparing result of fibre property shows, Fiber linear density deviation ratio, fracture strength CV value, extension at break CV value and the evenness fault that embodiment 29 and embodiment 30 prepare Rate CV value is less than comparative example 1, under the conditions of same process is described, uses the fibroid that the spinneret of spinneret orifice oval shaped arrangements prepares Can be better than using the spinneret of spinneret circular arrangement.
Embodiment 31～33
A kind of porous surpasses the preparation method of flexible polyester fiber POY silk, and porous surpasses flexible polyester fiber POY silk and uses porous Spinneret prepares, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to the center, hole of spinneret orifice Being positioned on concentration ellipse, concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear.
Be arranged as long axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.4, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.6mm, spinneret is circular jetting filament plate, and the diameter of circular jetting filament plate is oval with series The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 192 of spinneret, spray webbing The shape of cross section of the spinneret orifice of plate is square.
Modified poly ester, obtains Modified polyester chips through pelletizing；Again through measuring, extrude, cool down, oil and winding, prepare POY Silk, the temperature of the extrusion of POY silk is 280 DEG C, and the pathogenic wind-warm of cooling is 20 DEG C, and the speed of winding is 2500m/min；The porous prepared Porous surpass flexible polyester fiber POY silk at 80 DEG C the spatial joint clearance Magnification of fibrous inside molecule interchain, at 260 DEG C melt The mechanical performance data of viscosity rate of descent and fiber such as following table.
Embodiment 34～36
A kind of porous surpasses the preparation method of flexible polyester fiber POY silk, and porous surpasses flexible polyester fiber POY silk and uses porous Spinneret prepares, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to the center, hole of spinneret orifice Being positioned on concentration ellipse, concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear.
Be arranged as short axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.4, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.7mm, spinneret is elliptical spinneret plate, and elliptical spinneret plate and series ellipse are The difference of big long axis length is 12mm, a diameter of 1.8mm of guide hole of spinneret orifice, and the spray webbing hole count of spinneret is 200, spinneret The shape of cross section of spinneret orifice be rhombus.
Modified poly ester, obtains Modified polyester chips through pelletizing；Again through measuring, extrude, cool down, oil and winding, prepare POY Silk, the temperature of the extrusion of POY silk is 280 DEG C, and the pathogenic wind-warm of cooling is 20 DEG C, and the speed of winding is 2600m/min；The porous prepared Porous surpasses flexible polyester fiber POY silk spatial joint clearance Magnification of fibrous inside molecule interchain, molten at 290 DEG C at 130 DEG C The mechanical performance data such as following table of body viscosity rate of descent and fiber.
Embodiment 37～39
A kind of porous surpasses the preparation method of flexible polyester fiber POY silk, and porous surpasses flexible polyester fiber POY silk and uses porous Spinneret prepares, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to the center, hole of spinneret orifice Being positioned on concentration ellipse, concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear.
Be arranged as major axis and short axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.4, adjacent spray webbing The spacing in hole is equal to the guide hole diameter of spinneret orifice plus 1.8mm, and spinneret is circular jetting filament plate, the diameter of circular jetting filament plate be The difference of the oval maximum long axis length of row is 13mm, and a diameter of 2.5mm of guide hole of spinneret orifice, the spray webbing hole count of spinneret is 200, the shape of cross section of the spinneret orifice of spinneret is yi word pattern.
Modified poly ester, obtains Modified polyester chips through pelletizing；Again through measuring, extrude, cool down, oil and winding, prepare POY Silk, the temperature of the extrusion of POY silk is 286 DEG C, and the pathogenic wind-warm of cooling is 21 DEG C, and the speed of winding is 2700m/min；The porous prepared Porous surpasses flexible polyester fiber POY silk spatial joint clearance Magnification of fibrous inside molecule interchain, molten at 290 DEG C at 100 DEG C The mechanical performance data such as following table of body viscosity rate of descent and fiber.
Embodiment 40～42
A kind of porous surpasses the preparation method of flexible polyester fiber POY silk, and porous surpasses flexible polyester fiber POY silk and uses porous Spinneret prepares, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to the center, hole of spinneret orifice Being positioned on concentration ellipse, concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear.
Be arranged as major axis and short axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.7, adjacent spray webbing The spacing in hole adds 1.9mm equal to the guide hole diameter of spinneret orifice, and spinneret is elliptical spinneret plate, elliptical spinneret plate and series The difference of oval maximum long axis length is 14mm, a diameter of 1.5mm of guide hole of spinneret orifice, and the spray webbing hole count of spinneret is 210, The shape of cross section of the spinneret orifice of spinneret is triangular form.
Modified poly ester, obtains Modified polyester chips through pelletizing；Again through measuring, extrude, cool down, oil and winding, prepare POY Silk, the temperature of the extrusion of POY silk is 281 DEG C, and the pathogenic wind-warm of cooling is 24 DEG C, and the speed of winding is 3000m/min；The porous prepared Porous surpasses flexible polyester fiber POY silk spatial joint clearance Magnification of fibrous inside molecule interchain, molten at 289 DEG C at 110 DEG C The mechanical performance data such as following table of body viscosity rate of descent and fiber.
Embodiment 43～45
A kind of porous surpasses the preparation method of flexible polyester fiber POY silk, and porous surpasses flexible polyester fiber POY silk and uses porous Spinneret prepares, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to the center, hole of spinneret orifice Being positioned on concentration ellipse, concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear.
Be arranged as short axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.8, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.5mm, spinneret is circular jetting filament plate, and the diameter of circular jetting filament plate is oval with series The difference of maximum long axis length is 15mm, and a diameter of 1.8mm of guide hole of spinneret orifice, the spray webbing hole count of spinneret is 240, spray webbing The shape of cross section of the spinneret orifice of plate is trilobal cross.
Modified poly ester, obtains Modified polyester chips through pelletizing；Again through measuring, extrude, cool down, oil and winding, prepare POY Silk, the temperature of the extrusion of POY silk is 284 DEG C, and the pathogenic wind-warm of cooling is 23 DEG C, and the speed of winding is 2760m/min；The porous prepared Porous surpasses flexible polyester fiber POY silk spatial joint clearance Magnification of fibrous inside molecule interchain, molten at 270 DEG C at 120 DEG C The mechanical performance data such as following table of body viscosity rate of descent and fiber.
Embodiment 46～49
A kind of porous surpasses the preparation method of flexible polyester fiber POY silk, and porous surpasses flexible polyester fiber POY silk and uses porous Spinneret prepares, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to the center, hole of spinneret orifice Being positioned on concentration ellipse, concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear.
Be arranged as long axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.8, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.6mm, spinneret is circular jetting filament plate, and the diameter of circular jetting filament plate is oval with series The difference of maximum long axis length is 16mm, and a diameter of 2.2mm of guide hole of spinneret orifice, the spray webbing hole count of spinneret is 250, spray webbing The shape of cross section of the spinneret orifice of plate is hollow type.
Modified poly ester, obtains Modified polyester chips through pelletizing；Again through measuring, extrude, cool down, oil and winding, prepare POY Silk, the temperature of the extrusion of POY silk is 286 DEG C, and the pathogenic wind-warm of cooling is 25 DEG C, and the speed of winding is 2600m/min；The porous prepared Porous surpass flexible polyester fiber POY silk at 80 DEG C the spatial joint clearance Magnification of fibrous inside molecule interchain, at 275 DEG C melt The mechanical performance data of viscosity rate of descent and fiber such as following table.
Embodiment 50～53
A kind of porous surpasses the preparation method of flexible polyester fiber POY silk, and porous surpasses flexible polyester fiber POY silk and uses porous Spinneret prepares, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to the center, hole of spinneret orifice Being positioned on concentration ellipse, concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear.
Be arranged as short axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.8, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.8mm, spinneret is circular jetting filament plate, and the diameter of circular jetting filament plate is oval with series The difference of maximum long axis length is 15mm, and a diameter of 2.5mm of guide hole of spinneret orifice, the spray webbing hole count of spinneret is 260, spray webbing The shape of cross section of the spinneret orifice of plate is platypelloid type.
Modified poly ester, obtains Modified polyester chips through pelletizing；Again through measuring, extrude, cool down, oil and winding, prepare POY Silk, the temperature of the extrusion of POY silk is 285 DEG C, and the pathogenic wind-warm of cooling is 23 DEG C, and the speed of winding is 2550m/min；The porous prepared Porous surpass flexible polyester fiber POY silk at 80 DEG C the spatial joint clearance Magnification of fibrous inside molecule interchain, at 289 DEG C melt The mechanical performance data of viscosity rate of descent and fiber such as following table.
Embodiment 54～57
A kind of porous surpasses the preparation method of flexible polyester fiber POY silk, and porous surpasses flexible polyester fiber POY silk and uses porous Spinneret prepares, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to the center, hole of spinneret orifice Being positioned on concentration ellipse, concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear.
Be arranged as long axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.8, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.5mm, spinneret is circular jetting filament plate, and the diameter of circular jetting filament plate is oval with series The difference of maximum long axis length is 16mm, and a diameter of 1.8mm of guide hole of spinneret orifice, the spray webbing hole count of spinneret is 300, spray webbing The shape of cross section of the spinneret orifice of plate is hollow type.
Modified poly ester, obtains Modified polyester chips through pelletizing；Again through measuring, extrude, cool down, oil and winding, prepare POY Silk, the temperature of the extrusion of POY silk is 290 DEG C, and the pathogenic wind-warm of cooling is 25 DEG C, and the speed of winding is 2650m/min；The porous prepared Porous surpasses flexible polyester fiber POY silk spatial joint clearance Magnification of fibrous inside molecule interchain, molten at 260 DEG C at 130 DEG C The mechanical performance data such as following table of body viscosity rate of descent and fiber.
Embodiment 58
Porous surpasses the dyeing of flexible polyester fiber POY silk:
The porous porous preparing embodiment 29 surpasses flexible polyester fiber POY silk and dyes in High Temperature High Pressure machine, tool Concrete conditions in the establishment of a specific crime is: before dyeing, porous surpass flexible polyester fiber POY silk nonionic surfactant 60 DEG C process 30 minutes, so In rear addition dyeing liquor, the disperse dyes consumption in dyeing liquor is 2.0% (o.w.f)；Dispersant NNO, the concentration of dispersant NNO 1.2g/L；PH value is 5, and bath raio is 1:50, enters dye, then heat to 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C and 130 at 60 DEG C DEG C each constant temperature dyeing 1h.
Use identical dyeing condition that general fibre is dyeed.Porous porous after dyed surpasses flexible polyester fiber The dye uptake of POY silk obtains by the following method:
Dye uptake uses residual liquid colorimetry to determine, draws appropriate dyeing stock solution and dyeing residual liquid, adds N, N-2 first Base Methanamide (DMF) and distilled water, DMF and the ratio of water in dye liquor to be measured are 70/30 (v/v), and dye liquor absorbance uses purple Outward-visible spectrophotometer measures, and calculates dye uptake with following formula.
In above formula, A0 and A1 is respectively dyeing stock solution and the absorbance of dyeing residual liquid.
When disperse dyes are Disperse Red 3B, disperse blue SE-2R or when disperseing bright blue S-GL, it is fine that porous porous surpasses flexible polyester Dimension POY silk and the dye uptake result such as following table of general fibre:
The Color contrast of flexible polyester fiber POY silk and general fibre is surpassed, it can be seen that porous by porous porous The Color of super flexible polyester fiber POY silk is substantially better than general fibre, the modification that also from side illustration prepared by the present invention The hexanediol segment containing side chain contained in polyester macromolecule, makes the increasing degree of free volume be far longer than unbranched polyester The characteristic of macromolecular chain, the increase of free volume improves molecule and enters the degree within polyester, is modified polyester and prepares The free volume of polyester fiber be far longer than unbranched polyester fiber at equal temperature, increase the diffusion of dyestuff, carry The dyeability of superpolyester fiber.
Embodiment 59
Porous surpasses the dyeing of flexible polyester fiber POY silk:
The porous porous preparing embodiment 31 surpasses flexible polyester fiber POY silk and dyes in High Temperature High Pressure machine, tool Concrete conditions in the establishment of a specific crime is: before dyeing, porous surpass flexible polyester fiber POY silk nonionic surfactant 60 DEG C process 30 minutes, so In rear addition dyeing liquor, the disperse dyes consumption in dyeing liquor is 2.0% (o.w.f)；Dispersant NNO, the concentration of dispersant NNO 1.2g/L；PH value is 5, and bath raio is 1:50, enters dye, then heat to 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C and 130 at 60 DEG C DEG C each constant temperature dyeing 1h.
Use identical dyeing condition that general fibre is dyeed.Porous porous after dyed surpasses flexible polyester fiber The dye uptake of POY silk obtains by the following method:
Dye uptake uses residual liquid colorimetry to determine, draws appropriate dyeing stock solution and dyeing residual liquid, adds N, N-2 first Base Methanamide (DMF) and distilled water, DMF and the ratio of water in dye liquor to be measured are 70/30 (v/v), and dye liquor absorbance uses purple Outward-visible spectrophotometer measures, and calculates dye uptake with following formula.
In above formula, A0 and A1 is respectively dyeing stock solution and the absorbance of dyeing residual liquid.
When disperse dyes are Disperse Red 3B, disperse blue SE-2R or when disperseing bright blue S-GL, it is fine that porous porous surpasses flexible polyester Dimension POY silk and the dye uptake result such as following table of general fibre:
The Color contrast of flexible polyester fiber POY silk and general fibre is surpassed, it can be seen that porous is super soft by porous The Color of soft polyester fiber POY silk is substantially better than general fibre, the modified poly ester that also from side illustration prepared by the present invention The hexanediol segment containing side chain contained in macromole, makes the increasing degree of free volume be far longer than unbranched polyester and divides greatly The characteristic of subchain, the increase of free volume improves molecule and enters degree polyester within, and be modified prepared by polyester gathers The free volume of ester fiber is far longer than unbranched polyester fiber at equal temperature, increases the diffusion of dyestuff, improves poly- The dyeability of ester fiber.

Claims (10)

1. porous surpasses a flexible polyester fiber POY silk, it is characterized in that: described porous surpasses the material of flexible polyester fiber POY silk For modified poly ester, described modified poly ester is made up of p-phthalic acid segment, ethylene glycol segment and the hexanediol segment containing side chain, institute State on the non-end group carbon that the hexanediol segment containing side chain refers to that side chain is positioned in hexanediol segment and side chain is for containing 5-10 The hexanediol segment of the linear carbon chain of individual carbon atom；
It is 0.3～2.0dtex that described porous surpasses the filament number of flexible polyester fiber POY silk, initial modulus≤60cN/dtex, Fracture strength >=2.6cN/dtex, elongation at break is 100.0 ± 10.0%；Described porous surpasses flexible polyester fiber POY silk and exists Temperature is at 80～130 DEG C, and the spatial joint clearance of fibrous inside molecule interchain increases 10～30v/v%, at 260～290 DEG C, molten Body viscosity declines 10～20%；Described porous surpasses line density deviation ratio≤0.2% of flexible polyester fiber POY silk, fracture strength CV value≤2.5%, extension at break CV value≤5.0%, the spatial joint clearance increase of described molecule interchain refers to that modified poly ester is with often Rule polyester is in the contrast of the spatial joint clearance of mutually synthermal molecule interchain.
A kind of porous the most as claimed in claim 1 surpasses the preparation method of flexible polyester fiber POY silk, it is characterized in that: by modification Polyester employing porous spinneret spinning prepares porous and surpasses flexible polyester fiber POY silk；The row of spinneret orifice on described porous spinneret Row mode is oval shaped arrangements, and described oval shaped arrangements refers to that the hole of spinneret orifice is centrally located on concentration ellipse, described the most ellipse Circle is oval for series, the major axis conllinear of all ellipses, and short axle conllinear；
Described porous surpasses the preparation method of flexible polyester fiber POY silk: modified poly ester obtains Modified polyester chips through pelletizing, changes Property polyester slice is through measuring, extrude, cool down, oil and wind prepared modified poly ester POY silk；
The preparation process of described modified poly ester is:
(1) preparation of p-phthalic acid binary alcohol esters；
After p-phthalic acid is made into slurry with the hexanediol containing side chain, under the catalytic action of concentrated sulphuric acid, carry out esterification Obtain p-phthalic acid binary alcohol esters；The described hexanediol containing side chain refers to the non-end group that side chain is positioned in hexanediol segment On carbon and dihydroxylic alcohols that side chain is the linear carbon chain containing 5-10 carbon atom；
(2) preparation of ethylene glycol terephthalate；
After p-phthalic acid and ethylene glycol are made into slurry, carry out esterification, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester；
After esterification in step (2) terminates, adding the p-phthalic acid binary alcohol esters of preparation in step (1), stirring is mixed Close, under the effect of catalyst and stabilizer, under conditions of negative pressure, carry out polycondensation reaction and the Gao Zhen in coarse vacuum stage successively The polycondensation reaction in empty stage, prepares modified poly ester.
A kind of porous the most according to claim 2 surpasses the preparation method of flexible polyester fiber POY silk, it is characterised in that institute The concrete preparation process stating modified poly ester is:
(1) preparation of p-phthalic acid binary alcohol esters；
P-phthalic acid is made into slurry with the hexanediol containing side chain, under the catalytic action of concentrated sulphuric acid, carries out esterification, ester Changing reaction compressive reaction in nitrogen atmosphere, moulding pressure is normal pressure～0.3MPa, and temperature is 180～240 DEG C, works as esterification In water quantity of distillate reach theoretical value more than 90% time be esterification terminal, obtain p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate；
After p-phthalic acid and ethylene glycol are made into slurry, carrying out esterification, esterification is compressive reaction in nitrogen atmosphere, Moulding pressure is normal pressure～0.3MPa, and temperature is 250～260 DEG C, when the water quantity of distillate in esterification reaches theoretical value It is esterification terminal when more than 90%, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester；
After esterification in step (2) terminates, adding the p-phthalic acid binary alcohol esters of preparation in step (1), stirring is mixed Close 15-20 minute, under the effect of catalyst and stabilizer, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, This staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, and temperature controls at 260～270 DEG C, the response time be 30～ 50 minutes；Then proceed to evacuation, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure and be less than 100Pa, reaction temperature controls at 275～280 DEG C, response time 50～90 minutes, prepares modified poly ester；
Described porous surpasses the main spinning technology parameter of flexible polyester fiber POY silk:
The temperature of extrusion: 280～290 DEG C；
The pathogenic wind-warm of cooling: 20～25 DEG C；
The speed of winding: 2500～3000m/min.
A kind of porous the most according to claim 2 surpasses the preparation method of flexible polyester fiber POY silk, it is characterised in that step Suddenly, in (1), p-phthalic acid is 1:1.3-1.5 with the mol ratio of the hexanediol containing side chain；Concentrated sulphuric acid addition is terephthaldehyde The 0.3-0.5% of acid weight；The concentration of described concentrated sulphuric acid is 50-60wt%；
In step (2), p-phthalic acid is 1:1.2～2.0 with the mol ratio of ethylene glycol；
In step (3), the Mole percent ratio of described p-phthalic acid binary alcohol esters and ethylene glycol terephthalate be 2～ 5%；Described catalyst is antimony oxide, antimony glycol or antimony acetate, and catalyst charge is p-phthalic acid gross weight 0.01%～0.05%；Described stabilizer is triphenyl phosphate, trimethyl phosphate or NSC 6513, and stabilizer addition is The 0.01%～0.05% of described p-phthalic acid gross weight；
The number-average molecular weight of described modified poly ester is 15000～30000.
A kind of porous the most according to claim 2 surpasses the preparation method of flexible polyester fiber POY silk, it is characterised in that institute Stating the hexanediol containing side chain is 2-amyl group-1,6 hexanediol, 2-hexyl-1,6 hexanediol, 2-heptyl-1,6 hexanediol, 2-octyl group- More than one in 1,6 hexanediol, 2-nonyl-1,6 hexanediol or 2-decyl-1,6 hexanediol.
A kind of porous the most according to claim 2 surpasses the preparation method of flexible polyester fiber POY silk, it is characterised in that institute That states spinneret orifice is arranged as major axis and/or short axial symmetry.
A kind of porous the most according to claim 2 surpasses the preparation method of flexible polyester fiber POY silk, it is characterised in that ellipse The major axis of circle is 1.3～1.8 with the ratio of minor axis length；The spacing of adjacent spinneret orifice adds more than or equal to the guide hole diameter of spinneret orifice Upper 1.5mm.
A kind of porous the most according to claim 2 surpasses the preparation method of flexible polyester fiber POY silk, it is characterised in that institute Stating spinneret is circular jetting filament plate or elliptical spinneret plate；The long axial length that the diameter of described circular jetting filament plate is maximum with series ellipse The difference of degree is more than 10mm, and the difference of the long axis length that described elliptical spinneret plate is maximum with series ellipse is more than 10mm.
A kind of porous the most according to claim 2 surpasses the preparation method of flexible polyester fiber POY silk, it is characterised in that institute State the guide hole a diameter of 1.5～2.5mm of spinneret orifice；The spray webbing hole count of described spinneret is more than or equal to 192.
A kind of porous the most according to claim 2 surpasses the preparation method of flexible polyester fiber POY silk, it is characterised in that institute The shape of cross section of the spinneret orifice stating spinneret is circle, square, rhombus, yi word pattern, triangular form, trilobal cross, hollow type Or platypelloid type.
CN201610788733.5A 2016-08-31 2016-08-31 Porous super flexible polyester fiber POY of one kind and preparation method thereof Active CN106283264B (en)

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