CN106283253A - A kind of porous polyester fiber DTY silk and preparation method thereof - Google Patents

A kind of porous polyester fiber DTY silk and preparation method thereof Download PDF

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Publication number
CN106283253A
CN106283253A CN201610788732.0A CN201610788732A CN106283253A CN 106283253 A CN106283253 A CN 106283253A CN 201610788732 A CN201610788732 A CN 201610788732A CN 106283253 A CN106283253 A CN 106283253A
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phthalic acid
preparation
polyester fiber
modified poly
poly ester
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CN201610788732.0A
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CN106283253B (en
Inventor
范红卫
沈建根
马文平
陈德伟
杨超明
王锋宾
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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
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
    • 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
    • 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
    • C08G63/78—Preparation processes
    • 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
    • D01D4/00—Spinnerette packs; Cleaning thereof
    • D01D4/02—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
    • D01D5/08—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
    • D01D5/092—Cooling filaments, threads or the like, leaving the spinnerettes in shafts or chimneys

Abstract

The present invention relates to a kind of porous polyester fiber DTY silk and preparation method thereof, modified poly ester uses porous spinneret spinning prepare porous polyester fiber DTY 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 polyester fiber DTY silk is processed further preparing after being prepared POY silk by modified poly ester, the preparation method of modified poly ester is: p-phthalic acid and glycol reaction prepare ethylene glycol terephthalate, add the p-phthalic acid binary alcohol esters that p-phthalic acid prepares with the diol reaction containing side chain, continue reaction and obtain modified poly ester.The fibre property that the present invention prepares is excellent, line density deviation ratio≤2.0% of DTY silk, fracture strength CV value≤4.0%, extension at break CV value≤8.0%, crimp contraction coefficient of variation CV value≤8.0%.

Description

A kind of porous polyester fiber DTY silk and preparation method thereof
Technical field
The invention belongs to field of polyester fiber, relate to a kind of porous polyester fiber DTY 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 the preparation method of a kind of porous polyester fiber DTY silk.The raw material of the polyester fiber of the present invention is modified Polyester, introduces the dihydroxylic alcohols segment containing side chain, is modified porous polyester fiber DTY prepared by polyester in the strand of modified poly ester Silk, under the conditions of uniform temperature, the increasing degree of the spatial joint clearance of porous polyester fiber DTY silk interior molecules interchain is far longer than same The degree within molecule entrance such as unbranched conventional polyester fiber, beneficially stain under equitemperature, improves dyeing speed Rate；The melt viscosity of porous polyester fiber DTY silk reduces, and reduces processing temperature, reduces degradation rate, is conducive to processing；Additionally Dihydroxylic alcohols segment containing side chain does not has big destruction to the structural regularity of porous polyester fiber DTY silk, maintains polyester fiber Premium properties.Using the spinneret of spinneret orifice oval shaped arrangements in spinning process of the present invention, beneficially fiber is in spinning process In uniform, sufficiently cool, performance between fiber and structure difference are less, improve dyeing uniformity and the mechanical property of fiber Energy.
For reaching above-mentioned purpose, the technical solution used in the present invention is:
A kind of porous polyester fiber DTY silk, the material of described porous polyester fiber DTY silk is modified poly ester, described modification Polyester is made up of p-phthalic acid segment, ethylene glycol segment and the dihydroxylic alcohols segment containing side chain, the described dihydroxylic alcohols chain containing side chain Section refers on the non-end group carbon that side chain is positioned in dihydroxylic alcohols segment and side chain is the linear carbon chain containing 5-10 carbon atom Dihydroxylic alcohols segment；
The filament number of described porous polyester fiber DTY silk is 0.3～1.0dtex, fracture strength >=1.9cN/dtex, disconnected Splitting percentage elongation is 30.0 ± 5.0%；Described porous polyester fiber DTY silk at temperature is 80～130 DEG C, fibrous inside strand Between spatial joint clearance increase 10～30v/v%；Line density deviation ratio≤2.0% of described porous polyester fiber DTY silk, fracture is strong Degree CV value≤4.0%, extension at break CV value≤8.0%, crimp contraction coefficient of variation CV value≤8.0%, boiling water shrinkage is 11.0 ± 0.8%, crimp contraction is 3.50 ± 2.0%, and oil content is 1.0 ± 0.2%, and internet pricing is 100 ± 5/m.
The spatial joint clearance increase of described molecule interchain refers to that modified poly ester and normal polyester are at mutually synthermal strand Between the contrast of spatial joint clearance.
Present invention also offers the preparation method of a kind of porous polyester fiber DTY silk, modified poly ester is used porous spray webbing Plate spinning prepares porous polyester fiber DTY silk；On described porous spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, 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 oval, all ellipses Major axis conllinear, and short axle conllinear；
The preparation method of described porous polyester fiber DTY silk is: p-phthalic acid, dihydroxylic alcohols containing side chain and ethylene glycol contracting Poly-prepared modified poly ester, then obtain Modified polyester chips through pelletizing；Again through measuring, extrude, cool down, oil and winding, prepare POY Silk；POY silk through wire leading pipe, network, add hot-stretch, false twisting, thermal finalization and coiling and molding and prepare DTY 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 dihydroxylic alcohols containing side chain, under the catalytic action of concentrated sulphuric acid, it is esterified Reaction obtains p-phthalic acid binary alcohol esters；The described dihydroxylic alcohols containing side chain refer to one that side chain is positioned in dihydroxylic alcohols segment non- On end group carbon and dihydroxylic alcohols that side chain is the linear carbon chain containing 5-10 carbon atom；
For the dihydroxylic alcohols 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 dihydroxylic alcohols containing side chain and terephthaldehyde The reactivity of acid, less than ethylene glycol, according to the mixing of same ethylene glycol and terephthaldehyde's acid reaction, can cause the binary containing side chain Alcohol reaction is imperfect, thus the ratio that the dihydroxylic alcohols 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 dihydroxylic alcohols 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 dihydroxylic alcohols 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:
The preparation method of a kind of porous polyester fiber DTY silk as above, the concrete preparation process of described modified poly ester For:
(1) preparation of p-phthalic acid binary alcohol esters；
P-phthalic acid is made into slurry with the dihydroxylic alcohols 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；
The main spinning technology parameter of described POY silk is:
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；
The main spinning technology parameter of described DTY silk is:
Spin speed: 550-680m/min；
T1:210-245 DEG C；
T2:210-245 DEG C；
Pressure sky: 0.09-0.12MPa；
Oil tanker rotating speed: 0.50r/min.
The preparation method of a kind of porous polyester fiber DTY silk as above, in step (1), p-phthalic acid props up with containing The mol ratio of the dihydroxylic alcohols of chain is 1:1.3-1.5；Concentrated sulphuric acid addition is the 0.3-0.5% of p-phthalic acid weight；Described dense The concentration of 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.
The preparation method of a kind of porous polyester fiber DTY silk as above, the described dihydroxylic alcohols containing side chain be 2-amyl group- 1,3 propylene glycol, 2-hexyl-1,3 propylene glycol, 2-heptyl-1,3 propylene glycol, 2-octyl group-1,3 propylene glycol, 2-nonyl-1,3 the third two Alcohol, 2-decyl-1,3 propylene glycol, 2-amyl group-1,4 butanediol, 2-hexyl-1,4 butanediol, 2-heptyl-1,4 butanediol, 2-are pungent Base-1,4 butanediol, 2-nonyl-1,4 butanediol, 2-decyl-1,4 butanediol, 2-amyl group-1,5 pentanediol, 2-hexyl-1,5 penta Glycol, 2-heptyl-1,5 pentanediol, 2-octyl group-1,5 pentanediol, 2-nonyl-1,5 pentanediol, 2-decyl-1,5 pentanediol, 2-penta Base-1,6 hexanediol, 2-hexyl-1,6 hexanediol, 2-heptyl-1,6 hexanediol, 2-octyl group-1,6 hexanediol, 2-nonyl-1,6 are own More than one in glycol or 2-decyl-1,6 hexanediol.
The preparation method of a kind of porous polyester fiber DTY silk as above, described spinneret orifice be arranged as major axis and/or Short axial symmetry.
The preparation method of a kind of porous polyester fiber DTY silk as above, oval major axis and the ratio of minor axis length It is 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.Significant surface when spinneret Long-pending mutually simultaneously as the girth of ellipse is more than circular girth, the number of plies of spinneret orifice oval shaped arrangements is less than circular arrangement The number of plies, 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 beneficially ring blows The cooling of wind, improves the cooling effectiveness of ring blowing, and the fibre property of preparation is the most more excellent.The ratio of major axis and minor axis length is more Close to 1, ellipse is more similar to circle, and the difference of cooling effectiveness and cooling effect is little；Major axis is 1.3 with the ratio of minor axis length Time, 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 Improving relatively big, 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 conventional concentric circle row The number of turns of row reduces, it is easy to cooling wind is saturating, makes the fiber cooling condition of Internal and external cycle evenly；Major axis and the ratio of minor axis length During more than 1.8, ellipse is partial to form flat shape, is difficult to punching, and cooling no longer raises.Therefore, series is ellipse The major axis of circle is 1.3～1.8 with the ratio of minor axis length, it is possible to reach higher cooling effectiveness and preferable cooling effect.
The preparation method of a kind of porous polyester fiber DTY silk as above, described spinneret is circular jetting filament plate or ellipse Circular jetting filament 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, described ellipse The difference of the long axis length that circular jetting filament plate is maximum with series ellipse is more than 10mm.
The preparation method of a kind of porous polyester fiber DTY silk as above, the guide hole a diameter of 1.5 of described spinneret orifice～ 2.5mm；The spray webbing hole count of described spinneret is more than or equal to 192.
The preparation method of a kind of porous polyester fiber DTY silk as above, the spinneret orifice of described spinneret transversal Face is generally circular in shape, 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 dihydroxylic alcohols 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 dihydroxylic alcohols 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) material of the porous polyester fiber DTY silk that the present invention prepares is modified poly ester, contains in modified poly ester macromole The dihydroxylic alcohols segment containing side chain, when temperature higher than vitrification point time, side chain, prior to backbone motion, makes the increase of free volume Amplitude is far longer than the characteristic of unbranched polyester macromolecule chain, and the increase of free volume improves molecule and enters in polyester The degree in portion, is added the free volume diffusion with increase dyestuff of polyester fiber, improves polyester fiber by side chain Dyeability.
4) the porous polyester fiber DTY silk that the present invention prepares, the increase of polyester fiber free volume advantageously reduces melt Viscosity, is conducive to improving its processing characteristics.
5) the porous polyester fiber DTY silk that the present invention prepares, the dihydroxylic alcohols segment containing side chain introduce to polyester fiber Structural regularity there is no big destruction, maintain the premium properties of polyester fiber.
6) present invention prepares porous polyester fiber DTY silk dyeability and good mechanical performance, porous polyester fiber DTY Line density deviation ratio≤2.0% of silk, fracture strength CV value≤4.0%, extension at break CV value≤8.0%, crimp contraction becomes Different coefficient CV value≤8.0%.
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-1,3 propylene glycol 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 and addition that amount is the 0.01% of p-phthalic acid gross weight are p-phthalic acid gross weight Under the effect of the stabilizer triphenyl phosphate of 0.01%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank It is 500Pa that section pressure is steadily evacuated to absolute pressure by normal pressure, and temperature controls at 260 DEG C, and the response time is 30 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 100Pa, and reaction temperature controls 275 DEG C, in 50 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 15000, and modified poly ester is by p-phthalic acid segment, ethylene glycol segment and 2-penta Base-1,3 propylene glycol segment compositions, the dihydroxylic alcohols segment containing side chain is 2% with the Mole percent ratio of ethylene glycol segment.
Table 1: embodiment 2-12 important technological parameters
Embodiment 2
The preparation method of the modified poly ester of embodiment 2, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 16 minutes, in addition be The catalytic antimony trioxide of the 0.011% of p-phthalic acid gross weight and addition is p-phthalic acid gross weight 0.02% 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 490Pa by normal pressure, temperature controls at 262 DEG C, and the response time is 31 minutes；Then proceed to evacuation, Carrying out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 90Pa, reaction temperature controls at 276 DEG C, reaction 51 minutes time, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 16000, and modified poly ester is own by p-phthalic acid segment, ethylene glycol segment and 2- Base-1,3 propylene glycol segment compositions, 2-hexyl-1,3 propylene glycol segments are 2.1% with the Mole percent ratio of ethylene glycol segment.
Embodiment 3
The preparation method of the modified poly ester of embodiment 3, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 16 minutes, in addition be The catalytic antimony trioxide of the 0.03% of p-phthalic acid gross weight and addition is p-phthalic acid gross weight 0.02% 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 498Pa by normal pressure, temperature controls at 263 DEG C, and the response time is 32 minutes；Then proceed to evacuation, Carrying out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 90Pa, reaction temperature controls at 277 DEG C, reaction 57 minutes time, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 15900, and modified poly ester is by p-phthalic acid segment, ethylene glycol segment and 2-heptan Base-1,3 propylene glycol segment compositions, 2-heptyl-1,3 propylene glycol segments are 2.2% with the Mole percent ratio of ethylene glycol segment.
Embodiment 4
The preparation method of the modified poly ester of embodiment 4, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 17 minutes, in addition be The catalytic antimony trioxide of the 0.033% of p-phthalic acid gross weight and addition are p-phthalic acid gross 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 modified poly ester is 15800, and modified poly ester is pungent by p-phthalic acid segment, ethylene glycol segment and 2- Base-1,3 propylene glycol segment compositions, 2-octyl group-1,3 propylene glycol segments are 2.3% with the Mole percent ratio of ethylene glycol segment.
Embodiment 5
The preparation method of the modified poly ester of embodiment 5, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 17 minutes, in addition be The catalytic antimony trioxide of the 0.034% of p-phthalic acid gross weight and addition are p-phthalic acid gross 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 80Pa, and reaction temperature controls 277 DEG C, in 59 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 15900, and modified poly ester is by p-phthalic acid segment, ethylene glycol segment and 2-nonyl Base-1,3 propylene glycol segment compositions, 2-nonyl-1,3 propylene glycol segments are 2.4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 6
The preparation method of the modified poly ester of embodiment 6, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 18 minutes, in addition be The catalytic antimony trioxide of the 0.035% of p-phthalic acid gross weight and addition are p-phthalic acid gross 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 is 16000, and modified poly ester is by p-phthalic acid segment, ethylene glycol segment and 2-last of the ten Heavenly stems Base-1,3 propylene glycol segment compositions, 2-decyl-1,3 propylene glycol segments are 2.5% with the Mole percent ratio of ethylene glycol segment.
Embodiment 7
The preparation method of the modified poly ester of embodiment 7, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 19 minutes, in addition be The catalytic antimony trioxide of the 0.036% of p-phthalic acid gross weight and addition are p-phthalic acid gross 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 modified poly ester is 16000, and the number-average molecular weight of modified poly ester is 16000, and modified poly ester is by right Phthalic acid segment, ethylene glycol segment and 2-amyl group-Isosorbide-5-Nitrae butanediol segment composition, 2-amyl group-Isosorbide-5-Nitrae butanediol segment and second two The Mole percent ratio of alcohol segment is 2.6%.
Embodiment 8
The preparation method of the modified poly ester of embodiment 8, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 19 minutes, in addition be The catalytic antimony trioxide of the 0.036% of p-phthalic acid gross weight and addition are p-phthalic acid gross 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 modified poly ester is 17000, and modified poly ester is own by p-phthalic acid segment, ethylene glycol segment and 2- Base-Isosorbide-5-Nitrae butanediol segment composition, 2-hexyl-Isosorbide-5-Nitrae butanediol segment is 2.7% with the Mole percent ratio of ethylene glycol segment.
Embodiment 9
The preparation method of the modified poly ester of embodiment 9, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 16 minutes, in addition be The catalyst glycol antimony of the 0.04% of p-phthalic acid gross weight and addition is p-phthalic acid gross weight 0.026% 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 268 DEG C, and the response time is 38 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 60Pa, and reaction temperature controls at 279 DEG C, reaction 62 minutes time, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 17000, and modified poly ester is by p-phthalic acid segment, ethylene glycol segment and 2-heptan Base-Isosorbide-5-Nitrae butanediol segment composition, 2-heptyl-Isosorbide-5-Nitrae butanediol segment is 2.8% with the Mole percent ratio of ethylene glycol segment.
Embodiment 10
The preparation method of the modified poly ester of embodiment 10, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 17 minutes, in addition be The catalyst glycol antimony of the 0.03% of p-phthalic acid gross weight and addition is p-phthalic acid gross 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 60Pa, and reaction temperature controls at 278 DEG C, reaction 64 minutes time, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 17000, and modified poly ester is pungent by p-phthalic acid segment, ethylene glycol segment and 2- Base-Isosorbide-5-Nitrae butanediol segment composition, 2-octyl group-Isosorbide-5-Nitrae butanediol segment is 3% with the Mole percent ratio of ethylene glycol segment.
Embodiment 11
The preparation method of the modified poly ester of embodiment 11, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 18 minutes, in addition be The catalyst glycol antimony of the 0.04% of p-phthalic acid gross weight and addition is p-phthalic acid gross 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 60Pa, and reaction temperature controls at 277 DEG C, reaction 63 minutes time, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 18000, and modified poly ester is by p-phthalic acid segment, ethylene glycol segment and 2-nonyl Base-Isosorbide-5-Nitrae butanediol segment composition, 2-nonyl-Isosorbide-5-Nitrae butanediol segment is 4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 12
The preparation method of the modified poly ester of embodiment 12, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 18 minutes, in addition be The catalyst acetic acid antimony of the 0.038% of p-phthalic acid weight and addition is p-phthalic acid weight 0.03% stabilizer Under the effect of NSC 6513, starting the polycondensation reaction in coarse vacuum stage under conditions of negative pressure, this staged pressure is by normal pressure Steadily being evacuated to absolute pressure 497Pa, temperature controls at 265 DEG C, and the response time is 42 minutes；Then proceed to evacuation, carry out height The polycondensation reaction of vacuum stages, making reaction pressure be down to absolute pressure is 40Pa, and reaction temperature controls at 277 DEG C, the response time 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-Isosorbide-5-Nitrae butanediol segment composition, 2-decyl-Isosorbide-5-Nitrae butanediol segment is 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-1,5 pentanediols 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-1,5 pentanediol segment compositions, 2-decyl-1,5 pentanediol 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-1,5 pentanediols 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-1,5 pentanediol segment compositions, 2-nonyl-1,5 pentanediol 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-1,5 pentanediols 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-1,5 pentanediol segment compositions, 2-octyl group-1,5 pentanediol 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-1,5 pentanediols 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-1,5 pentanediol segment compositions, 2-heptyl-1,5 pentanediol 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-1,5 pentanediols 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-1,5 pentanediol segment compositions, 2-hexyl-1,5 pentanediol 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-1,5 pentanediols 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-1,5 pentanediol segment compositions, 2-amyl group-1,5 pentanediol 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-1,5 pentanediol and 2-amyl group-1,4 butanediol Compound is made into slurry and adds in reactor, wherein 2-hexyl-1, and the mol ratio of 5 pentanediols and 2-amyl group-Isosorbide-5-Nitrae butanediol 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- 1,5 pentanediol segment and 2-amyl group-Isosorbide-5-Nitrae butanediol segment composition, 2-hexyl-1,5 pentanediol 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 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-1,5 pentanediol 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 5 pentanediols 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-1,5 pentanediol segment compositions, 2-octyl group-1,6 hexanediol segments and 2-amyl group-1,5 penta 2 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-1,5 pentanediol and 2-amyl group-1,4 butanediol Compound is made into slurry and adds in reactor, wherein 2-hexyl-1, and the mol ratio of 5 pentanediols and 2-amyl group-Isosorbide-5-Nitrae butanediol 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- 1,5 pentanediol segment and 2-amyl group-Isosorbide-5-Nitrae butanediol segment composition, 2-hexyl-1,5 pentanediol 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-1,3 propylene glycol, 2-amyl group-1,4 butanediol 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-1,3 propylene glycol segments, 2-amyl group-Isosorbide-5-Nitrae butanediol chain 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 preparation method of porous polyester fiber DTY silk, porous polyester fiber DTY silk uses porous spinneret to prepare, On spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located at concentration ellipse On, 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.
The modified poly ester that embodiment 1 prepares, obtains Modified polyester chips through pelletizing；Again through measuring, extrude, cool down, oiling And winding, preparing POY silk, 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 3000m/ min；POY silk through wire leading pipe, network, add hot-stretch, false twisting, thermal finalization and coiling and molding and prepare DTY silk, the speed of spinning of DTY silk is 650m/min, T1 are 230 DEG C, and T2 is 230 DEG C, and pressure sky is 0.11MPa, and oil tanker rotating speed is 0.50r/min.
The filament number of the porous polyester fiber DTY silk prepared is 0.7dtex, and fracture strength is 2.7cN/dtex, fracture Percentage elongation is 32.3%；Porous polyester fiber DTY silk is at temperature is 80 DEG C, and the spatial joint clearance of fibrous inside molecule interchain increases 15v/v%；The line density deviation ratio of porous polyester fiber DTY silk is 1.4%, and fracture strength CV value is 2.7%, extension at break CV Value is 6.7%, and crimp contraction coefficient of variation CV value is 6.1%, and boiling water shrinkage is 10.8%, and crimp contraction is 2.8%, Oil content is 1.0%, and internet pricing is 98/m.
Embodiment 30
A kind of preparation method of porous polyester fiber DTY silk, porous polyester fiber DTY silk uses porous spinneret to prepare, On spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located at concentration ellipse On, 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.
The modified poly ester that embodiment 1 prepares, obtains Modified polyester chips through pelletizing；Again through measuring, extrude, cool down, oiling And winding, preparing POY silk, 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 3000m/ min；POY silk through wire leading pipe, network, add hot-stretch, false twisting, thermal finalization and coiling and molding and prepare DTY silk, the speed of spinning of DTY silk is 650m/min, T1 are 230 DEG C, and T2 is 230 DEG C, and pressure sky is 0.11MPa, and oil tanker rotating speed is 0.50r/min.
The filament number of the porous polyester fiber DTY silk prepared is 0.3dtex, and fracture strength is 3.2cN/dtex, fracture Percentage elongation is 33.7%；Porous polyester fiber DTY silk is at temperature is 80 DEG C, and the spatial joint clearance of fibrous inside molecule interchain increases 15v/v%；The line density deviation ratio of porous polyester fiber DTY silk is 1.1%, and fracture strength CV value is 2.1%, extension at break CV Value is 5.9%, and crimp contraction coefficient of variation CV value is 4.3%, and boiling water shrinkage is 11.5%, and crimp contraction is 2.7%, Oil content is 1.1%, and internet pricing is 103/m.
Comparative example 1
A kind of preparation method of porous polyester fiber DTY silk, porous polyester fiber DTY silk uses porous spinneret to prepare, 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 on concentric circular, with Heart circle is circular for series.As in figure 2 it is shown, the spacing of adjacent spinneret orifice adds 1.5mm, spinneret equal to the guide hole diameter of spinneret orifice For circular jetting filament plate, the difference of the diameter that the diameter of circular jetting filament plate is maximum with series circle is 11mm, and the guide hole of spinneret orifice is straight Footpath is 2.0mm, and the spray webbing hole count of spinneret is 370, and the shape of cross section of the spinneret orifice of spinneret is circular.
The modified poly ester that embodiment 1 prepares, obtains Modified polyester chips through pelletizing；Again through measuring, extrude, cool down, oiling And winding, preparing POY silk, 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 3000m/ min；POY silk through wire leading pipe, network, add hot-stretch, false twisting, thermal finalization and coiling and molding and prepare DTY silk, the speed of spinning of DTY silk is 650m/min, T1 are 230 DEG C, and T2 is 230 DEG C, and pressure sky is 0.11MPa, and oil tanker rotating speed is 0.50r/min.
The filament number of the porous polyester fiber DTY silk prepared is 1.0dtex, and fracture strength is 1.7cN/dtex, fracture Percentage elongation is 25.0%；Porous polyester fiber DTY silk is at temperature is 80 DEG C, and the spatial joint clearance of fibrous inside molecule interchain increases 15v/v%；The line density deviation ratio of porous polyester fiber DTY silk is 3.8%, and fracture strength CV value is 6.7%, extension at break CV Value is 9.4%, and crimp contraction coefficient of variation CV value is 9.1%, and boiling water shrinkage is 7.2%, and crimp contraction is 2.8%, Oil content is 0.8%, and internet pricing is 83/m.
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 preparation method of porous polyester fiber DTY silk, porous polyester fiber DTY silk uses porous spinneret to prepare, On spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located at concentration ellipse On, 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；POY silk is through leading Fiber tube, network, adding hot-stretch, false twisting, thermal finalization and coiling and molding and prepare DTY silk, the speed of spinning of DTY silk for 550m/min, T1 is 210 DEG C, T2 is 210 DEG C, and pressure sky is 0.09MPa, and oil tanker rotating speed is 0.50r/min.The porous polyester fiber DTY silk prepared is 80 The spatial joint clearance Magnification of fibrous inside molecule interchain and the mechanical performance data such as following table of fiber at DEG C.
Embodiment 34～36
A kind of preparation method of porous polyester fiber DTY silk, porous polyester fiber DTY silk uses porous spinneret to prepare, On spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located at concentration ellipse On, 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 290 DEG C, and the pathogenic wind-warm of cooling is 25 DEG C, and the speed of winding is 3000m/min；POY silk is through leading Fiber tube, network, adding hot-stretch, false twisting, thermal finalization and coiling and molding and prepare DTY silk, the speed of spinning of DTY silk for 680m/min, T1 is 245 DEG C, T2 is 245 DEG C, and pressure sky is 0.12MPa, and oil tanker rotating speed is 0.50r/min.The porous polyester fiber DTY silk prepared is 90 The spatial joint clearance Magnification of fibrous inside molecule interchain and the mechanical performance data such as following table of fiber at DEG C.
Embodiment 37～39
A kind of preparation method of porous polyester fiber DTY silk, porous polyester fiber DTY silk uses porous spinneret to prepare, On spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located at concentration ellipse On, 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 285 DEG C, and the pathogenic wind-warm of cooling is 20 DEG C, and the speed of winding is 2700m/min；POY silk is through leading Fiber tube, network, adding hot-stretch, false twisting, thermal finalization and coiling and molding and prepare DTY silk, the speed of spinning of DTY silk for 600m/min, T1 is 220 DEG C, T2 is 220 DEG C, and pressure sky is 0.10MPa, and oil tanker rotating speed is 0.50r/min.The porous polyester fiber DTY silk prepared exists The spatial joint clearance Magnification of fibrous inside molecule interchain and the mechanical performance data such as following table of fiber at 100 DEG C.
Embodiment 40～42
A kind of preparation method of porous polyester fiber DTY silk, porous polyester fiber DTY silk uses porous spinneret to prepare, On spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located at concentration ellipse On, 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 280 DEG C, and the pathogenic wind-warm of cooling is 25 DEG C, and the speed of winding is 2800m/min；POY silk is through leading Fiber tube, network, adding hot-stretch, false twisting, thermal finalization and coiling and molding and prepare DTY silk, the speed of spinning of DTY silk for 630m/min, T1 is 225 DEG C, T2 is 225 DEG C, and pressure sky is 0.09MPa, and oil tanker rotating speed is 0.50r/min.The porous polyester fiber DTY silk prepared exists The spatial joint clearance Magnification of fibrous inside molecule interchain and the mechanical performance data such as following table of fiber at 110 DEG C.
Embodiment 43～45
A kind of preparation method of porous polyester fiber DTY silk, porous polyester fiber DTY silk uses porous spinneret to prepare, On spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located at concentration ellipse On, 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 285 DEG C, and the pathogenic wind-warm of cooling is 22 DEG C, and the speed of winding is 2600m/min；POY silk is through leading Fiber tube, network, adding hot-stretch, false twisting, thermal finalization and coiling and molding and prepare DTY silk, the speed of spinning of DTY silk for 600m/min, T1 is 215 DEG C, T2 is 215 DEG C, and pressure sky is 0.10MPa, and oil tanker rotating speed is 0.50r/min.The porous polyester fiber DTY silk prepared exists The spatial joint clearance Magnification of fibrous inside molecule interchain and the mechanical performance data such as following table of fiber at 120 DEG C.
Embodiment 46～49
A kind of preparation method of porous polyester fiber DTY silk, porous polyester fiber DTY silk uses porous spinneret to prepare, On spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located at concentration ellipse On, 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 290 DEG C, and the pathogenic wind-warm of cooling is 23 DEG C, and the speed of winding is 2700m/min；POY silk is through leading Fiber tube, network, adding hot-stretch, false twisting, thermal finalization and coiling and molding and prepare DTY silk, the speed of spinning of DTY silk for 580m/min, T1 is 220 DEG C, T2 is 220 DEG C, and pressure sky is 0.10MPa, and oil tanker rotating speed is 0.50r/min.The porous polyester fiber DTY silk prepared exists The spatial joint clearance Magnification of fibrous inside molecule interchain and the mechanical performance data such as following table of fiber at 130 DEG C.
Embodiment 50～53
A kind of preparation method of porous polyester fiber DTY silk, porous polyester fiber DTY silk uses porous spinneret to prepare, On spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located at concentration ellipse On, 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 280 DEG C, and the pathogenic wind-warm of cooling is 20 DEG C, and the speed of winding is 2600m/min；POY silk is through leading Fiber tube, network, adding hot-stretch, false twisting, thermal finalization and coiling and molding and prepare DTY silk, the speed of spinning of DTY silk for 590m/min, T1 is 225 DEG C, T2 is 225 DEG C, and pressure sky is 0.11MPa, and oil tanker rotating speed is 0.50r/min.The porous polyester fiber DTY silk prepared exists The spatial joint clearance Magnification of fibrous inside molecule interchain and the mechanical performance data such as following table of fiber at 100 DEG C.
Embodiment 54～57
A kind of preparation method of porous polyester fiber DTY silk, porous polyester fiber DTY silk uses porous spinneret to prepare, On spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located at concentration ellipse On, 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 287 DEG C, and the pathogenic wind-warm of cooling is 22 DEG C, and the speed of winding is 2700m/min；POY silk is through leading Fiber tube, network, adding hot-stretch, false twisting, thermal finalization and coiling and molding and prepare DTY silk, the speed of spinning of DTY silk for 620m/min, T1 is 230 DEG C, T2 is 230 DEG C, and pressure sky is 0.10MPa, and oil tanker rotating speed is 0.50r/min.The porous polyester fiber DTY silk prepared exists The spatial joint clearance Magnification of fibrous inside molecule interchain and the mechanical performance data such as following table of fiber at 120 DEG C.
Embodiment 58
The dyeing of porous polyester fiber DTY silk:
Dyeing the porous polyester fiber DTY silk of embodiment 29 preparation in High Temperature High Pressure machine, actual conditions is: dye Before color, porous polyester fiber DTY silk nonionic surfactant processes 30 minutes at 60 DEG C, is subsequently adding in dyeing liquor, dye Disperse dyes consumption in color liquid is 2.0% (o.w.f)；Dispersant NNO, concentration 1.2g/L of dispersant NNO；PH value is 5, bath Ratio is 1:50, enters dye, then heat to each constant temperature dyeing 1h of 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C and 130 DEG C at 60 DEG C.
Use identical dyeing condition that general fibre is dyeed.Porous polyester fiber DTY silk after dyed upper Dye percentage rate 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, porous polyester fiber DTY silk and The dye uptake result such as following table of general fibre:
Contrasted by the Color of porous polyester fiber DTY silk with general fibre, it can be seen that porous polyester fiber DTY The Color of silk is substantially better than general fibre, contains the modified poly ester macromole that also from side illustration prepared by the present invention Dihydroxylic alcohols segment containing side chain, makes the increasing degree of free volume be far longer than the characteristic of unbranched polyester macromolecule chain, from Improve molecule by the increase of volume and enter the degree within polyester, be modified the free body of polyester fiber prepared by polyester Amass and be far longer than unbranched polyester fiber at equal temperature, increase the diffusion of dyestuff, improve the dyeability of polyester fiber Energy.
Embodiment 59
The dyeing of porous polyester fiber DTY silk:
Dyeing the porous polyester fiber DTY silk of embodiment 31 preparation in High Temperature High Pressure machine, actual conditions is: dye Before color, porous polyester fiber DTY silk nonionic surfactant processes 30 minutes at 60 DEG C, is subsequently adding in dyeing liquor, dye Disperse dyes consumption in color liquid is 2.0% (o.w.f)；Dispersant NNO, concentration 1.2g/L of dispersant NNO；PH value is 5, bath Ratio is 1:50, enters dye, then heat to each constant temperature dyeing 1h of 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C and 130 DEG C at 60 DEG C.
Use identical dyeing condition that general fibre is dyeed.Porous polyester fiber DTY silk after dyed upper Dye percentage rate 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, porous polyester fiber DTY silk and The dye uptake result such as following table of general fibre:
Contrasted by the Color of porous polyester fiber DTY silk with general fibre, it can be seen that porous polyester fiber DTY The Color of silk is substantially better than general fibre, contains the modified poly ester macromole that also from side illustration prepared by the present invention Dihydroxylic alcohols segment containing side chain, makes the increasing degree of free volume be far longer than the characteristic of unbranched polyester macromolecule chain, from Improve molecule by the increase of volume and enter the degree within polyester, be modified the free body of polyester fiber prepared by polyester Amass and be far longer than unbranched polyester fiber at equal temperature, increase the diffusion of dyestuff, improve the dyeability of polyester fiber Energy.
Embodiment 60
The dyeing of porous polyester fiber DTY silk:
Dyeing the porous polyester fiber DTY silk of embodiment 35 preparation in High Temperature High Pressure machine, actual conditions is: dye Before color, porous polyester fiber DTY silk nonionic surfactant processes 30 minutes at 60 DEG C, is subsequently adding in dyeing liquor, dye Disperse dyes consumption in color liquid is 2.0% (o.w.f)；Dispersant NNO, concentration 1.2g/L of dispersant NNO；PH value is 5, bath Ratio is 1:50, enters dye, then heat to each constant temperature dyeing 1h of 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C and 130 DEG C at 60 DEG C.
Use identical dyeing condition that general fibre is dyeed.Porous polyester fiber DTY silk after dyed upper Dye percentage rate 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, porous polyester fiber DTY silk and The dye uptake result such as following table of general fibre:
Contrasted by the Color of porous polyester fiber DTY silk with general fibre, it can be seen that porous polyester fiber DTY The Color of silk is substantially better than general fibre, contains the modified poly ester macromole that also from side illustration prepared by the present invention Dihydroxylic alcohols segment containing side chain, makes the increasing degree of free volume be far longer than the characteristic of unbranched polyester macromolecule chain, from Improve molecule by the increase of volume and enter the degree within polyester, be modified the free body of polyester fiber prepared by polyester Amass and be far longer than unbranched polyester fiber at equal temperature, increase the diffusion of dyestuff, improve the dyeability of polyester fiber Energy.

Claims (10)

1. a porous polyester fiber DTY silk, is characterized in that: the material of described porous polyester fiber DTY silk is modified poly ester, institute State modified poly ester and form by p-phthalic acid segment, ethylene glycol segment with containing the dihydroxylic alcohols segment of side chain, described containing side chain two Unit's alcohol segment refers on the non-end group carbon that side chain is positioned in dihydroxylic alcohols segment and side chain is straight containing 5-10 carbon atom The dihydroxylic alcohols segment of chain carbochain；
The filament number of described porous polyester fiber DTY silk is 0.3～1.0dtex, and fracture strength >=1.9cN/dtex, fracture is stretched Long rate is 30.0 ± 5.0%；Described porous polyester fiber DTY silk at temperature is 80～130 DEG C, fibrous inside molecule interchain Spatial joint clearance increases 10～30v/v%；Line density deviation ratio≤2.0% of described porous polyester fiber DTY silk, fracture strength CV Value≤4.0%, extension at break CV value≤8.0%, crimp contraction coefficient of variation CV value≤8.0%, boiling water shrinkage is 11.0 ± 0.8%, crimp contraction is 3.50 ± 2.0%, and oil content is 1.0 ± 0.2%, and internet pricing is 100 ± 5/m.
The preparation method of a kind of porous polyester fiber DTY silk the most as claimed in claim 1, is characterized in that: adopted by modified poly ester Porous polyester fiber DTY silk is prepared with porous spinneret spinning；On described porous spinneret, the arrangement mode of spinneret orifice is oval Shape arranges, and 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 oval, The major axis conllinear of all ellipses, and short axle conllinear；
The preparation method of described porous polyester fiber DTY silk is: p-phthalic acid, dihydroxylic alcohols containing side chain and ethylene glycol polycondensation system Obtain modified poly ester, then obtain Modified polyester chips through pelletizing；Again through measuring, extrude, cool down, oil and winding, prepare POY silk； POY silk through wire leading pipe, network, add hot-stretch, false twisting, thermal finalization and coiling and molding and prepare DTY 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 dihydroxylic alcohols containing side chain, under the catalytic action of concentrated sulphuric acid, carry out esterification Obtain p-phthalic acid binary alcohol esters；The described dihydroxylic alcohols containing side chain refers to the non-end group that side chain is positioned in dihydroxylic alcohols 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.
The preparation method of a kind of porous polyester fiber DTY silk the most according to claim 2, it is characterised in that described modification The concrete preparation process of polyester is:
(1) preparation of p-phthalic acid binary alcohol esters；
P-phthalic acid is made into slurry with the dihydroxylic alcohols 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；
The main spinning technology parameter of described POY silk is:
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；
The main spinning technology parameter of described DTY silk is:
Spin speed: 550-680m/min；
T1:210-245 DEG C；
T2:210-245 DEG C；
Pressure sky: 0.09-0.12MPa；
Oil tanker rotating speed: 0.50r/min.
The preparation method of a kind of porous polyester fiber DTY silk the most according to claim 2, it is characterised in that step (1) In, p-phthalic acid is 1:1.3-1.5 with the mol ratio of the dihydroxylic alcohols containing side chain；Concentrated sulphuric acid addition is p-phthalic acid weight 0.3-0.5%；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.
The preparation method of a kind of porous polyester fiber DTY silk the most according to claim 2, it is characterised in that described containing propping up The dihydroxylic alcohols of chain is 2-amyl group-1,3 propylene glycol, 2-hexyl-1,3 propylene glycol, 2-heptyl-1,3 propylene glycol, 2-octyl group-1,3 the third two Alcohol, 2-nonyl-1,3 propylene glycol, 2-decyl-1,3 propylene glycol, 2-amyl group-1,4 butanediol, 2-hexyl-1,4 butanediol, 2-heptan Base-1,4 butanediol, 2-octyl group-1,4 butanediol, 2-nonyl-1,4 butanediol, 2-decyl-1,4 butanediol, 2-amyl group-1,5 penta Glycol, 2-hexyl-1,5 pentanediol, 2-heptyl-1,5 pentanediol, 2-octyl group-1,5 pentanediol, 2-nonyl-1,5 pentanediol, 2-last of the ten Heavenly stems Base-1,5 pentanediol, 2-amyl group-1,6 hexanediol, 2-hexyl-1,6 hexanediol, 2-heptyl-1,6 hexanediol, 2-octyl group-1,6 are own More than one in glycol, 2-nonyl-1,6 hexanediol or 2-decyl-1,6 hexanediol.
The preparation method of a kind of porous polyester fiber DTY silk the most according to claim 2, it is characterised in that described spray webbing Hole be arranged as major axis and/or short axial symmetry.
The preparation method of a kind of porous polyester fiber DTY silk the most according to claim 2, it is characterised in that oval length Axle 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 1.5mm。
The preparation method of a kind of porous polyester fiber DTY silk the most according to claim 2, it is characterised in that described spray webbing Plate is circular jetting filament 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 Value 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.
The preparation method of a kind of porous polyester fiber DTY silk the most according to claim 2, it is characterised in that described spray webbing The guide hole a diameter of 1.5～2.5mm in hole；The spray webbing hole count of described spinneret is more than or equal to 192.
The preparation method of a kind of porous polyester fiber DTY silk the most according to claim 2, it is characterised in that described spray webbing The shape of cross section of the spinneret orifice of plate is circle, square, rhombus, yi word pattern, triangular form, trilobal cross, hollow type or flat Type.
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