CN106381548A - Porous soft polyester fiber POY and preparation method thereof - Google Patents

Porous soft polyester fiber POY and preparation method thereof Download PDF

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Publication number
CN106381548A
CN106381548A CN201610780470.3A CN201610780470A CN106381548A CN 106381548 A CN106381548 A CN 106381548A CN 201610780470 A CN201610780470 A CN 201610780470A CN 106381548 A CN106381548 A CN 106381548A
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Prior art keywords
phthalic acid
preparation
esterification
ethylene glycol
polyester fiber
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CN201610780470.3A
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CN106381548B (en
Inventor
范红卫
尹立新
晏金龙
王丽丽
杨超明
邵义伟
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D4/00—Spinnerette packs; Cleaning thereof
    • D01D4/02—Spinnerettes
    • D01D4/025—Melt-blowing or solution-blowing dies
    • 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
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor

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

Abstract

The invention relates to porous soft polyester fiber POY and a preparation method thereof. Modified polyester undergoes spinning by a porous spinneret plate to prepare porous soft polyester fiber POY. The arrangement mode of spinneret orifices on the porous spinneret plate is elliptical arrangement. That is to say, the centers of the spinneret orifices are positioned at concentric ellipses which are series ellipses. Long axis of all the ellipses is collinear, and minor axis is collinear. According to the porous soft polyester fiber POY, modified polyester undergoes grain-sized dicing to obtain modified polyester chip; and the modified polyester chip undergoes metering, extrusion, cooling, oiling and winding so as to prepare the product. A preparation method of the modified polyester comprises the following steps: letting terephthalic acid and glycol react to prepare ethylene glycol terephthalate, adding terephthalic acid and dihydric alcohol containing branched chain and reacting to prepare terephthalic dibasic alcohol ester, and continuously reacting to the modified polyester. The prepared fiber has excellent properties. Deviation ratio of linear density is less than or equal to 0.2%; breaking strength CV value is less than or equal to 2.5%; and breaking elongation CV value is less than or equal to 5.0%.

Description

A kind of porous flexible polyester fiber POY silk and preparation method thereof
Technical field
The invention belongs to field of polyester fiber, it is related to a kind of porous flexible polyester fiber POY silk and preparation method thereof.
Background technology
Polyethylene terephthalate (PET or polyester fiber) fiber since the advent of the world, 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 of stiffness is good, is widely used in the fields such as clothing, home textile.
But because the degree of crystallinity of PET is high, the functional group that compact structure, and strand are not combined with dyestuff, cause Dye molecule hardly enters fibrous inside, and dyeing is difficult.People cannot be met to bright-coloured beautiful, unique style fabric demand.
PET dyeing is caused to belong to symmetric straight chain macromolecular for PET the reason difficult, strand does not contain side chain radical Group, regularity is very good, and its main chain contains rigid phenyl ring and flexible alkyl, and the ester group being directly connected with phenyl ring and Phenyl ring constitutes rigid conjugated system again, thus constraining rotating freely of its soft segment.Such a structure increases molecule The wall ridge of sub-chain motion, leads to the glass transition temperature of PET higher, needs to promote dye molecule under very high temperature conditionss To the diffusion of fibrous inside, complete staining procedure.In addition, the strand of PET is regular, good crystallinity, molecule chain alignment is tight, and And the polar group not having an effect with dye molecule on strand, make the colouring of PET more difficult.
Therefore, under the general High Temperature High Pressure of the 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 not high, but the energy consumption brought of high temperature and high pressure method and dye-uptake low be the subject matter facing now.In addition, PET melt viscosity is higher, is unfavorable for processing.
The method of preparation PET is a lot, and wherein melt spinning method is more one kind in current commercial production application.Molten Melt and in spinning process, have many parameters, these parameters determine the course of fiberizing and spin structure and the performance of fiber, produce Upper is exactly the fiber of desired properties to be obtained by controlling these parameters.The main spinning that can control in producing according to technical process 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 its uniformity 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 empty around strand The convection current of gas, makes ectonexine strand cool down uniformly, is to create condition using porous spinneret；Cooling blowing can make as-spun fibre Quality advance, tensile property improves, and is conducive to the production capacity of raising equipment.
Experimental branch line all adopts 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, increasingly improves to chemical fibre performance and quality requirements with people, and the exploitation of chemical-fibres filaments new product is to high added value The cooling blowing condition it is desirable to higher is developed in fibre in differentiation direction, then proposes ring blowing device.Ring blowing device is not only Possess the uniform advantage of every synnema wind-engaging, and energy consumption is compared relatively low, effectively solves cross air blasting because blowing area is big The wind energy loss problem causing.
In spinning process, although ring blowing has obvious advantage, still have problems：Due to spun silk from After circular spinneret extrusion, by ring wind quenching, due to the circular spinneret number of turns more so that ring blowing hardly enter interior Layer, leads to that the silk of innermost layer may be also uncolled after cooling in outermost silk, thus the silk of gained fiber number irregular, Intensity is irregular, the problems such as uneven dyeing, cause follow-up to silk be processed further difficulty occurs.
Content of the invention
The purpose of the present invention is to overcome the problems such as existing dyeing polyester fibers are irregular, mechanical property is poor, realizes extensive The production spinning changed, provides a kind of porous flexible polyester fiber POY silk and preparation method thereof.The raw material of the polyester fiber of the present invention For modified poly ester, in the strand of modified poly ester, introduce the dihydroxylic alcohols segment containing side chain, the porous of modified polyester preparation is soft Polyester fiber POY silk, under the conditions of uniform temperature, the increasing of the spatial joint clearance of porous flexible polyester fiber POY silk interior molecules interchain Plus amplitude is far longer than unbranched conventional polyester fiber at equal temperature, be conducive within the entrance of the molecules such as stain Degree, improves dyeing rate；The melt viscosity of porous flexible polyester fiber POY silk reduces, and reduces processing temperature, reduces degraded speed Rate, is conducive to processing；In addition the dihydroxylic alcohols segment containing side chain is not big to the structural regularity of porous flexible polyester fiber POY silk Destruction, maintain the premium properties of polyester fiber.The spinneret of spinneret orifice oval shaped arrangements is adopted in spinning process of the present invention, Be conducive to fiber uniform, sufficiently cool in spinning process, the performance between fiber and structure difference are less, improve fiber Dyeing uniformity and mechanical property.
For reaching above-mentioned purpose, the technical solution used in the present invention is：
A kind of porous flexible polyester fiber POY silk, the material of described porous flexible polyester fiber POY silk is modified poly ester, Described modified poly ester form by p-phthalic acid segment, ethylene glycol segment and containing the dihydroxylic alcohols segment of side chain, described containing side chain Dihydroxylic alcohols segment refers to that side chain is located on one of dihydroxylic alcohols segment non-end group carbon and side chain is containing 5-10 carbon atom The dihydroxylic alcohols segment of linear carbon chain；
The filament number of described porous flexible polyester fiber POY silk is 0.3～2.0dtex, initial moduluss≤70cN/ Dtex, fracture strength >=2.6cN/dtex, elongation at break is 100.0 ± 10.0%；Described porous flexible polyester fiber POY silk At temperature is 80～130 DEG C, the spatial joint clearance of fibrous inside molecule interchain increases 10～30v/v%, at 260～290 DEG C, Melt viscosity declines 10～20%；Line density deviation ratio≤0.2% of described porous flexible polyester fiber POY silk, fracture strength CV value≤2.5%, extension at break CV value≤5.0%.
Present invention also offers a kind of preparation method of porous flexible polyester fiber POY silk, modified poly ester is adopted porous Spinneret spinning is obtained porous flexible polyester fiber POY silk；On described porous spinneret, the arrangement mode of spinneret orifice is ellipse Arrangement, described oval shaped arrangements refer to that the hole of spinneret orifice is centrally located on concentration ellipse, and described concentration ellipse is that series is oval, institute There is the major axis of ellipse conllinear, and short axle is conllinear；
The preparation method of described porous flexible polyester fiber POY silk is：Modified poly ester obtains Modified polyester chips through pelletizing, Modified polyester chips are through measuring, extruding, cool down, oil and wind prepared modified poly ester POY silk；
The preparation process of described modified poly ester is：
(1) preparation of p-phthalic acid binary alcohol esters；
P-phthalic acid is made into after slurry with the dihydroxylic alcohols containing side chain, under the catalytic action of concentrated sulphuric acid, is esterified Reaction obtains p-phthalic acid binary alcohol esters；The described dihydroxylic alcohols segment containing side chain refers to that side chain is located in dihydroxylic alcohols segment On individual non-end group carbon and side chain is the dihydroxylic alcohols segment of 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 presence of side chain, makes strand Spatial volume increases, and solvation diminishes, and in dihydroxylic alcohols, proton is difficult to dissociate so that containing dihydroxylic alcohols and the terephthaldehyde of side chain The reactivity of acid is 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 ratio in polyester macromolecule for the dihydroxylic alcohols containing side chain for the impact, and then affect the performance of polyester.This Using first the dihydroxylic alcohols containing side chain being carried out esterification with p-phthalic acid under the catalytic action of sulphuric acid, its product exists for invention Ethylene glycol and p phthalic acid esterification add it is ensured that containing the stability of the dihydroxylic alcohols proportioning of side chain after terminating；
(2) preparation of ethylene glycol terephthalate；
P-phthalic acid and ethylene glycol are made into after slurry, carry out esterification, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester；
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), stir Mix mixing, in the presence 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, prepared modified poly ester.
As preferred technical scheme：
A kind of preparation method of porous flexible polyester fiber POY silk as above, the concrete preparation of described modified poly ester Step 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 anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is normal pressure～0.3MPa, and temperature is 180～240 DEG C, works as ester It is esterification terminal that water quantity of distillate in change reaction reaches during more than the 90% of theoretical value, obtains p-phthalic acid dihydroxylic alcohols Ester；
(2) preparation of ethylene glycol terephthalate；
P-phthalic acid and ethylene glycol are made into after slurry, carry 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% when be esterification terminal, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester；
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), stir Mix mixing 15-20 minute, in the presence 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 at 260～270 DEG C, the response time is temperature control 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, 50～90 minutes response time, prepared modified poly ester；
The main spinning technology parameter of described porous flexible polyester fiber 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.
A kind of preparation method of porous flexible polyester fiber POY silk as above, in step (1), p-phthalic acid with The mol ratio of the dihydroxylic alcohols containing side chain is 1:1.3-1.5；Concentrated sulphuric acid addition is the 0.3-0.5% of p-phthalic acid weight；Institute The concentration stating concentrated sulphuric acid is 50-60wt%；
In step (2), p-phthalic acid is 1 with the mol ratio of ethylene glycol:1.2～2.0；
In step (3), described p-phthalic acid binary alcohol esters are 2 with the Mole percent ratio of ethylene glycol terephthalate ～5%；Described catalyst is antimony oxide, antimony glycol or antimony acetate, and catalyst charge is p-phthalic acid gross weight 0.01%～0.05%；Described stabilizer is triphenyl phosphate, trimethyl phosphate or NSC 6513, stabilizer addition For described p-phthalic acid gross weight 0.01%～0.05%；
The number-average molecular weight of described modified poly ester is 15000～30000.
A kind of preparation method of porous flexible polyester fiber POY silk as above, the described dihydroxylic alcohols containing side chain are 2- Amyl group -1,4 butanediol, 2- hexyl -1,4 butanediol, 2- heptyl -1,4 butanediol, 2- octyl group -1,4 butanediol, 2- nonyl -1,4 Butanediol, 2- decyl -1,4 butanediol, 2- amyl group -1,5 pentanediol, 2- hexyl -1,5 pentanediol, 2- heptyl -1,5 pentanediol, 2- One or more of octyl group -1,5 pentanediol, 2- nonyl -1,5 pentanediol or 2- decyl -1,5 pentanediol.
A kind of preparation method of porous flexible polyester fiber POY silk as above, described spinneret orifice be arranged as major axis And/or short axle is symmetrical.
A kind of preparation method of porous flexible polyester fiber POY silk as above, oval major axis and minor axis length Ratio is 1.3～1.8；The guide hole diameter that the spacing of adjacent spinneret orifice is more than or equal to spinneret orifice adds 1.5mm.When having of spinneret 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 row to effect area phase The number of plies of row, 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 are conducive to The cooling of ring blowing, improves the cooling effectiveness of ring blowing, and the fibre property of preparation is also more excellent.Major axis and the ratio of minor axis length Value is closer to 1, and ellipse is more similar to justify, and the difference of cooling effectiveness and cooling effect is little；Major axis and the ratio of minor axis length During for 1.3, cooling effect significantly improves, and individual pen hole count is corresponding to increase by 16%；When the ratio of major axis and minor axis length is 1.8, cold But effect raising is larger, and individual pen hole count is corresponding to increase by 33%, in the case of identical hole count, and the oval shaped arrangements of the present invention are more same than conventional The number of turns of heart circle best-fit reduces it is easy to cooling wind thoroughly, makes the fiber cooling condition of Internal and external cycle evenly；Major axis and minor axis length Ratio when being more than 1.8, ellipse is partial to form flat shape, is difficult to punch, cooling no longer raises.Therefore, The oval major axis of series is 1.3～1.8 with the ratio of minor axis length, can reach higher cooling effectiveness and preferable cooling effect Really.
A kind of preparation method of porous flexible polyester fiber POY silk as above, described spinneret is circular spinneret Or elliptical spinneret plate；The diameter of described circle spinneret is more than 10mm, institute with the difference of the oval maximum long axis length of series The difference stating elliptical spinneret plate with the oval maximum long axis length of series is more than 10mm.
A kind of preparation method of porous flexible polyester fiber POY silk as above, the guide hole of described spinneret orifice is a diameter of 1.5～2.5mm；The spray webbing hole count of described spinneret is more than or equal to 192.
A kind of preparation method of porous flexible polyester fiber POY silk as above, the spinneret orifice of described spinneret Shape of cross section is circle, square, rhombus, yi word pattern, triangular form, trilobal cross, hollow type or platypelloid type.
The principle of the present invention is：
For unbranched polyester fiber, its molecular chain structure is the linear macromolecule containing benzene ring structure, on strand Functional group's marshalling, regularity is good, flexible poor；When temperature raises, its free volume increments is little, and these characteristics hinder Hinder dyestuff to enter inside polyester fiber, thus dyeability is poor.
The raw material of the polyester fiber of the present invention is modified poly ester, the dihydroxylic alcohols containing side chain containing 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 and no props up The characteristic of the polyester macromolecule chain of chain, the increase of free volume improves the degree within molecule entrance polyester, modified The free volume of the polyester fiber of polyester preparation is far longer than unbranched polyester fiber at equal temperature, increases the diffusion of dyestuff Degree, improves the dyeability of polyester fiber.Meanwhile, the polyester fiber of modified poly ester preparation 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 have 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, 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 is more than the hole count of circular arrangement, using spray The spinneret of silk hole oval shaped arrangements enables to that fiber is quick, uniformly cools down, and between fiber, the difference of structure and performance is less, Be conducive to improving the even dyeing rate of fiber and the performance 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 When, the number of plies of spinneret orifice oval shaped arrangements is less than the number of plies of circular arrangement, and ring blowing is easier to blow through dynamic analysis of spinning, dynamic analysis of spinning Cooling effect more preferably, the fibre property of preparation is also 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 When, the hole count of spinneret orifice oval shaped arrangements is more than the hole count of circular arrangement, and oval shaped arrangements are capable of greatly cooling down, Significantly improve cooling effectiveness.
3) material of the porous flexible polyester fiber POY silk that the present invention is obtained is modified poly ester, in modified poly ester macromole The dihydroxylic alcohols segment containing side chain containing, when temperature is higher than vitrification point, side chain, prior to backbone motion, makes free volume Increasing degree is far longer than the characteristic of unbranched polyester macromolecule chain, and the increase of free volume improves molecule and enters and gathers Degree within ester, increases the diffusion of dyestuff by the free volume that side chain increased polyester fiber, improves polyester fine The dyeability of dimension.
4) the porous flexible polyester fiber POY silk that the present invention is obtained, the increase of polyester fiber free volume advantageously reduces Melt viscosity, is conducive to improving its processing characteristics.
5) the porous flexible polyester fiber POY silk that the present invention is obtained, the dihydroxylic alcohols segment containing side chain introducing to polyester The structural regularity of fiber does not have big destruction, maintains the premium properties of polyester fiber.
6) present invention is obtained porous flexible polyester fiber POY silk dyeability and good mechanical performance, initial moduluss≤ 70cN/dtex, line density deviation ratio≤0.2% of porous flexible polyester fiber POY silk, fracture strength CV value≤2.5%, fracture Elongation CV value≤5.0%.
Brief description
Fig. 1 is the oval shaped arrangements figure of 374 spinneret orifices, and the aperture of spinneret orifice is 2.0mm, the length of transverse and 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, the length of transverse and short axle Degree ratio is 1.6.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It 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 of present invention instruction, art technology Personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited Fixed scope.
Embodiment 1
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:1.3 p-phthalic acid and 2- amyl group-Isosorbide-5-Nitrae butanediol are made into slurry and add in reactor, Concentration is 50wt%, and addition is under the catalytic action of 0.3% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is normal pressure, and temperature is 180 DEG C, when the water in esterification distillates It is esterification terminal that amount reaches during the 90% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.2 p-phthalic acids and ethylene glycol add in reactor after being made into slurry, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is normal pressure, and temperature is 250 DEG C, when the water in esterification distillates It is esterification terminal that amount reaches during the 90% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 2% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 15 minutes is adding Measure for p-phthalic acid weight 0.01% the catalytic antimony trioxide and addition be p-phthalic acid weight 0.01% Stabilizer triphenyl phosphate in the presence of, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure Steadily being evacuated to absolute pressure by normal pressure is 500Pa, and at 260 DEG C, the response time is 30 minutes to temperature control；Then proceed to take out very Sky, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 100Pa, and reaction temperature controls 275 DEG C, 50 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 15000, by p-phthalic acid segment, ethylene glycol segment and 2- penta Base-Isosorbide-5-Nitrae butanediol segment composition, 2- amyl group-Isosorbide-5-Nitrae butanediol segment is 2% with the Mole percent ratio of ethylene glycol segment.
Embodiment 2
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:1.38 p-phthalic acid and 2- hexyl-Isosorbide-5-Nitrae butanediol are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of 0.32% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.13MPa, and temperature is 181 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 91% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.3 p-phthalic acids and ethylene glycol add in reactor after being made into slurry, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.12MPa, and temperature is 251 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 91% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 2.1% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 16 minutes is adding Entering 0.011% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.02% stabilizer triphenyl phosphate, start the polycondensation reaction in coarse vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 262 DEG C, the response time is 31 minutes to temperature control；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 99Pa, and reaction temperature controls at 276 DEG C, 51 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 16000, 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 2.1% with the Mole percent ratio of ethylene glycol segment.
Embodiment 3
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:1.33 p-phthalic acid and 2- heptyl-Isosorbide-5-Nitrae butanediol are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of 0.33% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.12MPa, and temperature is 183 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.31 p-phthalic acids and ethylene glycol add in reactor after being made into slurry, carry out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.31MPa, and temperature is 252 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 2.2% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 16 minutes is adding Entering 0.03% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.02% stabilizer triphenyl phosphate, start the polycondensation reaction in coarse vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 498Pa by normal pressure, and at 263 DEG C, the response time is 32 minutes to temperature control；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 80Pa, and reaction temperature controls at 277 DEG C, 57 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 15900, 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 2.2% with the Mole percent ratio of ethylene glycol segment.
Embodiment 4
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:1.34 p-phthalic acid and 2- octyl group-Isosorbide-5-Nitrae butanediol are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of 0.34% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.13MPa, and temperature is 184 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 93% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.32 p-phthalic acids and ethylene glycol add in reactor after being made into slurry, carry out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.33MPa, and temperature is 253 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 93% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 2.3% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 17 minutes is adding Entering 0.033% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.023% stabilizer triphenyl phosphate, start the polycondensation reaction in coarse vacuum stage, this rank It is 497Pa that section pressure is steadily evacuated to absolute pressure by normal pressure, and at 264 DEG C, the response time is 33 minutes to temperature control；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, 58 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 15800, 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 2.3% with the Mole percent ratio of ethylene glycol segment.
Embodiment 5
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:1.35 p-phthalic acid and 2- nonyl-Isosorbide-5-Nitrae butanediol are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of 0.36% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.14MPa, and temperature is 185 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 93.2% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.33 p-phthalic acids and ethylene glycol add in reactor after being made into slurry, carry out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.14MPa, and temperature is 254 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 93.2% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 2.4% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 17 minutes is adding Entering 0.034% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.024% stabilizer triphenyl phosphate, start the polycondensation reaction in coarse vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and at 265 DEG C, the response time is 34 minutes to temperature control；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 70Pa, and reaction temperature controls 277 DEG C, 59 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 15900, 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 2.4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 6
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:1.36 p-phthalic acid and 2- decyl-Isosorbide-5-Nitrae butanediol are made into slurry and add in reactor, Concentration is 50wt%, and addition is under the catalytic action of 0.37% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.15MPa, and temperature is 186 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 93.3% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.34 p-phthalic acids and ethylene glycol add in reactor after being made into slurry, carry out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.15MPa, and temperature is 255 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 93.3% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 2.5% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Entering 0.035% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.025% stabilizer triphenyl phosphate, start the polycondensation reaction in coarse vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 266 DEG C, the response time is 35 minutes to temperature control；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, 60 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 16000, by p-phthalic acid segment, ethylene glycol segment and the 2- last of the ten Heavenly stems Base-Isosorbide-5-Nitrae butanediol segment composition, 2- decyl-Isosorbide-5-Nitrae butanediol segment is 2.5% with the Mole percent ratio of ethylene glycol segment.
Embodiment 7
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:1.37 p-phthalic acid and 2- amyl group-Isosorbide-5-Nitrae butanediol are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of 0.38% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.16MPa, and temperature is 187 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 93.4% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.36 p-phthalic acids and ethylene glycol add in reactor after being made into slurry, carry out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.16MPa, and temperature is 256 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 93.4% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 2.6% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 19 minutes is adding Entering 0.036% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.025% stabilizer triphenyl phosphate, start the polycondensation reaction in coarse vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and at 267 DEG C, the response time is 36 minutes to temperature control；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, 61 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 16000, by p-phthalic acid segment, ethylene glycol segment and 2- penta Base-Isosorbide-5-Nitrae butanediol segment composition, 2- amyl group-Isosorbide-5-Nitrae butanediol segment is 2.6% with the Mole percent ratio of ethylene glycol segment.
Embodiment 8
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:1.38 p-phthalic acid and 2- hexyl-Isosorbide-5-Nitrae butanediol are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of 0.39% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.17MPa, and temperature is 188 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 93.5% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.37 p-phthalic acids and ethylene glycol add in reactor after being made into slurry, carry out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.17MPa, and temperature is 257 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 93.5% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 2.7% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 19 minutes is adding Entering 0.036% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.025% stabilizer triphenyl phosphate, start the polycondensation reaction in coarse vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and at 267 DEG C, the response time is 36 minutes to temperature control；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 60Pa, and reaction temperature controls 278 DEG C, 61 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 17000, 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
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:1.39 p-phthalic acid and 2- heptyl-Isosorbide-5-Nitrae butanediol are made into slurry and add in reactor, Concentration is 50wt%, and addition is under the catalytic action of 0.4% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.17MPa, and temperature is 188 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 93.5% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.37 p-phthalic acids and ethylene glycol add in reactor after being made into slurry, carry out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.17MPa, and temperature is 257 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 93.5% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 2.8% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 16 minutes is adding Entering 0.04% catalyst glycol antimony that amount is p-phthalic acid weight and addition is the 0.026% of p-phthalic acid weight Stabilizer trimethyl phosphate in the presence of, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure Absolute pressure 497Pa is steadily evacuated to by normal pressure, at 268 DEG C, the response time is 38 minutes to temperature control；Then proceed to evacuation, Carry out the polycondensation reaction of high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 50Pa, and reaction temperature controls at 279 DEG C, instead 62 minutes between seasonable, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 18000, 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
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:1.4 p-phthalic acid and 2- octyl group-Isosorbide-5-Nitrae butanediol are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of 0.4% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.17MPa, and temperature is 188 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 93.5% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.38 p-phthalic acids and ethylene glycol add in reactor after being made into slurry, carry out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.18MPa, and temperature is 257.8 DEG C, when in esterification Water quantity of distillate reach theoretical value 93.6% when be esterification terminal, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 3% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 17 minutes is adding Measure for p-phthalic acid weight 0.03% catalyst glycol antimony and addition be the 0.027% of p-phthalic acid weight In the presence 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 at 269 DEG C, the response time is 39 minutes to temperature control；Then proceed to evacuation, enter The polycondensation reaction of row high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 50Pa, and reaction temperature controls at 278 DEG C, reaction 64 minutes time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 19000, 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
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:1.4 p-phthalic acid and 2- nonyl-Isosorbide-5-Nitrae butanediol are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of 0.4% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.18MPa, and temperature is 189 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 93.6% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.39 p-phthalic acids and ethylene glycol add in reactor after being made into slurry, carry out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.19MPa, and temperature is 258.8 DEG C, when in esterification Water quantity of distillate reach theoretical value 94% when be esterification terminal, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Measure for p-phthalic acid weight 0.04% catalyst glycol antimony and addition be the 0.03% of p-phthalic acid weight In the presence 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 at 260 DEG C, the response time is 40 minutes to temperature control；Then proceed to evacuation, enter The polycondensation reaction of row high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 40Pa, and reaction temperature controls at 277 DEG C, reaction 63 minutes time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 20000, 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
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:1.4 p-phthalic acid and 2- nonyl-Isosorbide-5-Nitrae butanediol are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of 0.4% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.2MPa, and temperature is 200 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 94% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.6 p-phthalic acids and ethylene glycol add in reactor after being made into slurry, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.2MPa, and temperature is 256 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 94% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.5% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Enter that amount is 0.038% catalyst acetic acid antimony of p-phthalic acid weight and addition is p-phthalic acid weight 0.03% Under conditions of negative pressure, in the presence of stabilizer NSC 6513, start the polycondensation reaction in coarse vacuum stage, this staged pressure Absolute pressure 497Pa is steadily evacuated to by normal pressure, at 265 DEG C, the response time is 42 minutes to temperature control；Then proceed to evacuation, Carry out the polycondensation reaction of high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 40Pa, and reaction temperature controls at 277 DEG C, instead 70 minutes between seasonable, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 26000, by p-phthalic acid segment, ethylene glycol segment and the 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
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:1.5 p-phthalic acid and 2- decyl -1,5 pentanediols are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of 0.5% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.3MPa, and temperature is 240 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during 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 acids and ethylene glycol add in reactor after being made into slurry, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.3MPa, and temperature is 260 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 5% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 20 minutes is adding Measure for p-phthalic acid weight 0.05% catalyst acetic acid antimony and addition be p-phthalic acid weight 0.05% steady In the presence of determining 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 at 270 DEG C, the response time is 50 minutes to temperature control；Then proceed to evacuation, Carry 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 90 minutes between seasonable, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 30000, by p-phthalic acid segment, ethylene glycol segment and the 2- last of the ten Heavenly stems Base -1,5 pentanediol segment compositions, 2- decyl -1,5 pentanediol segments are 5% with the Mole percent ratio of ethylene glycol segment.
Embodiment 14
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:1.47 p-phthalic acid 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 0.47% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 220 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during 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 acids and ethylene glycol add in reactor after being made into slurry, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27MPa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Measure for p-phthalic acid weight 0.04% catalyst glycol antimony and addition be the 0.04% of p-phthalic acid weight In the presence 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 at 263 DEG C, the response time is 47 minutes to temperature control；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, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester 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% with the Mole percent ratio of ethylene glycol segment.
Embodiment 15
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:1.46 p-phthalic acid 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 0.49% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 233 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during 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 acids and ethylene glycol add in reactor after being made into slurry, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 259 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.5% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 19 minutes is adding Entering 0.044% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.046% stabilizer triphenyl phosphate, start the polycondensation reaction in coarse vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 269 DEG C, the response time is 48 minutes to temperature control；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, 87 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 29000, 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 4.5% with the Mole percent ratio of ethylene glycol segment.
Embodiment 16
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:1.49 p-phthalic acid and 2- heptyl -1,5 pentanediols are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of 0.48% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 230 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during 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 acids and ethylene glycol add in reactor after being made into slurry, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.7% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 19 minutes is adding Entering 0.048% catalyst glycol antimony that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.047% stabilizer triphenyl phosphate, start the polycondensation reaction in coarse vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 460Pa by normal pressure, and at 267 DEG C, the response time is 48 minutes to temperature control；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, 83 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 27000, by p-phthalic acid segment, ethylene glycol segment and 2- heptan Base -1,5 pentanediol segment compositions, 2- heptyl -1,5 pentanediol segments are 4.7% with the Mole percent ratio of ethylene glycol segment.
Embodiment 17
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:1.467 p-phthalic acid and 2- hexyl -1,5 pentanediols are made into slurry and add in reactor, It is 60wt% in concentration, addition is under the catalytic action of 0.47% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27MPa, and temperature is 236 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during 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 acids and ethylene glycol add in reactor after being made into slurry, carry out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 258 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.3% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Entering 0.04% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.041% stabilizer NSC 6513, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 268 DEG C, the response time is 48 minutes to temperature control；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, reaction temperature controls 278 DEG C, 85 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 29000, own by p-phthalic acid segment, ethylene glycol segment and 2- Base -1,5 pentanediol segment compositions, 2- hexyl -1,5 pentanediol segments are 4.3% with the Mole percent ratio of ethylene glycol segment.
Embodiment 18
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:1.48 p-phthalic acid 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 0.46% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 230 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during 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 acids and ethylene glycol add in reactor after being made into slurry, carry out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 256 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.7% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Entering 0.047% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.047% stabilizer triphenyl phosphate, start the polycondensation reaction in coarse vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 480Pa by normal pressure, and at 265 DEG C, the response time is 47 minutes to temperature control；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, 85 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 28000, 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 4.7% with the Mole percent ratio of ethylene glycol segment.
Embodiment 19
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:1.46 p-phthalic acid 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 0.47% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 238 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during 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 acids and ethylene glycol add in reactor after being made into slurry, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 259 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during more than the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.7% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 19 minutes is adding Entering the 0.046% catalyst acetic acid antimony that amount is p-phthalic acid weight and addition is the 0.048% of p-phthalic acid weight Stabilizer NSC 6513 in the presence of, 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 at 267 DEG C, the response time is 49 minutes to temperature control；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, 87 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 29000, by p-phthalic acid segment, ethylene glycol segment and the 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
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:1.46 p-phthalic acid 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 0.46% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.26MPa, and temperature is 221 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during 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 acids and ethylene glycol add in reactor after being made into slurry, carry out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.25MPa, and temperature is 259 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.1% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Entering 0.041% catalyst glycol antimony that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.042% stabilizer trimethyl phosphate, start the polycondensation reaction in coarse vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 460Pa by normal pressure, and at 265 DEG C, the response time is 47 minutes to temperature control；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, 85 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester 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
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:1.43 p-phthalic acid 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 0.47% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27MPa, and temperature is 235 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during 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 acids and ethylene glycol add in reactor after being made into slurry, carry out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.26MPa, and temperature is 255 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.3% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 17 minutes is adding Entering 0.043% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.049% stabilizer triphenyl phosphate, start the polycondensation reaction in coarse vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 268 DEG C, the response time is 46 minutes to temperature control；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, 85 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester 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
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:1.43 p-phthalic acid 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 0.45% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.29MPa, and temperature is 235 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during 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 acids and ethylene glycol add in reactor after being made into slurry, carry out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27MPa, and temperature is 255 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.6% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Entering 0.047% catalyst glycol antimony that amount is p-phthalic acid weight and addition is the 0.04% of p-phthalic acid weight Stabilizer triphenyl phosphate in the presence of, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure Absolute pressure 470Pa is steadily evacuated to by normal pressure, at 268 DEG C, the response time is 45 minutes to temperature control；Then proceed to evacuation, Carry 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, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester 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
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:1.457 p-phthalic acid and 2- hexyl -1,5 pentanediols are made into slurry and add in reactor, It is 55% in concentration, addition is under the catalytic action of 0.46% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 239 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during 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 acids and ethylene glycol add in reactor after being made into slurry, carry out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27MPa, and temperature is 255 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.41% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 19 minutes, Addition is 0.042% the catalytic antimony trioxide of p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.048% stabilizer NSC 6513, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the response time is 45 minutes to temperature control；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50Pa, reaction temperature controls 275 DEG C, 85 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester 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
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:1.47 p-phthalic acid 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 0.48% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27MPa, and temperature is 245 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during 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 acids and ethylene glycol add in reactor after being made into slurry, carry out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27MPa, and temperature is 259 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.67% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 19 minutes, Addition is 0.041% the catalytic antimony trioxide of p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.042% stabilizer triphenyl phosphate, start the polycondensation reaction in coarse vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 485Pa by normal pressure, and at 268 DEG C, the response time is 46 minutes to temperature control；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, 89 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester 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
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:1.45 p-phthalic acid and 2- hexyl -1,5 pentanediol and 2- amyl group -1,4 butanediol mixed 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, It is 55% in concentration, addition is under the catalytic action of 0.49% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.26MPa, and temperature is 236 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during 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 acids and ethylene glycol add in reactor after being made into slurry, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.4% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Entering 0.042% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.047% stabilizer NSC 6513, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the response time is 49 minutes to temperature control；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50Pa, reaction temperature controls 278 DEG C, 88 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester be 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
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:2- octyl group -1,5 pentanediol of 1.45 p-phthalic acid sum 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 0.45% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 239 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during 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 acids and ethylene glycol add in reactor after being made into slurry, carry out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.29MPa, and temperature is 255 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.6% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Entering 0.0423% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.045% stabilizer NSC 6513, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the response time is 45 minutes to temperature control；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50Pa, reaction temperature controls 278 DEG C, 85 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester be 28000, by p-phthalic acid segment, ethylene glycol segment, 2- octyl group- 1,5 pentanediol segment and 2- amyl group -1,5 pentanediol segment compositions, 2- octyl group -1,5 pentanediol 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
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:1.45 p-phthalic acid and 2- hexyl -1,5 pentanediol and 2- amyl group -1,4 butanediol mixed 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, It is 55% in concentration, addition is under the catalytic action of 0.49% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.26MPa, and temperature is 236 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during 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 acids and ethylene glycol add in reactor after being made into slurry, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.4% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Entering 0.042% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.047% stabilizer NSC 6513, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the response time is 49 minutes to temperature control；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50Pa, reaction temperature controls 278 DEG C, 88 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester be 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
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of p-phthalic acid binary alcohol esters：
Mol ratio is 1:1.45 p-phthalic acid is own with 2- octyl group -1,5 pentanediol, 2- amyl group -1,4 butanediol and 2- Base -1, the mixture of 5 pentanediols is made into slurry and adds in reactor, wherein 2- octyl group -1,5 pentanediols, 2- amyl group-Isosorbide-5-Nitrae fourth two The mol ratio of alcohol and 2- hexyl -1,5 pentanediol is 3:2:1, it is 60% in concentration, addition is p-phthalic acid weight Under the catalytic action of 0.47% concentrated sulphuric acid, carry out esterification, esterification 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 acids and ethylene glycol add in reactor after being made into slurry, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27MPa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.71% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, Addition is 0.04% the catalytic antimony trioxide of p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.041% stabilizer NSC 6513, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 268 DEG C, the response time is 49 minutes to temperature control；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50Pa, reaction temperature controls 277 DEG C, 84 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 29000, by p-phthalic acid segment, ethylene glycol segment, band side chain Glycol segment composition, wherein branched glycol segment be 2- octyl group -1,5 pentanediol segments, 2- amyl group-Isosorbide-5-Nitrae butanediol chain Section and 2- hexyl -1,5 pentanediol segments form, and branched glycol segment with the Mole percent ratio of ethylene glycol segment is 4.71%.
Embodiment 29
A kind of preparation method of porous flexible polyester fiber POY silk, porous flexible polyester fiber POY silk adopts porous spray webbing Plate is obtained, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located at On concentration ellipse, concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear.
As shown in figure 1, the major axis of ellipse is 1.3 with the ratio of minor axis length, the spacing of adjacent spinneret orifice is equal to spinneret orifice Guide hole diameter add 1.5mm, spinneret is circular spinneret, the diameter of circular spinneret oval maximum long axial length with series The difference of degree is 11mm, a diameter of 2.0mm of guide hole of spinneret orifice, and the spray webbing hole count of spinneret is 374, the spinneret orifice of spinneret Shape of cross section be circle.
The modified modified polyester that embodiment 1 is obtained, obtains Modified polyester chips through pelletizing；Again through metering, extrusion, cold But, oil and wind, prepared 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, the speed of winding For 2500m/min；
The filament number of prepared porous flexible polyester fiber POY silk is 1.4dtex, initial moduluss 68cN/dtex, fracture Intensity is 4.7cN/dtex, and elongation at break is 105.6%；Porous flexible polyester fiber POY silk temperature be 80 DEG C at, fiber The spatial joint clearance of interior molecules interchain increases 15v/v%, and at 289 DEG C, melt viscosity declines 16%；Porous flexible polyester fiber The line density deviation ratio of POY silk is 0.13%, and fracture strength CV value is 2.2%, and extension at break CV value is 3.9%.
Embodiment 30
A kind of preparation method of porous flexible polyester fiber POY silk, porous flexible polyester fiber POY silk adopts porous spray webbing Plate is obtained, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located at On concentration ellipse, concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear.
As shown in figure 3, the major axis of ellipse is 1.6 with the ratio of minor axis length, the spacing of adjacent spinneret orifice is equal to spinneret orifice Guide hole diameter add 1.5mm, spinneret is circular spinneret, the diameter of circular spinneret oval maximum long axial length with series The difference of degree is 11mm, a diameter of 2.0mm of guide hole of spinneret orifice, and the spray webbing hole count of spinneret is 382, the spinneret orifice of spinneret Shape of cross section be circle.
The modified modified polyester that embodiment 1 is obtained, obtains Modified polyester chips through pelletizing；Again through metering, extrusion, cold But, oil and wind, prepared 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, the speed of winding For 2500m/min；
The filament number of prepared porous flexible polyester fiber POY silk is 1.7dtex, initial moduluss 70cN/dtex, fracture Intensity is 5.6N/dtex, and elongation at break is 109.6%；Porous flexible polyester fiber POY silk temperature be 80 DEG C at, fiber The spatial joint clearance of interior molecules interchain increases 15v/v%, and at 289 DEG C, melt viscosity declines 16%；Porous flexible polyester fiber The line density deviation ratio of POY silk is 0.11%, and fracture strength CV value is 2.1%, and extension at break CV value is 3.6%.
Comparative example 1
A kind of preparation method of porous flexible polyester fiber POY silk, porous flexible polyester fiber POY silk adopts porous spray webbing Plate is obtained, and on spinneret, the arrangement mode of spinneret orifice is circular arrangement, and circular arrangement refers to that the hole of spinneret orifice is centrally located at one heart On circle, concentric circular is that series is circular.As shown in Fig. 2 the guide hole diameter that the spacing of adjacent spinneret orifice is equal to spinneret orifice adds 1.5mm, spinneret is circular spinneret, and the diameter of circular spinneret is 11mm with the difference of the circular maximum diameter of series, spray The a diameter of 2.0mm of guide hole in silk hole, the spray webbing hole count of spinneret is 370, and the shape of cross section of the spinneret orifice of spinneret is circle Shape.
The modified modified polyester that embodiment 1 is obtained, obtains Modified polyester chips through pelletizing；Again through metering, extrusion, cold But, oil and wind, prepared 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, the speed of winding For 2500m/min；
The filament number of prepared porous flexible polyester fiber POY silk is 1.0dtex, initial moduluss 65cN/dtex, fracture Intensity is 2.7cN/dtex, and elongation at break is 108.6%；Porous flexible polyester fiber POY silk temperature be 80 DEG C at, fiber The spatial joint clearance of interior molecules interchain increases 15v/v%, and at 289 DEG C, melt viscosity declines 16%；Porous flexible polyester fiber The line density deviation ratio of POY silk is 0.23%, and fracture strength CV value is 2.7%, and extension at break CV value is 5.9%.
When identical with the effective area that embodiment 29 contrast can be seen that spinneret, (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 identical with the effective area that embodiment 30 contrast can be seen that spinneret, 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 evenness fault that embodiment 29 and embodiment 30 are obtained Rate CV value is less than comparative example 1, under the conditions of same process is described, using the prepared fibroids of the spinneret of spinneret orifice oval shaped arrangements Can be better than the spinneret using spinneret circular arrangement.
Embodiment 31～33
A kind of preparation method of porous flexible polyester fiber POY silk, porous flexible polyester fiber POY silk adopts porous spray webbing Plate is obtained, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located at On concentration ellipse, concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear.
Spinneret orifice be arranged as long axial symmetry, oval major axis is 1.4 with the ratio of minor axis length, between adjacent spinneret orifice Add 1.6mm away from the guide hole diameter equal to spinneret orifice, spinneret is circular spinneret, the diameter of circular spinneret 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, extruding, cool down, oil and wind, prepared 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；Prepared porous Porous flexible polyester fiber POY silk at 80 DEG C the spatial joint clearance Magnification of fibrous inside molecule interchain, at 260 DEG C melt glue Degree rate of descent and the mechanical performance data such as following table of fiber.
Embodiment 34～36
A kind of preparation method of porous flexible polyester fiber POY silk, porous flexible polyester fiber POY silk adopts porous spray webbing Plate is obtained, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located at On concentration ellipse, concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear.
Spinneret orifice be arranged as that short axle is symmetrical, oval major axis is 1.4 with the ratio of minor axis length, between adjacent spinneret orifice Add 1.7mm away from the guide hole diameter equal to spinneret orifice, spinneret is elliptical spinneret plate, elliptical spinneret plate is with serial ellipse 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 Spinneret orifice shape of cross section be rhombus.
Modified poly ester, obtains Modified polyester chips through pelletizing；Again through measuring, extruding, cool down, oil and wind, prepared 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；Prepared porous Porous flexible polyester fiber POY silk at 130 DEG C the spatial joint clearance Magnification of fibrous inside molecule interchain, at 290 DEG C melt The mechanical performance data of viscosity rate of descent and fiber such as following table.
Embodiment 37～39
A kind of preparation method of porous flexible polyester fiber POY silk, porous flexible polyester fiber POY silk adopts porous spray webbing Plate is obtained, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located at On concentration ellipse, concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear.
Spinneret orifice be arranged as that major axis and short axle are symmetrical, oval major axis is 1.4 with the ratio of minor axis length, adjacent spray webbing The guide hole diameter that the spacing in hole is equal to spinneret orifice adds 1.8mm, and spinneret is circular spinneret, the diameter of circular spinneret be The difference of the oval maximum long axis length of row is 13mm, a diameter of 2.5mm of guide hole of spinneret orifice, and 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, extruding, cool down, oil and wind, prepared POY Silk, the temperature of the extrusion of POY silk is 286 DEG C, and the pathogenic wind-warm of cooling is 21 DEG C, and the speed of winding is 2700m/min；Prepared porous Porous flexible polyester fiber POY silk at 100 DEG C the spatial joint clearance Magnification of fibrous inside molecule interchain, at 290 DEG C melt The mechanical performance data of viscosity rate of descent and fiber such as following table.
Embodiment 40～42
A kind of preparation method of porous flexible polyester fiber POY silk, porous flexible polyester fiber POY silk adopts porous spray webbing Plate is obtained, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located at On concentration ellipse, concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear.
Spinneret orifice be arranged as that major axis and short axle are symmetrical, oval major axis is 1.7 with the ratio of minor axis length, adjacent spray webbing The spacing in hole be equal to spinneret orifice guide hole diameter add 1.9mm, spinneret be elliptical spinneret plate, elliptical spinneret plate with 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, extruding, cool down, oil and wind, prepared POY Silk, the temperature of the extrusion of POY silk is 281 DEG C, and the pathogenic wind-warm of cooling is 24 DEG C, and the speed of winding is 3000m/min；Prepared porous Porous flexible polyester fiber POY silk at 110 DEG C the spatial joint clearance Magnification of fibrous inside molecule interchain, at 289 DEG C melt The mechanical performance data of viscosity rate of descent and fiber such as following table.
Embodiment 43～45
A kind of preparation method of porous flexible polyester fiber POY silk, porous flexible polyester fiber POY silk adopts porous spray webbing Plate is obtained, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located at On concentration ellipse, concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear.
Spinneret orifice be arranged as that short axle is symmetrical, oval major axis is 1.8 with the ratio of minor axis length, between adjacent spinneret orifice Add 1.5mm away from the guide hole diameter equal to spinneret orifice, spinneret is circular spinneret, the diameter of circular spinneret is oval with series The difference of maximum long axis length is 15mm, a diameter of 1.8mm of guide hole of spinneret orifice, and 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, extruding, cool down, oil and wind, prepared POY Silk, the temperature of the extrusion of POY silk is 284 DEG C, and the pathogenic wind-warm of cooling is 23 DEG C, and the speed of winding is 2760m/min；Prepared porous Porous flexible polyester fiber POY silk at 120 DEG C the spatial joint clearance Magnification of fibrous inside molecule interchain, at 270 DEG C melt The mechanical performance data of viscosity rate of descent and fiber such as following table.
Embodiment 46～49
A kind of preparation method of porous flexible polyester fiber POY silk, porous flexible polyester fiber POY silk adopts porous spray webbing Plate is obtained, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located at On concentration ellipse, concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear.
Spinneret orifice be arranged as long axial symmetry, oval major axis is 1.8 with the ratio of minor axis length, between adjacent spinneret orifice Add 1.6mm away from the guide hole diameter equal to spinneret orifice, spinneret is circular spinneret, the diameter of circular spinneret is oval with series The difference of maximum long axis length is 16mm, a diameter of 2.2mm of guide hole of spinneret orifice, and 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, extruding, cool down, oil and wind, prepared POY Silk, the temperature of the extrusion of POY silk is 286 DEG C, and the pathogenic wind-warm of cooling is 25 DEG C, and the speed of winding is 2600m/min；Prepared porous Porous flexible polyester fiber POY silk at 80 DEG C the spatial joint clearance Magnification of fibrous inside molecule interchain, at 275 DEG C melt glue Degree rate of descent and the mechanical performance data such as following table of fiber.
Embodiment 50～53
A kind of preparation method of porous flexible polyester fiber POY silk, porous flexible polyester fiber POY silk adopts porous spray webbing Plate is obtained, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located at On concentration ellipse, concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear.
Spinneret orifice be arranged as that short axle is symmetrical, oval major axis is 1.8 with the ratio of minor axis length, between adjacent spinneret orifice Add 1.8mm away from the guide hole diameter equal to spinneret orifice, spinneret is circular spinneret, the diameter of circular spinneret is oval with series The difference of maximum long axis length is 15mm, a diameter of 2.5mm of guide hole of spinneret orifice, and 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, extruding, cool down, oil and wind, prepared POY Silk, the temperature of the extrusion of POY silk is 285 DEG C, and the pathogenic wind-warm of cooling is 23 DEG C, and the speed of winding is 2550m/min；Prepared porous Porous flexible polyester fiber POY silk at 80 DEG C the spatial joint clearance Magnification of fibrous inside molecule interchain, at 289 DEG C melt glue Degree rate of descent and the mechanical performance data such as following table of fiber.
Embodiment 54～57
A kind of preparation method of porous flexible polyester fiber POY silk, porous flexible polyester fiber POY silk adopts porous spray webbing Plate is obtained, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located at On concentration ellipse, concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear.
Spinneret orifice be arranged as long axial symmetry, oval major axis is 1.8 with the ratio of minor axis length, between adjacent spinneret orifice Add 1.5mm away from the guide hole diameter equal to spinneret orifice, spinneret is circular spinneret, the diameter of circular spinneret is oval with series The difference of maximum long axis length is 16mm, a diameter of 1.8mm of guide hole of spinneret orifice, and 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, extruding, cool down, oil and wind, prepared POY Silk, the temperature of the extrusion of POY silk is 290 DEG C, and the pathogenic wind-warm of cooling is 25 DEG C, and the speed of winding is 2650m/min；Prepared porous Porous flexible polyester fiber POY silk at 130 DEG C the spatial joint clearance Magnification of fibrous inside molecule interchain, at 260 DEG C melt The mechanical performance data of viscosity rate of descent and fiber such as following table.
Embodiment 58
The dyeing of porous flexible polyester fiber POY silk：
The porous porous flexible polyester fiber POY silk of embodiment 29 preparation is dyeed in High Temperature High Pressure machine, specifically Condition is：Before dyeing, porous flexible polyester fiber POY silk nonionic surfactant is processed 30 minutes at 60 DEG C, Ran Houjia Enter in dyeing liquor, the disperse dyes consumption in dyeing liquor is 2.0% (o.w.f)；Dispersant NNO, the concentration of dispersant NNO 1.2g/L；PH value is 5, and bath raio is 1:50, enter dye at 60 DEG C, then heat to 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C and 130 DEG C each constant temperature dyeing 1h.
Using identical dyeing condition, general fibre is dyeed.Porous porous flexible polyester fiber after dyed The dye uptake of POY silk obtains by the following method：
Dye uptake adopts 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, the DMF in dye liquor to be measured and the ratio of water are 70/30 (v/v), and dye liquor absorbance is using purple Outward-visible spectrophotometer measures, and calculates dye uptake with following formula.
In above formula, A0 and A1 is respectively the absorbance dyeing stock solution and dyeing residual liquid.
When disperse dyes are Disperse Red 3B, when disperse blue SE-2R or the bright blue S-GL of dispersion, porous porous flexible polyester fiber The dye uptake result such as following table of POY silk and general fibre：
Contrasted it can be seen that porous is soft by the Color of porous porous flexible polyester fiber POY silk and general fibre The Color of soft polyester fiber POY silk is substantially better than general fibre, also from side illustration present invention preparation modified poly ester The dihydroxylic alcohols segment containing side chain containing in macromole, makes the increasing degree of free volume be far longer than unbranched polyester and divides greatly The characteristic of subchain, the increase of free volume improves the degree within molecule entrance polyester, and prepared by modified polyester poly- The free volume of ester fiber is far longer than unbranched polyester fiber at equal temperature, increases the diffusion of dyestuff, improves poly- The dyeability of ester fiber.
Embodiment 59
The dyeing of porous flexible polyester fiber POY silk：
The porous porous flexible polyester fiber POY silk of embodiment 31 preparation is dyeed in High Temperature High Pressure machine, specifically Condition is：Before dyeing, porous flexible polyester fiber POY silk nonionic surfactant is processed 30 minutes at 60 DEG C, Ran Houjia Enter in dyeing liquor, the disperse dyes consumption in dyeing liquor is 2.0% (o.w.f)；Dispersant NNO, the concentration of dispersant NNO 1.2g/L；PH value is 5, and bath raio is 1:50, enter dye at 60 DEG C, then heat to 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C and 130 DEG C each constant temperature dyeing 1h.
Using identical dyeing condition, general fibre is dyeed.Porous porous flexible polyester fiber after dyed The dye uptake of POY silk obtains by the following method：
Dye uptake adopts 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, the DMF in dye liquor to be measured and the ratio of water are 70/30 (v/v), and dye liquor absorbance is using purple Outward-visible spectrophotometer measures, and calculates dye uptake with following formula.
In above formula, A0 and A1 is respectively the absorbance dyeing stock solution and dyeing residual liquid.
When disperse dyes are Disperse Red 3B, when disperse blue SE-2R or the bright blue S-GL of dispersion, porous porous flexible polyester fiber The dye uptake result such as following table of POY silk and general fibre：
Contrasted by the Color of porous flexible polyester fiber POY silk and general fibre it can be seen that porous is soft poly- The Color of ester fiber POY silk is substantially better than general fibre, and also from side illustration, the modified poly ester of present invention preparation divides greatly The dihydroxylic alcohols segment containing side chain containing in son, makes the increasing degree of free volume be far longer than unbranched polyester macromolecule chain Characteristic, the increase of free volume improves molecule and enters the internal degree of polyester, the polyester fibre of modified polyester preparation The free volume of dimension is far longer than unbranched polyester fiber at equal temperature, increases the diffusion of dyestuff, improves polyester fine The dyeability of dimension.

Claims (10)

1. a kind of porous flexible polyester fiber POY silk, is characterized in that：The material of described porous flexible polyester fiber POY silk is to change Property polyester, described modified poly ester form by p-phthalic acid segment, ethylene glycol segment and containing the dihydroxylic alcohols segment of side chain, described contains The dihydroxylic alcohols segment of side chain refers to that side chain is located on one of dihydroxylic alcohols segment non-end group carbon and side chain is containing 5-10 carbon The dihydroxylic alcohols segment of the linear carbon chain of atom；
The filament number of described porous flexible polyester fiber POY silk is 0.3～2.0dtex, and initial moduluss≤70cN/dtex break Resistance to spalling >=2.6cN/dtex, elongation at break is 100.0 ± 10.0%；Described porous flexible polyester fiber POY silk is in temperature For, at 80～130 DEG C, the spatial joint clearance of fibrous inside molecule interchain increases 10～30v/v%, at 260～290 DEG C, melt glues Degree decline 10～20%；Line density deviation ratio≤0.2% of described porous flexible polyester fiber POY silk, fracture strength CV value≤ 2.5%, extension at break CV value≤5.0%, the spatial joint clearance increase of described molecule interchain refers to modified poly ester and normal polyester Contrast in the spatial joint clearance of mutually synthermal molecule interchain.
2. a kind of preparation method of porous flexible polyester fiber POY silk as claimed in claim 1, is characterized in that：Will be modified poly- Ester adopts porous spinneret spinning that porous flexible polyester fiber POY silk is obtained；The arrangement side of spinneret orifice on described porous spinneret Formula is oval shaped arrangements, and described oval shaped arrangements refer to that the hole of spinneret orifice is centrally located on concentration ellipse, and described concentration ellipse is Series is oval, and all oval major axis are conllinear, and short axle is conllinear；
The preparation method of described porous flexible polyester fiber POY silk is：Modified poly ester obtains Modified polyester chips through pelletizing, modified Polyester slice is through measuring, extruding, cool down, oil and wind prepared modified poly ester POY silk；
The preparation process of described modified poly ester is：
(1) preparation of p-phthalic acid binary alcohol esters；
P-phthalic acid is made into after slurry with the dihydroxylic alcohols containing side chain, under the catalytic action of concentrated sulphuric acid, carries out esterification Obtain p-phthalic acid binary alcohol esters；The described dihydroxylic alcohols containing side chain refer to that side chain is located at the non-end group of one of dihydroxylic alcohols segment On carbon and side chain is the dihydroxylic alcohols of the linear carbon chain containing 5-10 carbon atom；
(2) preparation of ethylene glycol terephthalate；
P-phthalic acid and ethylene glycol are made into after slurry, carry out esterification, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester；
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), stirring is mixed Close, in the presence 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, prepared modified poly ester.
3. a kind of preparation method of porous flexible polyester fiber POY silk according to claim 2 is it is characterised in that described The concrete preparation process of modified poly ester 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 Change reaction compressive reaction in nitrogen atmosphere, moulding pressure is normal pressure～0.3MPa, temperature is 180～240 DEG C, works as esterification In water quantity of distillate reach theoretical value more than 90% when be esterification terminal, obtain p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate；
P-phthalic acid and ethylene glycol are made into after slurry, carry out esterification, esterification 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%, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester；
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), stirring is mixed Close 15-20 minute, under conditions of negative pressure, in the presence of catalyst and stabilizer, start the polycondensation reaction in coarse vacuum stage, This staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature control 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, 50～90 minutes response time, prepared modified poly ester；
The main spinning technology parameter of described porous flexible polyester fiber 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.
4. a kind of preparation method of porous flexible polyester fiber POY silk according to claim 2 is it is characterised in that step (1), in, p-phthalic acid is 1 with the mol ratio of the dihydroxylic alcohols containing side chain:1.3-1.5；Concentrated sulphuric acid addition is p-phthalic acid The 0.3-0.5% of weight；The concentration of described concentrated sulphuric acid is 50-60wt%；
In step (2), p-phthalic acid is 1 with the mol ratio of ethylene glycol:1.2～2.0；
In step (3), the Mole percent ratio of described p-phthalic acid binary alcohol esters and ethylene glycol terephthalate is 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.
5. a kind of preparation method of porous flexible polyester fiber POY silk according to claim 2 is it is characterised in that described Dihydroxylic alcohols containing side chain are 2- amyl group -1,4 butanediol, 2- hexyl -1,4 butanediol, 2- heptyl -1,4 butanediol, 2- octyl group -1,4 Butanediol, 2- nonyl -1,4 butanediol, 2- decyl -1,4 butanediol, 2- amyl group -1,5 pentanediol, 2- hexyl -1,5 pentanediol, 2- One of heptyl -1,5 pentanediol, 2- octyl group -1,5 pentanediol, 2- nonyl -1,5 pentanediol or 2- decyl -1,5 pentanediol with On.
6. a kind of preparation method of porous flexible polyester fiber POY silk according to claim 2 is it is characterised in that described Spinneret orifice be arranged as major axis and/or short axle is symmetrical.
7. a kind of preparation method of porous flexible polyester fiber POY silk according to claim 2 is it is characterised in that ellipse The ratio of major axis and minor axis length be 1.3～1.8；The guide hole diameter that the spacing of adjacent spinneret orifice is more than or equal to spinneret orifice adds 1.5mm.
8. a kind of preparation method of porous flexible polyester fiber POY silk according to claim 2 is it is characterised in that described Spinneret is circular spinneret or elliptical spinneret plate；The diameter of described circle spinneret oval maximum long axis length with series Difference be more than 10mm, the difference of the described elliptical spinneret plate long axis length oval maximum with series is more than 10mm.
9. a kind of preparation method of porous flexible polyester fiber POY silk according to claim 2 is it is characterised in that described A diameter of 1.5～the 2.5mm of guide hole of spinneret orifice；The spray webbing hole count of described spinneret is more than or equal to 192.
10. a kind of preparation method of porous flexible polyester fiber POY silk according to claim 2 is it is characterised in that described The shape of cross section of the spinneret orifice of spinneret be circle, square, rhombus, yi word pattern, triangular form, trilobal cross, hollow type or Platypelloid type.
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