CN106400167A - Porous superfine denier flat yarn and preparation method thereof - Google Patents
Porous superfine denier flat yarn and preparation method thereof Download PDFInfo
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- CN106400167A CN106400167A CN201610785479.3A CN201610785479A CN106400167A CN 106400167 A CN106400167 A CN 106400167A CN 201610785479 A CN201610785479 A CN 201610785479A CN 106400167 A CN106400167 A CN 106400167A
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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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
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- 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
- D01D5/247—Discontinuous hollow structure or microporous structure
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- 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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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
Abstract
The invention relates to a porous superfine denier flat yarn and a preparation method thereof. Modified polyester is spun by a porous spinneret plate to prepare the porous superfine denier flat yarn; the arrangement form of spinneret holes in the porous spinneret plate is in an ellipse, namely that the hole center of each spinneret hole is positioned on concentric ellipses, the concentric ellipses are a series of ellipses, the long axes of all the ellipses are collinear, and the short axes of all the ellipses are collinear. The modified polyester is subjected to slicing, solid-phase polycondensation and viscosity increasing, so as to prepare the porous superfine denier flat yarn. A preparation method of the modified polyester comprises the following steps of reacting terephthalic acid and ethylene glycol to prepare ethylene terephthalate; adding ethylene terephthalate prepared by reaction of terephthalic acid and branch chain-containing ethylene glycol, and continuously reacting, so as to prepare the ethylene terephthalate; continuing to react, so as to obtain the modified polyester. The porous superfine denier flat yarn has the advantages that the prepared fiber property is excellent; the linear density deviation is smaller than or equal to 0.5%, a break strength CV (coefficient of variation) value is smaller than or equal to 4.0%, a break elongation CV value is smaller than or equal to 8.0%, and a yarn unevenness CV value is smaller than or equal to 2.0%.
Description
Technical field
The invention belongs to field of polyester fiber, it is related to ultra-fine denier flat filament of a kind of porous 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, but still the cooling of porous yarn cannot be solved well
Uneven problem.Because spun silk is after circular spinneret is extruded, by ring wind quenching, due to the circular spinneret number of turns relatively
Many lead to that the silk of innermost layer may be also uncolled after cooling in outermost silk so that ring blowing hardly enters innermost layer,
Thus the silk of gained occurs, and fiber number is irregular, intensity is irregular, the problems such as uneven dyeing, cause follow-up to silk be processed further occur
Difficulty.
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 preparation method of the ultra-fine denier flat filament of porous.The raw material of the polyester fiber of the present invention is modification
Polyester, the dihydroxylic alcohols segment containing side chain for the introducing in the strand of modified poly ester, the modified polyester fiber of modified polyester preparation, one
Under the conditions of constant temperature degree, the increasing degree of the spatial joint clearance of modified polyester fiber interior molecules interchain is far longer than at equal temperature no
The conventional polyester fiber of side chain, is conducive to the degree within the entrance of the molecules such as stain, improves dyeing rate；Modified poly ester
The melt viscosity of fiber reduces, and reduces processing temperature, reduces degradation rate, is conducive to processing；In addition contain the dihydroxylic alcohols chain of side chain
Section does not have big destruction to the structural regularity of modified polyester fiber, maintains the premium properties of polyester fiber.Spinning of the present invention
During using spinneret orifice oval shaped arrangements spinneret, be conducive to fiber uniform, sufficiently cool in spinning process, fiber
Between performance and structure difference less, improve dyeing uniformity and the mechanical property of fiber.
For reaching above-mentioned purpose, the technical solution used in the present invention is：
A kind of ultra-fine denier flat filament of porous, the material of the ultra-fine denier flat filament of described porous is modified poly ester, described modified poly-
Ester is made up of p-phthalic acid segment, ethylene glycol segment and the dihydroxylic alcohols segment containing side chain, the described dihydroxylic alcohols segment containing side chain
Refer to that side chain is located on one of dihydroxylic alcohols segment non-end group carbon and side chain is the linear carbon chain containing 5-10 carbon atom
Dihydroxylic alcohols segment；
Fracture strength >=the 3.8cN/dtex of the ultra-fine denier flat filament of described porous, elongation at break is 33.0 ± 3.0%；Institute
State the ultra-fine denier flat filament of porous at temperature is 80～130 DEG C, the spatial joint clearance of fibrous inside molecule interchain increases 10～30v/
V%；Line density deviation ratio≤0.5% of the ultra-fine denier flat filament of described porous, fracture strength CV value≤4.0%, extension at break CV
Value≤8.0%, yarn unevenness CV value≤2.0%, filament number is 0.3～0.5dtex.
The spatial joint clearance increase of described molecule interchain refers to modified poly ester and normal polyester in mutually synthermal strand
Between spatial joint clearance contrast.
Described melt viscosity declines the contrast referring to modified poly ester and normal polyester in mutually synthermal melt viscosity.
Present invention also offers a kind of preparation method of the ultra-fine denier flat filament of porous, modified poly ester is adopted spinneret orifice
Shape of cross section is that the porous spinneret spinning of platypelloid type is obtained the ultra-fine denier flat filament of porous；Spinneret orifice on described porous spinneret
Arrangement mode be oval shaped arrangements, described oval shaped arrangements refer to that the hole of spinneret orifice is centrally located on concentration ellipse, described with
The heart is oval oval for series, and all oval major axis are conllinear, and short axle is conllinear；
The preparation method of the ultra-fine denier flat filament of described porous is：Modified poly ester is obtained Modified polyester chips through pelletizing, then
Through measuring, extruding, cool down, oil, stretch, thermal finalization and winding, the ultra-fine denier flat filament of prepared porous；
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；It is non-that the described dihydroxylic alcohols containing side chain refer to that side chain is located at one of dihydroxylic alcohols segment
On end group carbon and side chain is the dihydroxylic alcohols 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：
The preparation method of the ultra-fine denier flat filament of a kind of porous as above, the concrete preparation process of described modified poly ester
For：
(1) preparation of p-phthalic acid binary alcohol esters；
P-phthalic acid is made into slurry with the dihydroxylic alcohols containing side chain, under the catalytic action of concentrated sulphuric acid, carries out esterification anti-
Should, esterification 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 the ultra-fine denier flat filament of described porous is：
The temperature of extrusion：280～290 DEG C；
The pathogenic wind-warm of cooling：20～25 DEG C；
The speed of winding：4000～4600m/min.
The preparation method of the ultra-fine denier flat filament of a kind of porous as above, in step (1), p-phthalic acid with containing side chain
Dihydroxylic alcohols mol ratio be 1:1.3-1.5；Concentrated sulphuric acid addition is the 0.3-0.5% of p-phthalic acid weight；Described dense sulfur
The concentration of 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.
The preparation method of the ultra-fine denier flat filament of a kind of porous as above, the described dihydroxylic alcohols containing side chain be 2- amyl group-
1,3 propylene glycol, 2- hexyl -1,3 propylene glycol, 2- heptyl -1,3 propylene glycol, 2- octyl group -1,3 propylene glycol, 2- nonyl -1,3 the third two
Alcohol, 2- decyl -1,3 propylene glycol, 2- amyl group -1,4 butanediol, 2- hexyl -1,4 butanediol, 2- heptyl -1,4 butanediol, 2- are pungent
Base -1,4 butanediol, 2- nonyl -1,4 butanediol, 2- decyl -1,4 butanediol, 2- amyl group -1,5 pentanediol, 2- hexyl -1,5 penta
Glycol, 2- heptyl -1,5 pentanediol, 2- octyl group -1,5 pentanediol, 2- nonyl -1,5 pentanediol, 2- decyl -1,5 pentanediol, 2- penta
Base -1,6 hexanediol, 2- hexyl -1,6 hexanediol, 2- heptyl -1,6 hexanediol, 2- octyl group -1,6 hexanediol, 2- nonyl -1,6 are own
One or more of glycol or 2- decyl -1,6 hexanediol.
The preparation method of the ultra-fine denier flat filament of a kind of porous as above, described spinneret orifice be arranged as major axis and/or
Short axle is symmetrical.
The preparation method of the ultra-fine denier flat filament of a kind of porous as above, oval major axis with the ratio of minor axis length 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.Effective area when spinneret
Mutually simultaneously as the girth of ellipse is more than circular girth, the number of plies of spinneret orifice oval shaped arrangements is less than the layer of circular arrangement
Number, 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 ring to dry
Cooling, improve the cooling effectiveness of ring blowing, the fibre property of preparation is also more excellent.Major axis is more connect with the ratio of minor axis length
It is bordering on 1, ellipse is more similar to justify, and the difference of cooling effectiveness and cooling effect is little；Major axis is 1.3 with the ratio of minor axis length
When, 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, cooling effect
Improve larger, 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 than conventional concentric circle row
The number of turns of row reduces it is easy to cooling wind thoroughly, makes the fiber cooling condition of Internal and external cycle evenly；Major axis and the ratio of minor axis length
During more than 1.8, ellipse is partial to form flat shape, is difficult to punch, cooling no longer raises.Therefore, series is ellipse
The major axis of circle is 1.3～1.8 with the ratio of minor axis length, can reach higher cooling effectiveness and preferable cooling effect.
The preparation method of the ultra-fine denier flat filament of a kind of porous as above, described spinneret is circular spinneret or ellipse
Shape spinneret；The diameter of described circle spinneret is more than 10mm, described ellipse with the difference of the oval maximum long axis length of series
Shape spinneret is more than 10mm with the difference of the oval maximum long axis length of series.
The preparation method of the ultra-fine denier flat filament of a kind of porous 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.
The preparation method of the ultra-fine denier flat filament of a kind of porous as above, the shape of cross section of described spinneret orifice is flat
Flat pattern refers to that spinneret orifice is slotted hole, and the ratio of the length and width of described slotted hole is 4～7.
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 ultra-fine denier flat filament of porous that the present invention is obtained is modified poly ester, contains in modified poly ester macromole
Dihydroxylic alcohols segment containing side chain, when temperature is higher than vitrification point, side chain, prior to backbone motion, makes the increase width of free volume
Degree is far longer than the characteristic of unbranched polyester macromolecule chain, and the increase of free volume improves molecule and enters inside polyester
Degree, increase the diffusion of dyestuff by the free volume that side chain increased polyester fiber, improve the dye of polyester fiber
Color performance.
4) the ultra-fine denier flat filament of porous that the present invention is obtained, the increase of polyester fiber free volume advantageously reduces melt and glues
Degree, is conducive to improving its processing characteristics.
5) present invention is obtained the ultra-fine denier flat filament of porous, the introducing of the dihydroxylic alcohols segment containing side chain to polyester fiber
Structural regularity does not have big destruction, maintains the premium properties of polyester fiber.
6) present invention is obtained porous ultra-fine denier flat filament dyeability and good mechanical performance, the ultra-fine denier flat filament of porous
Line density deviation ratio≤0.5%, fracture strength CV value≤4.0%, extension at break CV value≤8.0%, yarn unevenness CV value
≤ 2.0%.
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 -1,3 propylene glycol 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 gross weight 0.01% the catalytic antimony trioxide and addition be p-phthalic acid gross weight
Under conditions of negative pressure, in the presence of 0.01% stabilizer triphenyl phosphate, start the polycondensation reaction in coarse vacuum stage, this rank
It is 500Pa that section pressure is steadily evacuated to absolute pressure by normal pressure, and at 260 DEG C, the response time is 30 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 100Pa, and reaction temperature controls
275 DEG C, 50 minutes response time, prepared modified poly ester.
The number-average molecular weight of modified poly ester is 15000, and modified poly ester is by p-phthalic acid segment, ethylene glycol segment and 2- penta
Base -1,3 propylene glycol segment compositions, the dihydroxylic alcohols segment containing side chain is 2% with the Mole percent ratio of ethylene glycol segment.
Table 1：Embodiment 2-12 important technological parameters
Embodiment 2
The preparation process of the preparation method of the modified poly ester of embodiment 2, wherein modified poly ester with embodiment 1, wherein mainly
Technical parameter referring to table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 16 minutes, in addition be
The catalytic antimony trioxide of the 0.011% of p-phthalic acid gross weight and addition are the 0.02% of p-phthalic acid gross 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 490Pa is steadily evacuated to by normal pressure, at 262 DEG C, the response time is 31 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 90Pa, reaction temperature controls at 276 DEG C, reaction
51 minutes time, prepared modified poly ester.
The number-average molecular weight of modified poly ester is 16000, and modified poly ester is own by p-phthalic acid segment, ethylene glycol segment and 2-
Base -1,3 propylene glycol segment compositions, 2- hexyl -1,3 propylene glycol segments are 2.1% with the Mole percent ratio of ethylene glycol segment.
Embodiment 3
The preparation process of the preparation method of the modified poly ester of embodiment 3, wherein modified poly ester with embodiment 1, wherein mainly
Technical parameter referring to table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 16 minutes, in addition be
The catalytic antimony trioxide of the 0.03% of p-phthalic acid gross weight and addition are the 0.02% of p-phthalic acid gross 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 498Pa is steadily evacuated to by normal pressure, at 263 DEG C, the response time is 32 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 90Pa, reaction temperature controls at 277 DEG C, reaction
57 minutes time, prepared modified poly ester.
The number-average molecular weight of modified poly ester is 15900, and modified poly ester is by p-phthalic acid segment, ethylene glycol segment and 2- heptan
Base -1,3 propylene glycol segment compositions, 2- heptyl -1,3 propylene glycol segments are 2.2% with the Mole percent ratio of ethylene glycol segment.
Embodiment 4
The preparation process of the preparation method of the modified poly ester of embodiment 4, wherein modified poly ester with embodiment 1, wherein mainly
Technical parameter referring to table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 17 minutes, in addition be
The catalytic antimony trioxide of the 0.033% of p-phthalic acid gross weight and addition are p-phthalic acid gross weight
Under 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 modified poly ester is 15800, and modified poly ester is pungent by p-phthalic acid segment, ethylene glycol segment and 2-
Base -1,3 propylene glycol segment compositions, 2- octyl group -1,3 propylene glycol segments are 2.3% with the Mole percent ratio of ethylene glycol segment.
Embodiment 5
The preparation process of the preparation method of the modified poly ester of embodiment 5, wherein modified poly ester with embodiment 1, wherein mainly
Technical parameter referring to table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 17 minutes, in addition be
The catalytic antimony trioxide of the 0.034% of p-phthalic acid gross weight and addition are p-phthalic acid gross weight
Under 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 80Pa, and reaction temperature controls 277
DEG C, 59 minutes response time, prepared modified poly ester.
The number-average molecular weight of modified poly ester is 15900, and modified poly ester is by p-phthalic acid segment, ethylene glycol segment and 2- nonyl
Base -1,3 propylene glycol segment compositions, 2- nonyl -1,3 propylene glycol segments are 2.4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 6
The preparation process of the preparation method of the modified poly ester of embodiment 6, wherein modified poly ester with embodiment 1, wherein mainly
Technical parameter referring to table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 18 minutes, in addition be
The catalytic antimony trioxide of the 0.035% of p-phthalic acid gross weight and addition are p-phthalic acid gross weight
Under 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 modified poly ester is 16000, and modified poly ester is by p-phthalic acid segment, ethylene glycol segment and the 2- last of the ten Heavenly stems
Base -1,3 propylene glycol segment compositions, 2- decyl -1,3 propylene glycol segments are 2.5% with the Mole percent ratio of ethylene glycol segment.
Embodiment 7
The preparation process of the preparation method of the modified poly ester of embodiment 7, wherein modified poly ester with embodiment 1, wherein mainly
Technical parameter referring to table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 19 minutes, in addition be
The catalytic antimony trioxide of the 0.036% of p-phthalic acid gross weight and addition are p-phthalic acid gross weight
Under 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 modified poly ester is 16000, and the number-average molecular weight of modified poly ester is 16000, and modified poly ester is by right
Phthalic acid segment, ethylene glycol segment and 2- amyl group-Isosorbide-5-Nitrae butanediol segment composition, 2- amyl group-Isosorbide-5-Nitrae butanediol segment and second two
The Mole percent ratio of alcohol segment is 2.6%.
Embodiment 8
The preparation process of the preparation method of the modified poly ester of embodiment 8, wherein modified poly ester with embodiment 1, wherein mainly
Technical parameter referring to table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 19 minutes, in addition be
The catalytic antimony trioxide of the 0.036% of p-phthalic acid gross weight and addition are p-phthalic acid gross weight
Under 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 modified poly ester is 17000, and modified poly ester is own by p-phthalic acid segment, ethylene glycol segment and 2-
Base-Isosorbide-5-Nitrae butanediol segment composition, 2- hexyl-Isosorbide-5-Nitrae butanediol segment is 2.7% with the Mole percent ratio of ethylene glycol segment.
Embodiment 9
The preparation process of the preparation method of the modified poly ester of embodiment 9, wherein modified poly ester with embodiment 1, wherein mainly
Technical parameter referring to table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 16 minutes, in addition be
The catalyst glycol antimony of the 0.04% of p-phthalic acid gross weight and addition are the 0.026% of p-phthalic acid gross 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 268 DEG C, the response time is 38 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 60Pa, and reaction temperature controls at 279 DEG C, reaction
62 minutes time, prepared modified poly ester.
The number-average molecular weight of modified poly ester is 17000, and modified poly ester is by p-phthalic acid segment, ethylene glycol segment and 2- heptan
Base-Isosorbide-5-Nitrae butanediol segment composition, 2- heptyl-Isosorbide-5-Nitrae butanediol segment is 2.8% with the Mole percent ratio of ethylene glycol segment.
Embodiment 10
The preparation process of the preparation method of the modified poly ester of embodiment 10, wherein modified poly ester with embodiment 1, wherein mainly
Technical parameter referring to table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 17 minutes, in addition be
The catalyst glycol antimony of the 0.03% of p-phthalic acid gross weight and addition are the 0.027% of p-phthalic acid gross 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 60Pa, and reaction temperature controls at 278 DEG C, reaction
64 minutes time, prepared modified poly ester.
The number-average molecular weight of modified poly ester is 17000, and modified poly ester is pungent by p-phthalic acid segment, ethylene glycol segment and 2-
Base-Isosorbide-5-Nitrae butanediol segment composition, 2- octyl group-Isosorbide-5-Nitrae butanediol segment is 3% with the Mole percent ratio of ethylene glycol segment.
Embodiment 11
The preparation process of the preparation method of the modified poly ester of embodiment 11, wherein modified poly ester with embodiment 1, wherein mainly
Technical parameter referring to table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 18 minutes, in addition be
The catalyst glycol antimony of the 0.04% of p-phthalic acid gross weight and addition are the 0.03% of p-phthalic acid gross 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 60Pa, and reaction temperature controls at 277 DEG C, reaction
63 minutes time, prepared modified poly ester.
The number-average molecular weight of modified poly ester is 18000, and modified poly ester is by p-phthalic acid segment, ethylene glycol segment and 2- nonyl
Base-Isosorbide-5-Nitrae butanediol segment composition, 2- nonyl-Isosorbide-5-Nitrae butanediol segment is 4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 12
The preparation process of the preparation method of the modified poly ester of embodiment 12, wherein modified poly ester with embodiment 1, wherein mainly
Technical parameter referring to table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 18 minutes, in addition be
The catalyst acetic acid antimony of the 0.038% of p-phthalic acid weight and addition are the stabilizer of the 0.03% of p-phthalic acid weight
Under conditions of negative pressure, in the presence of NSC 6513, start the polycondensation reaction in coarse vacuum stage, this staged pressure is by normal pressure
Steadily it is evacuated to absolute pressure 497Pa, at 265 DEG C, the response time is 42 minutes to temperature control；Then proceed to evacuation, carry out height
The polycondensation reaction of vacuum stages, making reaction pressure be down to absolute pressure is 40Pa, and reaction temperature controls at 277 DEG C, the response time
70 minutes, 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 -1,6 hexanediol 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 -1,6 hexanediol segment compositions, 2- decyl -1,6 hexanediol 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 -1,6 hexanediol 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 -1,6 hexanediol segment compositions, 2- nonyl -1,6 hexanediol 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 -1,6 hexanediol 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 -1,6 hexanediol segment compositions, 2- octyl group -1,6 hexanediol segments are 4.5% with the Mole percent ratio of ethylene glycol segment.
Embodiment 16
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 -1,6 hexanediol 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 -1,6 hexanediol segment compositions, 2- heptyl -1,6 hexanediol 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 -1,6 hexanediol 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 -1,6 hexanediol segment compositions, 2- hexyl -1,6 hexanediol 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 -1,6 hexanediol 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 -1,6 hexanediol segment compositions, 2- amyl group -1,6 hexanediol segments are 4.7% with the Mole percent ratio of ethylene glycol segment.
Embodiment 19
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 -1,6 hexanediol 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-
1,6 hexanediol segment and 2- amyl group -1,5 pentanediol segment compositions, 2- octyl group -1,6 hexanediol segments and 2- amyl group -1,5 penta 2
Alcohol segment is 4.6% with the Mole percent ratio of ethylene glycol segment.
Embodiment 27
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 -1,3 propylene glycol, 2- amyl group -1,4 butanediol and 2-
Base -1, the mixture of 6 hexanediol is made into slurry and adds in reactor, wherein 2- octyl group -1,3 propylene glycol, 2- amyl group-Isosorbide-5-Nitrae fourth two
The mol ratio of alcohol and 2- hexyl -1,6 hexanediol 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 -1,3 propylene glycol segments, 2- amyl group-Isosorbide-5-Nitrae butanediol chain
Section and 2- hexyl -1,6 hexanediol 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 the ultra-fine denier flat filament of porous, the ultra-fine denier flat filament of porous adopts the cross section shape of spinneret orifice
Shape is that the porous spinneret of platypelloid type is obtained, for platypelloid type, the shape of cross section of spinneret orifice refers to that spinneret orifice is slotted hole,
The ratio of the length and width of slotted hole is 4, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements are
The hole referring to spinneret orifice is centrally located on concentration ellipse, and concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is altogether
Line.
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 modified poly ester that embodiment 1 is obtained, obtains Modified polyester chips through pelletizing；Again through metering, extrusion, cooling, on
Oil, stretching, thermal finalization and winding, the ultra-fine denier flat filament of prepared porous, the temperature of extrusion is 285 DEG C, and the pathogenic wind-warm of cooling is 25 DEG C,
The speed of winding is 4500m/min；
The filament number of the ultra-fine denier flat filament of prepared porous is 0.4dtex, and fracture strength is 4.7cN/dtex, and fracture is stretched
Long rate is 34.7%；At temperature is 80 DEG C, the spatial joint clearance of fibrous inside molecule interchain increases the ultra-fine denier flat filament of porous
15v/v%, at 289 DEG C, melt viscosity declines 16%；The line density deviation ratio of the ultra-fine denier flat filament of porous is 0.4%, fracture
Intensity CV value is 3.2%, and extension at break CV value is 6.9%, and yarn unevenness CV value is 1.8%.
Embodiment 30
A kind of preparation method of the ultra-fine denier flat filament of porous, the ultra-fine denier flat filament of porous adopts the cross section shape of spinneret orifice
Shape is that the porous spinneret of platypelloid type is obtained, for platypelloid type, the shape of cross section of spinneret orifice refers to that spinneret orifice is slotted hole,
The ratio of the length and width of slotted hole is 4, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements are
The hole referring to spinneret orifice is centrally located on concentration ellipse, and concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is altogether
Line.
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 modified poly ester that embodiment 1 is obtained, obtains Modified polyester chips through pelletizing；Again through metering, extrusion, cooling, on
Oil, stretching, thermal finalization and winding, the ultra-fine denier flat filament of prepared porous, the temperature of extrusion is 285 DEG C, and the pathogenic wind-warm of cooling is 25 DEG C,
The speed of winding is 4500m/min；
The filament number of the ultra-fine denier flat filament of prepared porous is 0.5dtex, initial moduluss 85cN/dtex, fracture strength
For 5.4cN/dtex, elongation at break is 35.2%；The ultra-fine denier flat filament of porous temperature be 80 DEG C at, fibrous inside strand
Between spatial joint clearance increase 15v/v%, at 289 DEG C, melt viscosity decline 16%；The line density of the ultra-fine denier flat filament of porous is inclined
Rate is 0.2%, and fracture strength CV value is 2.2%, and extension at break CV value is 5.9%, and yarn unevenness CV value is 1.4%.
Comparative example 1
A kind of preparation method of the ultra-fine denier flat filament of porous, the ultra-fine denier flat filament of porous adopts the cross section shape of spinneret orifice
Shape is that the porous spinneret of platypelloid type is obtained, for platypelloid type, the shape of cross section of spinneret orifice refers to that spinneret orifice is slotted hole,
The ratio of the length and width of slotted hole is 4, and on spinneret, the arrangement mode of spinneret orifice is circular arrangement, and circular arrangement refers to spray
The hole in silk hole is centrally located on concentric circular, and concentric circular is that series is circular.As shown in Fig. 2 the spacing of adjacent spinneret orifice is equal to spray webbing
The guide hole diameter in hole adds 1.5mm, and spinneret is circular spinneret, the diameter of circular spinneret circular maximum diameter with series
Difference be 11mm, a diameter of 2.0mm of guide hole of spinneret orifice, the spray webbing hole count of spinneret is 370.
The modified poly ester that embodiment 1 is obtained, obtains Modified polyester chips through pelletizing；Again through metering, extrusion, cooling, on
Oil, stretching, thermal finalization and winding, the ultra-fine denier flat filament of prepared porous, extrusion temperature is 285 DEG C, and the pathogenic wind-warm of cooling is 25 DEG C, volume
Around speed be 4500m/min；
The filament number of the ultra-fine denier flat filament of prepared porous is 0.4dtex, and fracture strength is 3.8cN/dtex, and fracture is stretched
Long rate is 36.0%；At temperature is 80 DEG C, the spatial joint clearance of fibrous inside molecule interchain increases the ultra-fine denier flat filament of porous
15v/v%, at 289 DEG C, melt viscosity declines 16%；The line density deviation ratio of the ultra-fine denier flat filament of porous is 0.7%, fracture
Intensity CV value is 5.2%, and extension at break CV value is 9.1%, and yarn unevenness CV value is 2.8%.
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 the ultra-fine denier flat filament of porous, the ultra-fine denier flat filament of porous adopts the cross section shape of spinneret orifice
Shape is that the porous spinneret of platypelloid type is obtained, for platypelloid type, the shape of cross section of spinneret orifice refers to that spinneret orifice is slotted hole,
The ratio of the length and width of slotted hole is 6, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements are
The hole referring to spinneret orifice is centrally located on concentration ellipse, and concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is altogether
Line.
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.
Modified poly ester, obtains Modified polyester chips through pelletizing；Again through measuring, extruding, cool down, oil, stretch, thermal finalization and
Winding, the ultra-fine denier flat filament of prepared porous, the temperature of porous ultra-fine denier flat filament extrusion is 280 DEG C, and the pathogenic wind-warm of cooling is 20 DEG C,
The speed of winding is 4000m/min；The ultra-fine denier flat filament of prepared porous is at 80 DEG C between the space of fibrous inside molecule interchain
The mechanical performance data of gap Magnification and fiber such as following table.
Embodiment 34～36
A kind of preparation method of the ultra-fine denier flat filament of porous, the ultra-fine denier flat filament of porous adopts the cross section shape of spinneret orifice
Shape is that the porous spinneret of platypelloid type is obtained, for platypelloid type, the shape of cross section of spinneret orifice refers to that spinneret orifice is slotted hole,
The ratio of the length and width of slotted hole is 6, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements are
The hole referring to spinneret orifice is centrally located on concentration ellipse, and concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is altogether
Line.
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.
The modified poly ester that embodiment 1 is obtained, obtains Modified polyester chips through pelletizing；Again through metering, extrusion, cooling, on
Oil, stretching, thermal finalization and winding, the ultra-fine denier flat filament of prepared porous, extrusion temperature is 290 DEG C, and the pathogenic wind-warm of cooling is 22 DEG C, volume
Around speed be 4300m/min；
The ultra-fine denier flat filament of prepared porous the spatial joint clearance Magnification of fibrous inside molecule interchain and fibre at 90 DEG C
The mechanical performance data such as following table of dimension.
Embodiment 37～39
A kind of preparation method of the ultra-fine denier flat filament of porous, the ultra-fine denier flat filament of porous adopts the cross section shape of spinneret orifice
Shape is that the porous spinneret of platypelloid type is obtained, for platypelloid type, the shape of cross section of spinneret orifice refers to that spinneret orifice is slotted hole,
The ratio of the length and width of slotted hole is 7, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements are
The hole referring to spinneret orifice is centrally located on concentration ellipse, and concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is altogether
Line.
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 modified poly ester that embodiment 1 is obtained, obtains Modified polyester chips through pelletizing；Again through metering, extrusion, cooling, on
Oil, stretching, thermal finalization and winding, the ultra-fine denier flat filament of prepared porous, extrusion temperature is 286 DEG C, and the pathogenic wind-warm of cooling is 22 DEG C, volume
Around speed be 4400m/min；The spatial joint clearance of the ultra-fine denier flat filament of prepared porous fibrous inside molecule interchain at 100 DEG C
The mechanical performance data of Magnification and fiber such as following table.
Embodiment 40～42
A kind of preparation method of the ultra-fine denier flat filament of porous, the ultra-fine denier flat filament of porous adopts the cross section shape of spinneret orifice
Shape is that the porous spinneret of platypelloid type is obtained, for platypelloid type, the shape of cross section of spinneret orifice refers to that spinneret orifice is slotted hole,
The ratio of the length and width of slotted hole is 7, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements are
The hole referring to spinneret orifice is centrally located on concentration ellipse, and concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is altogether
Line.
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 modified poly ester that embodiment 1 is obtained, obtains Modified polyester chips through pelletizing；Again through metering, extrusion, cooling, on
Oil, stretching, thermal finalization and winding, the ultra-fine denier flat filament of prepared porous, extrusion temperature is 281 DEG C, and the pathogenic wind-warm of cooling is 22 DEG C, volume
Around speed be 4350m/min；The spatial joint clearance of the ultra-fine denier flat filament of prepared porous fibrous inside molecule interchain at 110 DEG C
The mechanical performance data of Magnification and fiber such as following table.
Embodiment 43～45
A kind of preparation method of the ultra-fine denier flat filament of porous, the ultra-fine denier flat filament of porous adopts the cross section shape of spinneret orifice
Shape is that the porous spinneret of platypelloid type is obtained, for platypelloid type, the shape of cross section of spinneret orifice refers to that spinneret orifice is slotted hole,
The ratio of the length and width of slotted hole is 7, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements are
The hole referring to spinneret orifice is centrally located on concentration ellipse, and concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is altogether
Line.
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.
The modified poly ester that embodiment 1 is obtained, obtains Modified polyester chips through pelletizing；Again through metering, extrusion, cooling, on
Oil, stretching, thermal finalization and winding, the ultra-fine denier flat filament of prepared porous, extrusion temperature is 284 DEG C, and the pathogenic wind-warm of cooling is 22 DEG C, volume
Around speed be 4380m/min；The spatial joint clearance of the ultra-fine denier flat filament of prepared porous fibrous inside molecule interchain at 110 DEG C
The mechanical performance data of Magnification and fiber such as following table.
Embodiment 46～49
A kind of preparation method of the ultra-fine denier flat filament of porous, the ultra-fine denier flat filament of porous adopts the cross section shape of spinneret orifice
Shape is that the porous spinneret of platypelloid type is obtained, for platypelloid type, the shape of cross section of spinneret orifice refers to that spinneret orifice is slotted hole,
The ratio of the length and width of slotted hole is 5, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements are
The hole referring to spinneret orifice is centrally located on concentration ellipse, and concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is altogether
Line.
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.
The modified poly ester that embodiment 1 is obtained, obtains Modified polyester chips through pelletizing；Again through metering, extrusion, cooling, on
Oil, stretching, thermal finalization and winding, the ultra-fine denier flat filament of prepared porous, extrusion temperature is 284 DEG C, and the pathogenic wind-warm of cooling is 22 DEG C, volume
Around speed be 4380m/min；The spatial joint clearance of the ultra-fine denier flat filament of prepared porous fibrous inside molecule interchain at 110 DEG C
The mechanical performance data of Magnification and fiber such as following table.
Embodiment 50～53
A kind of preparation method of the ultra-fine denier flat filament of porous, the ultra-fine denier flat filament of porous adopts the cross section shape of spinneret orifice
Shape is that the porous spinneret of platypelloid type is obtained, for platypelloid type, the shape of cross section of spinneret orifice refers to that spinneret orifice is slotted hole,
The ratio of the length and width of slotted hole is 5, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements are
The hole referring to spinneret orifice is centrally located on concentration ellipse, and concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is altogether
Line.
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.
Modified poly ester, obtains Modified polyester chips through pelletizing；Again through measuring, extruding, cool down, oil, stretch, thermal finalization and
Winding, the ultra-fine denier flat filament of prepared porous, the temperature of extrusion is 285 DEG C, and the pathogenic wind-warm of cooling is 23 DEG C, and the speed of winding is
4550m/min；The ultra-fine denier flat filament of prepared porous at 100 DEG C the spatial joint clearance Magnification of fibrous inside molecule interchain and
The mechanical performance data of fiber such as following table.
Embodiment 54～57
A kind of preparation method of the ultra-fine denier flat filament of porous, the ultra-fine denier flat filament of porous adopts the cross section shape of spinneret orifice
Shape is that the porous spinneret of platypelloid type is obtained, for platypelloid type, the shape of cross section of spinneret orifice refers to that spinneret orifice is slotted hole,
The ratio of the length and width of slotted hole is 5, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements are
The hole referring to spinneret orifice is centrally located on concentration ellipse, and concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is altogether
Line.
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.
Modified poly ester, obtains Modified polyester chips through pelletizing；Again through measuring, extruding, cool down, oil, stretch, thermal finalization and
Winding, prepared porous super fine denier is flat, and the temperature of extrusion is 285 DEG C, and the pathogenic wind-warm of cooling is 23 DEG C, and the speed of winding is 4550m/
min；The ultra-fine denier flat filament of prepared porous the spatial joint clearance Magnification of fibrous inside molecule interchain and fiber at 120 DEG C
Mechanical performance data such as following table.
Embodiment 58
The dyeing of the ultra-fine denier flat filament of porous：
The ultra-fine denier flat filament of porous of embodiment 29 preparation is dyeed in High Temperature High Pressure machine, actual conditions is：Dye
Before color, porous ultra-fine denier flat filament nonionic surfactant is processed 30 minutes at 60 DEG C, is subsequently adding in dyeing liquor, dyeing
Disperse dyes consumption in liquid is 2.0% (o.w.f)；Dispersant NNO, concentration 1.2g/L of dispersant NNO；PH value is 5, bath raio
For 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 of each constant temperature dyeing 1h.
Using identical dyeing condition, general fibre is dyeed.The upper dye of the ultra-fine denier flat filament of the porous after dyed
Percentage rate 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, disperse blue SE-2R or when disperseing bright blue S-GL, the ultra-fine denier flat filament of porous and general
The dye uptake result such as following table of perforating fiber：
By the Color contrast of the ultra-fine denier flat filament of porous and general fibre it can be seen that the ultra-fine denier flat filament of porous
Color be substantially better than general fibre, also contain the modified poly ester macromole of present invention preparation from side illustration contains
The dihydroxylic alcohols segment of side chain, makes the increasing degree of free volume be far longer than the characteristic of unbranched polyester macromolecule chain, freely
The increase of volume improves the degree within molecule entrance polyester, the free volume of the polyester fiber of modified polyester preparation
It is far longer than unbranched polyester fiber at equal temperature, increases the diffusion of dyestuff, improve the dyeability of polyester fiber.
Embodiment 59
The dyeing of the ultra-fine denier flat filament of porous：
The ultra-fine denier flat filament of porous of embodiment 31 preparation is dyeed in High Temperature High Pressure machine, actual conditions is：Dye
Before color, porous ultra-fine denier flat filament nonionic surfactant is processed 30 minutes at 60 DEG C, is subsequently adding in dyeing liquor, dyeing
Disperse dyes consumption in liquid is 2.0% (o.w.f)；Dispersant NNO, concentration 1.2g/L of dispersant NNO；PH value is 5, bath raio
For 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 of each constant temperature dyeing 1h.
Using identical dyeing condition, general fibre is dyeed.The upper dye of the ultra-fine denier flat filament of the porous after dyed
Percentage rate 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, disperse blue SE-2R or when disperseing bright blue S-GL, the ultra-fine denier flat filament of porous and general
The dye uptake result such as following table of perforating fiber：
By the Color contrast of the ultra-fine denier flat filament of porous and general fibre it can be seen that the ultra-fine denier flat filament of porous
Color be substantially better than general fibre, also contain the modified poly ester macromole of present invention preparation from side illustration contains
The dihydroxylic alcohols segment of side chain, makes the increasing degree of free volume be far longer than the characteristic of unbranched polyester macromolecule chain, freely
The increase of volume improves the degree within molecule entrance polyester, the free volume of the polyester fiber of modified polyester preparation
It is far longer than unbranched polyester fiber at equal temperature, increases the diffusion of dyestuff, improve the dyeability of polyester fiber.
Embodiment 60
The dyeing of the ultra-fine denier flat filament of porous：
The ultra-fine denier flat filament of porous of embodiment 35 preparation is dyeed in High Temperature High Pressure machine, actual conditions is：Dye
Before color, porous ultra-fine denier flat filament nonionic surfactant is processed 30 minutes at 60 DEG C, is subsequently adding in dyeing liquor, dyeing
Disperse dyes consumption in liquid is 2.0% (o.w.f)；Dispersant NNO, concentration 1.2g/L of dispersant NNO；PH value is 5, bath raio
For 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 of each constant temperature dyeing 1h.
Using identical dyeing condition, general fibre is dyeed.The upper dye of the ultra-fine denier flat filament of the porous after dyed
Percentage rate 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, disperse blue SE-2R or when disperseing bright blue S-GL, the ultra-fine denier flat filament of porous and general
The dye uptake result such as following table of perforating fiber：
By the Color contrast of the ultra-fine denier flat filament of porous and general fibre it can be seen that the ultra-fine denier flat filament of porous
Color be substantially better than general fibre, also contain the modified poly ester macromole of present invention preparation from side illustration contains
The dihydroxylic alcohols segment of side chain, makes the increasing degree of free volume be far longer than the characteristic of unbranched polyester macromolecule chain, freely
The increase of volume improves the degree within molecule entrance polyester, the free volume of the polyester fiber of modified polyester preparation
It is far longer than unbranched polyester fiber at equal temperature, increases the diffusion of dyestuff, improve the dyeability of polyester fiber.
Claims (10)
1. a kind of ultra-fine denier flat filament of porous, is characterized in that：The ultra-fine denier flat filament of described porous is micro- through spray webbing by modified poly ester
Hole cross sectional shape obtains for pancake spinneret spinning；The material of the ultra-fine denier flat filament of described porous is modified poly ester, described
Modified poly ester is made up of p-phthalic acid segment, ethylene glycol segment and the dihydroxylic alcohols segment containing side chain, the described binary containing side chain
Alcohol segment refers to that side chain is located on one of dihydroxylic alcohols segment non-end group carbon and side chain is the straight chain containing 5-10 carbon atom
The dihydroxylic alcohols segment of carbochain；
Fracture strength >=the 3.8cN/dtex of the ultra-fine denier flat filament of described porous, elongation at break is 33.0 ± 3.0%；Described many
At temperature is 80～130 DEG C, the spatial joint clearance of fibrous inside molecule interchain increases 10～30v/v% to the ultra-fine denier flat filament in hole；
Line density deviation ratio≤0.5% of the ultra-fine denier flat filament of described porous, fracture strength CV value≤4.0%, extension at break CV value≤
8.0%, yarn unevenness CV value≤2.0%, filament number is 0.3～0.5dtex, and the spatial joint clearance of described molecule interchain increases
Refer to greatly the contrast of the spatial joint clearance with normal polyester in mutually synthermal molecule interchain for the modified poly ester.
2. a kind of preparation method of the ultra-fine denier flat filament of porous as claimed in claim 1, is characterized in that：Modified poly ester is adopted
The shape of cross section of spinneret orifice is that the porous spinneret spinning of platypelloid type is obtained the ultra-fine denier flat filament of porous；Described porous spray webbing
On plate, the arrangement mode of spinneret orifice is oval shaped arrangements, and described oval shaped arrangements refer to that the hole of spinneret orifice is centrally located at concentration ellipse
On, described concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear；
The preparation method of the ultra-fine denier flat filament of described porous is：Modified poly ester is obtained Modified polyester chips through pelletizing, then through meter
Measure, extrude, cooling down, oiling, stretching, thermal finalization and winding, the ultra-fine denier flat filament of prepared porous；
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 the ultra-fine denier flat filament of porous according to claim 2 is it is characterised in that described modified poly-
The concrete preparation process of 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 the ultra-fine denier flat filament of described porous is：
The temperature of extrusion：280～290 DEG C；
The pathogenic wind-warm of cooling：20～25 DEG C；
The speed of winding：4000～4600m/min.
4. a kind of preparation method of the ultra-fine denier flat filament of porous according to claim 2 is it is characterised in that in step (1),
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 weight
0.3-0.5%；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 ultra-fine denier flat filament of porous according to claim 2 preparation method it is characterised in that described containing side chain
Dihydroxylic alcohols be 2- amyl group -1,3 propylene glycol, 2- hexyl -1,3 propylene glycol, 2- heptyl -1,3 propylene glycol, 2- octyl group -1,3 the third two
Alcohol, 2- nonyl -1,3 propylene glycol, 2- decyl -1,3 propylene glycol, 2- amyl group -1,4 butanediol, 2- hexyl -1,4 butanediol, 2- heptan
Base -1,4 butanediol, 2- octyl group -1,4 butanediol, 2- nonyl -1,4 butanediol, 2- decyl -1,4 butanediol, 2- amyl group -1,5 penta
Glycol, 2- hexyl -1,5 pentanediol, 2- heptyl -1,5 pentanediol, 2- octyl group -1,5 pentanediol, 2- nonyl -1,5 pentanediol, the 2- last of the ten Heavenly stems
Base -1,5 pentanediol, 2- amyl group -1,6 hexanediol, 2- hexyl -1,6 hexanediol, 2- heptyl -1,6 hexanediol, 2- octyl group -1,6 are own
One or more of glycol, 2- nonyl -1,6 hexanediol or 2- decyl -1,6 hexanediol.
6. a kind of preparation method of the ultra-fine denier flat filament of porous 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 the ultra-fine denier flat filament of porous according to claim 2 is it is characterised in that the major axis of ellipse
Ratio with minor axis length 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.
8. a kind of preparation method of the ultra-fine denier flat filament of porous according to claim 2 is it is characterised in that described spinneret
For circular spinneret or elliptical spinneret plate；The diameter of described circle spinneret and the difference of the oval maximum long axis length of series
More than 10mm, described elliptical spinneret plate is more than 10mm with the difference of the oval maximum long axis length of series.
9. a kind of preparation method of the ultra-fine denier flat filament of porous according to claim 2 is it is characterised in that described spinneret orifice
The a diameter of 1.5～2.5mm of guide hole；The spray webbing hole count of described spinneret is more than or equal to 192.
10. a kind of preparation method of the ultra-fine denier flat filament of porous according to claim 2 is it is characterised in that described spray webbing
For platypelloid type, the shape of cross section of micropore refers to that spinneret orifice is slotted hole, the ratio of the length and width of described slotted hole is 4
～7.
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| CN108035007A (en) * | 2017-12-14 | 2018-05-15 | 江苏恒力化纤股份有限公司 | Superfine denier polyester drafting silk and preparation method thereof |
| CN108193309A (en) * | 2018-02-10 | 2018-06-22 | 海盐县硕创服装研究所 | Ultra-fine denier polyester filament yarn and preparation method thereof |
| CN109735924A (en) * | 2018-12-27 | 2019-05-10 | 江苏恒力化纤股份有限公司 | Superfine denier polyester drafting silk and preparation method thereof |
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