CN106400161A - Porous polyester fiber HOY filaments and preparation method thereof - Google Patents
Porous polyester fiber HOY filaments and preparation method thereof Download PDFInfo
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- CN106400161A CN106400161A CN201610776337.0A CN201610776337A CN106400161A CN 106400161 A CN106400161 A CN 106400161A CN 201610776337 A CN201610776337 A CN 201610776337A CN 106400161 A CN106400161 A CN 106400161A
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- terephthalic acid
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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
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to porous polyester fiber HOY filaments and a preparation method thereof; the porous polyester fiber HOY filaments are prepared by spinning modified polyester through a porous spinneret plate; an arrangement way of spinneret holes in the porous spinneret plate is in oval arrangement, that is to say, a hole center of the spinneret holes is located in concentric ellipses, the concentric ellipses are a series of ellipses, the long axes of all the ellipses are collinear, and the short axes are collinear. The porous polyester fiber HOY filaments are prepared by metering, extruding, cooling, oiling and high-speed coiling of the modified polyester, wherein a preparation method for the modified polyester comprises the steps: carrying out a reaction of terephthalic acid and ethylene glycol to prepare ethylene glycol terephthalate, adding terephthalic acid and branched chain-containing dihydric alcohol, carrying out a reaction to prepare dihydric alcohol terephthalate, and continuing to carry out a reaction to obtain the modified polyester. The prepared fiber is excellent in properties, the linear density deviation rate of the porous polyester fiber HOY filaments is less than or equal to 0.2%, the CV value of breaking strength is less than or equal to 2.5%, and the CV value of breaking elongation is less than or equal to 5.0%.
Description
Technical field
The invention belongs to field of polyester fiber, it is related to a kind of porous polyester fiber HOY silk and preparation method thereof.
Background technology
Polyethylene terephthalate (PET or polyester fiber) fiber since the advent of the world, have fracture strength and
Elastic modelling quantity is high, and resilience is moderate, and thermal finalization is excellent, and heat-resisting light resistance is good and acid-fast alkali-proof corrosion resistance etc. is a series of excellent
Performance, and fabric has wash and wear, the advantages of stiffness is good, is widely used in the fields such as clothes, 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, strand arrangement 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 HTHP 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 industrial 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 cooling velocity and its uniformity of polyester fondant thread, generally adopt in production
Take cooling blowing.Cooling blowing can accelerate the cooling velocity of melt stream, is conducive to improving spinning speed；Strengthen empty around strand
The convection current of gas, makes ectonexine strand cool down uniformly, is to create condition using porous spinneret；Cooling blowing can make as-spun fibre
Quality advance, tensile property improves, and is conducive to the production capacity of raising equipment.
Experimental branch line all adopts cross air blasting as the type of cooling for a long time, and energy resource consumption accounts for long filament production cost very
Major part, increasingly improves to chemical fibre performance and quality requirements with people, and the exploitation of chemical-fibres filaments new product is to high added value
The cooling blowing condition it is desirable to higher is developed in fibre in differentiation direction, then proposes ring blowing device.Ring blowing device is not only
Possess the uniform advantage of every synnema wind-engaging, and energy consumption is compared relatively low, effectively solves cross air blasting because blowing area is big
The wind energy loss problem causing.
In spinning process, although ring blowing has obvious advantage, still have problems：Due to spun silk from
After circular spinneret extrusion, by ring wind quenching, due to the circular spinneret number of turns more so that ring blowing hardly enter interior
Layer, leads to that the silk of innermost layer may be also uncolled after cooling in outermost silk, thus the silk of gained fiber number irregular,
Intensity is irregular, the problems such as uneven dyeing, cause follow-up to silk be processed further difficulty occurs.
HOY is high oriented fibers, has stable internal structure and preferable uniformity, and the degree of orientation is high, and crystal region orientation is filled
Point but amorphous area orientation is very low, dyeing is easier to inhale color and evenly than FDY.Routine FDY is low for strength ratio, and elongation is big, boiling water
Shrink low, therefore fiber softening is good, can directly weave use as final products.But HOY product typically need 6000m/min with
On super high-speed spinning technique productions, need special spinning oil, and high to equipment and technological requirement.
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 porous polyester fiber HOY silk.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 coloring agent, 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 porous polyester fiber HOY silk, the material of described porous polyester fiber HOY silk is modified poly ester, described modification
Polyester is made up of terephthalic acid (TPA) segment, ethylene glycol segment and the dihydroxylic alcohols segment containing side chain, the described dihydroxylic alcohols chain containing side chain
Section refers 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；
The filament number of described porous polyester fiber HOY silk is 0.5～2.0dtex, and fracture strength >=3.0cN/dtex is broken
Splitting percentage elongation is 50.0 ± 4.0%；Described porous polyester fiber HOY silk temperature be 80～130 DEG C at, fibrous inside strand
Between spatial joint clearance increase 10～30v/v%；Line density deviation ratio≤0.2% of described porous polyester fiber HOY silk, fracture is strong
Degree CV value≤2.5%, extension at break CV value≤5.0%, boiling water shrinkage≤5.5%.
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 porous polyester fiber HOY silk, modified poly ester is adopted porous spinneret
Plate spinning is obtained porous polyester fiber HOY silk；On described porous spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, described
Oval shaped arrangements refer to that the hole of spinneret orifice is centrally located on concentration ellipse, and described concentration ellipse is that series is oval, all ellipses
Major axis is conllinear, and short axle is conllinear；
The preparation method of described porous polyester fiber HOY silk is：Modified poly ester obtains Modified polyester chips through pelletizing；Warp again
Measure, extrude, cooling down, oiling and high-speed winding, prepared porous polyester fiber HOY silk；
The preparation process of described modified poly ester is：
(1) preparation of terephthalic acid (TPA) binary alcohol esters；
Terephthalic acid (TPA) is made into after slurry with the dihydroxylic alcohols containing side chain, under the catalytic action of the concentrated sulfuric acid, is esterified
Reaction obtains terephthalic acid (TPA) binary alcohol esters；It is non-that the described dihydroxylic alcohols containing side chain refers 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 terephthalic acid (TPA) under the catalytic action of sulfuric 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；
Terephthalic acid (TPA) 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 terephthalic acid (TPA) 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 low vacuum stage polycondensation reaction and
The polycondensation reaction of high vacuum stage of Fig, prepared modified poly ester.
As preferred technical scheme：
A kind of preparation method of porous polyester fiber HOY silk as above, the concrete preparation process of described modified poly ester
For：
(1) preparation of terephthalic acid (TPA) binary alcohol esters；
Terephthalic acid (TPA) is made into slurry with the dihydroxylic alcohols containing side chain, under the catalytic action of the concentrated sulfuric 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 terephthalic acid (TPA) dihydroxylic alcohols
Ester；
(2) preparation of ethylene glycol terephthalate；
Terephthalic acid (TPA) 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 terephthalic acid (TPA) 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 low 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 reaction time is temperature control
30～50 minutes；Then proceed to vacuumize, 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 reaction time, prepared modified poly ester；
The main spinning technology parameter of described porous polyester fiber HOY silk is：
The temperature of extrusion：290～300 DEG C；
The wind-warm syndrome of cooling：20～25 DEG C；
The speed of winding：6000～7000m/min.
A kind of preparation method of porous polyester fiber HOY silk as above, in step (1), terephthalic acid (TPA) props up with containing
The mol ratio of the dihydroxylic alcohols of chain is 1:1.3-1.5；Concentrated sulfuric acid addition is the 0.3-0.5% of terephthalic acid (TPA) weight；Described dense
The concentration of sulfuric acid is 50-60wt%；
In step (2), terephthalic acid (TPA) is 1 with the mol ratio of ethylene glycol:1.2～2.0；
In step (3), described terephthalic acid (TPA) 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 terephthalic acid (TPA) gross weight
0.01%～0.05%；Described stabilizer is triphenyl phosphate, trimethyl phosphate or Trimethyl phosphite, stabilizer addition
For described terephthalic acid (TPA) gross weight 0.01%～0.05%；
The number-average molecular weight of described modified poly ester is 15000～30000.
A kind of preparation method of porous polyester fiber HOY silk as above, the described dihydroxylic alcohols containing side chain be 2- amyl group-
1,3 propane diols, 2- hexyl -1,3 propane diols, 2- heptyl -1,3 propane diols, 2- octyl group -1,3 propane diols, 2- nonyl -1,3 the third two
Alcohol, 2- decyl -1,3 propane diols, 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 hexylene glycol, 2- hexyl -1,6 hexylene glycol, 2- heptyl -1,6 hexylene glycol, 2- octyl group -1,6 hexylene glycol, 2- nonyl -1,6 are own
One or more of glycol or 2- decyl -1,6 hexylene glycol.
A kind of preparation method of porous polyester fiber HOY silk as above, described spinneret orifice be arranged as major axis and/or
Short axle is symmetrical.
A kind of preparation method of porous polyester fiber HOY silk as above, the ratio of oval major axis and minor axis length
For 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.Significant surface when spinneret
Simultaneously as the girth of ellipse is more than circular girth, the number of plies of spinneret orifice oval shaped arrangements is less than circular arrangement to long-pending phase
The number of plies, the hole count of spinneret orifice oval shaped arrangements is more than the hole count of circular arrangement, and therefore, spinneret orifice oval shaped arrangements are conducive to ring to blow
The cooling of wind, improves the cooling effectiveness of ring blowing, and the fibre property of preparation is also more excellent.The ratio of major axis and minor axis length is got over
Close to 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.
A kind of preparation method of porous polyester fiber HOY silk as above, described spinneret is circular spinneret or ellipse
Circular spinneret；The diameter of described circle spinneret is more than 10mm with the difference of the oval maximum long axis length of series, described ellipse
Circular spinneret is more than 10mm with the difference of the oval maximum long axis length of series.
A kind of preparation method of porous polyester fiber HOY silk as above, the guide hole of described spinneret orifice is a diameter of 1.5～
2.5mm；The spinneret hole count of described spinneret is more than or equal to 192.
A kind of preparation method of porous polyester fiber HOY silk as above, the spinneret orifice of described spinneret transversal
Face is generally circular in shape, square, rhombus, yi word pattern, triangular form, trilobal cross, hollow type or platypelloid type.
The principle of the present invention is：
For unbranched polyester fiber, its molecular chain structure is the linear macromolecule containing benzene ring structure, on strand
Functional group's marshalling, regularity is good, flexible poor；When temperature raises, its free volume increments is little, and these characteristics hinder
Hinder dyestuff to enter inside polyester fiber, thus dyeability is poor.
The raw material of the polyester fiber of the present invention is modified poly ester, the dihydroxylic alcohols containing side chain containing in modified poly ester macromolecular
Segment, when temperature is higher than vitrification point, side chain, prior to backbone motion, makes the increasing degree of free volume be far longer than and no props up
The characteristic of the polyester macromolecule chain of chain, the increase of free volume improves the degree within molecule entrance polyester, modified
The free volume of the polyester fiber of polyester preparation is far longer than unbranched polyester fiber at equal temperature, increases the diffusion of dyestuff
Degree, improves the dyeability of polyester fiber.Meanwhile, the polyester fiber of modified poly ester preparation advantageously reduces melt viscosity, has
It is beneficial to improve its processing characteristics.The introducing of the dihydroxylic alcohols segment containing side chain does not have big destruction to polyester fiber structures regularity,
Maintain the premium properties of polyester fiber.
When the effective area phase of spinneret is simultaneously as the girth of ellipse is more than circular girth, spinneret orifice is oval
The number of plies of arrangement is less than the number of plies of circular arrangement, and the hole count of spinneret orifice oval shaped arrangements is more than the hole count of circular arrangement, using spray
The spinneret of silk hole oval shaped arrangements enables to that fiber is quick, uniformly cools down, and between fiber, the difference of structure and performance is less,
Be conducive to improving the even dyeing rate of fiber and the performance of fiber.
Beneficial effect：
1) on the spinneret of the present invention, the arrangement mode of spinneret orifice is oval shaped arrangements, and the effective area of spinneret is identical
When, the number of plies of spinneret orifice oval shaped arrangements is less than the number of plies of circular arrangement, and ring blowing is easier to blow through dynamic analysis of spinning, dynamic analysis of spinning
Cooling effect more preferably, the fibre property of preparation is also more excellent.
2) on the spinneret of the present invention, the arrangement mode of spinneret orifice is oval shaped arrangements, and the effective area of spinneret is identical
When, the hole count of spinneret orifice oval shaped arrangements is more than the hole count of circular arrangement, and oval shaped arrangements are capable of greatly cooling down,
Significantly improve cooling effectiveness.
3) material of the porous polyester fiber HOY silk that the present invention is obtained is modified poly ester, contains in modified poly ester macromolecular
The dihydroxylic alcohols segment containing side chain, when temperature be higher than vitrification point when, side chain, prior to backbone motion, makes the increase of free volume
Amplitude is far longer than the characteristic of unbranched polyester macromolecule chain, and the increase of free volume improves molecule and enters in polyester
The degree in portion, increases the diffusion of dyestuff by the free volume that side chain increased polyester fiber, improves polyester fiber
Dyeability.
4) the porous polyester fiber HOY silk that the present invention is obtained, the increase of polyester fiber free volume advantageously reduces melt
Viscosity, is conducive to improving its processing characteristics.
5) the porous polyester fiber HOY silk that the present invention is obtained, the dihydroxylic alcohols segment containing side chain introducing to polyester fiber
Structural regularity there is no big destruction, maintain the premium properties of polyester fiber.
6) present invention is obtained porous polyester fiber HOY silk dyeability and good mechanical performance, porous polyester fiber HOY
Line density deviation ratio≤0.2% of silk, fracture strength CV value≤2.5%, extension at break CV value≤5.0%.
Brief description
Fig. 1 is the oval shaped arrangements figure of 374 spinneret orifices, and the aperture of spinneret orifice is 2.0mm, the length of transverse and short axle
Degree ratio is 1.3；
Fig. 2 is the circular arrangement figure of 370 spinneret orifices, and the aperture of spinneret orifice is 2.0mm；
Fig. 3 is the oval shaped arrangements figure of 382 spinneret orifices, and the aperture of spinneret orifice is 2.0mm, the length of transverse and short axle
Degree ratio is 1.6.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate this
Bright rather than limit the scope of the present invention.In addition, it is to be understood that after having read the content of present invention instruction, art technology
Personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Fixed scope.
Embodiment 1
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.3 terephthalic acid (TPA) and 2- amyl group -1,3 propane diols are made into slurry and add in reactor,
Concentration is 50wt%, and addition is under the catalytic action of 0.3% concentrated sulfuric acid of terephthalic acid (TPA) 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 terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.2 terephthalic acid (TPA)s 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 terephthalic acid (TPA) 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 terephthalic acid (TPA) weight 0.01% the catalytic antimony trioxide and addition be terephthalic acid (TPA) weight 0.01%
Stabilizer triphenyl phosphate in the presence of, under conditions of negative pressure start the low vacuum stage polycondensation reaction, this staged pressure
Steadily being evacuated to absolute pressure by normal pressure is 500Pa, and at 260 DEG C, the reaction time is 30 minutes to temperature control；Then proceed to take out very
Sky, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 100Pa, and reaction temperature controls 275
DEG C, 50 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 15000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- penta
Base -1,3 propane diols 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
, with embodiment 1, wherein main technical parameter is referring to table 1 for the preparation process of the modified poly ester of embodiment 2；In step
(3), after adding terephthalic acid (TPA) binary alcohol esters, stirring mixing 16 minutes, is terephthalic acid (TPA) gross weight in addition
0.011% the catalytic antimony trioxide and addition are the stabilizer triphenyl phosphate of the 0.02% of terephthalic acid (TPA) gross weight
In the presence of, start the polycondensation reaction in low vacuum stage under conditions of negative pressure, this staged pressure is steadily evacuated to definitely by normal pressure
Pressure 490Pa, at 262 DEG C, the reaction time is 31 minutes to temperature control；Then proceed to vacuumize, carry out the contracting of high vacuum stage of Fig
Poly- reaction, makes reaction pressure be down to absolute pressure 90Pa, reaction temperature controls at 276 DEG C, in 51 minutes reaction time, modification is obtained
Polyester.
The number-average molecular weight of modified poly ester is 16000, and modified poly ester is own by terephthalic acid (TPA) segment, ethylene glycol segment and 2-
Base -1,3 propane diols segment compositions, 2- hexyl -1,3 propane diols segments are 2.1% with the Mole percent ratio of ethylene glycol segment.
Embodiment 3
, with embodiment 1, wherein main technical parameter is referring to table 1 for the preparation process of the modified poly ester of embodiment 3；In step
(3), after adding terephthalic acid (TPA) binary alcohol esters, stirring mixing 16 minutes, is the 0.03% of terephthalic acid (TPA) gross weight in addition
The catalytic antimony trioxide and addition be terephthalic acid (TPA) gross weight 0.02% stabilizer triphenyl phosphate effect
Under, start the polycondensation reaction in low vacuum stage under conditions of negative pressure, this staged pressure is steadily evacuated to absolute pressure by normal pressure
498Pa, at 263 DEG C, the reaction time is 32 minutes to temperature control；Then proceed to vacuumize, the polycondensation carrying out high vacuum stage of Fig is anti-
Should, make reaction pressure be down to absolute pressure 90Pa, reaction temperature controls at 277 DEG C, in 57 minutes reaction time, be obtained modified poly-
Ester.
The number-average molecular weight of modified poly ester is 15900, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- heptan
Base -1,3 propane diols segment compositions, 2- heptyl -1,3 propane diols segments are 2.2% with the Mole percent ratio of ethylene glycol segment.
Embodiment 4
, with embodiment 1, wherein main technical parameter is referring to table 1 for the preparation process of the modified poly ester of embodiment 4；In step
(3), after adding terephthalic acid (TPA) binary alcohol esters, stirring mixing 17 minutes, is terephthalic acid (TPA) gross weight in addition
0.033% the catalytic antimony trioxide and addition are the stabilizer phosphoric acid triphen of the 0.023% of terephthalic acid (TPA) gross weight
Under conditions of negative pressure, in the presence of ester, start the polycondensation reaction in low vacuum stage, this staged pressure is steadily evacuated to absolutely by normal pressure
It is 497Pa to pressure, at 264 DEG C, the reaction time is 33 minutes to temperature control；Then proceed to vacuumize, carry out high vacuum stage of Fig
Polycondensation reaction, make reaction pressure be down to absolute pressure be 80Pa, reaction temperature controls at 278 DEG C, 58 minutes reaction time, system
Obtain modified poly ester.
The number-average molecular weight of modified poly ester is 15800, and modified poly ester is pungent by terephthalic acid (TPA) segment, ethylene glycol segment and 2-
Base -1,3 propane diols segment compositions, 2- octyl group -1,3 propane diols segments are 2.3% with the Mole percent ratio of ethylene glycol segment.
Embodiment 5
, with embodiment 1, wherein main technical parameter is referring to table 1 for the preparation process of the modified poly ester of embodiment 5；In step
(3), after adding terephthalic acid (TPA) binary alcohol esters, stirring mixing 17 minutes, is terephthalic acid (TPA) gross weight in addition
0.034% the catalytic antimony trioxide and addition are the stabilizer phosphoric acid triphen of the 0.024% of terephthalic acid (TPA) gross weight
Under conditions of negative pressure, in the presence of ester, start the polycondensation reaction in low vacuum stage, this staged pressure is steadily evacuated to absolutely by normal pressure
To pressure 496Pa, at 265 DEG C, the reaction time is 34 minutes to temperature control；Then proceed to vacuumize, carry out high vacuum stage of Fig
Polycondensation reaction, making reaction pressure be down to absolute pressure is 80Pa, and reaction temperature controls at 277 DEG C, 59 minutes reaction time, is obtained
Modified poly ester.
The number-average molecular weight of modified poly ester is 15900, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- nonyl
Base -1,3 propane diols segment compositions, 2- nonyl -1,3 propane diols segments are 2.4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 6
, with embodiment 1, wherein main technical parameter is referring to table 1 for the preparation process of the modified poly ester of embodiment 6；In step
(3), after adding terephthalic acid (TPA) binary alcohol esters, stirring mixing 18 minutes, is terephthalic acid (TPA) gross weight in addition
0.035% the catalytic antimony trioxide and addition are the stabilizer phosphoric acid triphen of the 0.025% of terephthalic acid (TPA) gross weight
Under conditions of negative pressure, in the presence of ester, start the polycondensation reaction in low vacuum stage, this staged pressure is steadily evacuated to absolutely by normal pressure
To pressure 495Pa, at 266 DEG C, the reaction time is 35 minutes to temperature control；Then proceed to vacuumize, carry out high vacuum stage of Fig
Polycondensation reaction, making reaction pressure be down to absolute pressure is 70Pa, and reaction temperature controls at 278 DEG C, 60 minutes reaction time, is obtained
Modified poly ester.
The number-average molecular weight of modified poly ester is 16000, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and the 2- last of the ten Heavenly stems
Base -1,3 propane diols segment compositions, 2- decyl -1,3 propane diols segments are 2.5% with the Mole percent ratio of ethylene glycol segment.
Embodiment 7
, with embodiment 1, wherein main technical parameter is referring to table 1 for the preparation process of the modified poly ester of embodiment 7；In step
(3), after adding terephthalic acid (TPA) binary alcohol esters, stirring mixing 19 minutes, is terephthalic acid (TPA) gross weight in addition
0.036% the catalytic antimony trioxide and addition are the stabilizer phosphoric acid triphen of the 0.025% of terephthalic acid (TPA) gross weight
Under conditions of negative pressure, in the presence of ester, start the polycondensation reaction in low vacuum stage, this staged pressure is steadily evacuated to absolutely by normal pressure
To pressure 496Pa, at 267 DEG C, the reaction time is 36 minutes to temperature control；Then proceed to vacuumize, carry out high vacuum stage of Fig
Polycondensation reaction, making reaction pressure be down to absolute pressure is 70Pa, and reaction temperature controls at 278 DEG C, 61 minutes reaction time, is obtained
Modified poly ester.
The number-average molecular weight of modified poly ester is 16000, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- penta
Base-Isosorbide-5-Nitrae butanediol segment composition, 2- amyl group-Isosorbide-5-Nitrae butanediol segment is 2.6% with the Mole percent ratio of ethylene glycol segment.
Embodiment 8
, with embodiment 1, wherein main technical parameter is referring to table 1 for the preparation process of the modified poly ester of embodiment 8；In step
(3), after adding terephthalic acid (TPA) binary alcohol esters, stirring mixing 19 minutes, is terephthalic acid (TPA) gross weight in addition
0.036% the catalytic antimony trioxide and addition are the stabilizer phosphoric acid triphen of the 0.025% of terephthalic acid (TPA) gross weight
Under conditions of negative pressure, in the presence of ester, start the polycondensation reaction in low vacuum stage, this staged pressure is steadily evacuated to absolutely by normal pressure
To pressure 496Pa, at 267 DEG C, the reaction time is 36 minutes to temperature control；Then proceed to vacuumize, carry out high vacuum stage of Fig
Polycondensation reaction, making reaction pressure be down to absolute pressure is 70Pa, and reaction temperature controls at 278 DEG C, 61 minutes reaction time, is obtained
Modified poly ester.
The number-average molecular weight of modified poly ester is 17000, and modified poly ester is own by terephthalic acid (TPA) 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
, with embodiment 1, wherein main technical parameter is referring to table 1 for the preparation process of the modified poly ester of embodiment 9；In step
(3), after adding terephthalic acid (TPA) binary alcohol esters, stirring mixing 16 minutes, is the 0.04% of terephthalic acid (TPA) gross weight in addition
Catalyst glycol antimony and addition be terephthalic acid (TPA) gross weight 0.026% stabilizer trimethyl phosphate effect
Under, start the polycondensation reaction in low vacuum stage under conditions of negative pressure, this staged pressure is steadily evacuated to absolute pressure by normal pressure
497Pa, at 268 DEG C, the reaction time is 38 minutes to temperature control；Then proceed to vacuumize, the polycondensation carrying out high vacuum stage of Fig is anti-
Should, making reaction pressure be down to absolute pressure is 60Pa, and reaction temperature controls at 279 DEG C, 62 minutes reaction time, is obtained modified poly-
Ester.
The number-average molecular weight of modified poly ester is 17000, and modified poly ester is by terephthalic acid (TPA) 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
, with embodiment 1, wherein main technical parameter is referring to table 1 for the preparation process of the modified poly ester of embodiment 10；In step
Suddenly, after (3) add terephthalic acid (TPA) binary alcohol esters, stirring mixing 17 minutes, is terephthalic acid (TPA) gross weight in addition
0.03% catalyst glycol antimony and addition are 0.027% stabilizer trimethyl phosphate of terephthalic acid (TPA) gross weight
Under conditions of negative pressure, under effect, start the polycondensation reaction in low vacuum stage, this staged pressure is steadily evacuated to absolute pressure by normal pressure
Power 498Pa, at 269 DEG C, the reaction time is 39 minutes to temperature control；Then proceed to vacuumize, carry out the polycondensation of high vacuum stage of Fig
Reaction, making reaction pressure be down to absolute pressure is 60Pa, and reaction temperature controls at 278 DEG C, 64 minutes reaction time, and modification is obtained
Polyester.
The number-average molecular weight of modified poly ester is 17000, and modified poly ester is pungent by terephthalic acid (TPA) 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
, with embodiment 1, wherein main technical parameter is referring to table 1 for the preparation process of the modified poly ester of embodiment 11；In step
Suddenly, after (3) add terephthalic acid (TPA) binary alcohol esters, stirring mixing 18 minutes, is terephthalic acid (TPA) gross weight in addition
0.04% catalyst glycol antimony and addition are 0.03% stabilizer trimethyl phosphate of terephthalic acid (TPA) gross weight
Under conditions of negative pressure, under effect, start the polycondensation reaction in low vacuum stage, this staged pressure is steadily evacuated to absolute pressure by normal pressure
Power 497Pa, at 260 DEG C, the reaction time is 40 minutes to temperature control；Then proceed to vacuumize, carry out the polycondensation of high vacuum stage of Fig
Reaction, making reaction pressure be down to absolute pressure is 60Pa, and reaction temperature controls at 277 DEG C, 63 minutes reaction time, and modification is obtained
Polyester.
The number-average molecular weight of modified poly ester is 18000, and modified poly ester is by terephthalic acid (TPA) 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
, with embodiment 1, wherein main technical parameter is referring to table 1 for the preparation process of the modified poly ester of embodiment 2；In step
(3), after adding terephthalic acid (TPA) binary alcohol esters, stirring mixing 18 minutes, is the 0.038% of terephthalic acid (TPA) weight in addition
Catalyst acetic acid antimony and addition be terephthalic acid (TPA) weight 0.03% stabilizer Trimethyl phosphite in the presence of,
Start the polycondensation reaction in low vacuum stage, this staged pressure is steadily evacuated to absolute pressure 497Pa by normal pressure, temperature under conditions of negative pressure
Degree controls at 265 DEG C, and the reaction time is 42 minutes；Then proceed to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction
It is 40Pa that pressure is down to absolute pressure, and reaction temperature controls at 277 DEG C, 70 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 26000, by terephthalic acid (TPA) 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 terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.5 terephthalic acid (TPA) and 2- decyl -1,6 hexylene glycols are made into slurry and add in reactor,
Concentration is 60wt%, and addition is under the catalytic action of 0.5% concentrated sulfuric acid of terephthalic acid (TPA) 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 terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:2.0 terephthalic acid (TPA)s 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 terephthalic acid (TPA) 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 terephthalic acid (TPA) weight 0.05% catalyst acetic acid antimony and addition be terephthalic acid (TPA) weight 0.05% steady
In the presence of determining agent Trimethyl phosphite, under conditions of negative pressure start the low 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 reaction time is 50 minutes to temperature control；Then proceed to vacuumize,
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 terephthalic acid (TPA) segment, ethylene glycol segment and the 2- last of the ten Heavenly stems
Base -1,6 hexylene glycol segment compositions, 2- decyl -1,6 hexylene glycol 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 terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.47 terephthalic acid (TPA) and 2- nonyl -1,6 hexylene glycols are made into slurry and add in reactor,
Concentration is 60wt%, and addition is under the catalytic action of 0.47% concentrated sulfuric acid of terephthalic acid (TPA) 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 terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.8 terephthalic acid (TPA)s 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 terephthalic acid (TPA) 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 terephthalic acid (TPA) weight 0.04% catalyst glycol antimony and addition be the 0.04% of terephthalic acid (TPA) weight
In the presence of stabilizer trimethyl phosphate, under conditions of negative pressure start the low vacuum stage polycondensation reaction, this staged pressure by
Normal pressure is steadily evacuated to absolute pressure 460Pa, and at 263 DEG C, the reaction time is 47 minutes to temperature control；Then proceed to vacuumize, 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 terephthalic acid (TPA) segment, ethylene glycol segment and 2- nonyl
Base -1,6 hexylene glycol segment compositions, 2- nonyl -1,6 hexylene glycol 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 terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.46 terephthalic acid (TPA) and 2- octyl group -1,6 hexylene glycols are made into slurry and add in reactor,
Concentration is 60wt%, and addition is under the catalytic action of 0.49% concentrated sulfuric acid of terephthalic acid (TPA) 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 terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.8 terephthalic acid (TPA)s 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 terephthalic acid (TPA) 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 terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under conditions of negative pressure, in the presence of 0.046% stabilizer triphenyl phosphate, start the polycondensation reaction in low vacuum stage, this rank
Section pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 269 DEG C, the reaction 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 reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 29000, pungent by terephthalic acid (TPA) segment, ethylene glycol segment and 2-
Base -1,6 hexylene glycol segment compositions, 2- octyl group -1,6 hexylene glycol 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 terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.49 terephthalic acid (TPA) and 2- heptyl -1,6 hexylene glycols are made into slurry and add in reactor,
Concentration is 60wt%, and addition is under the catalytic action of 0.48% concentrated sulfuric acid of terephthalic acid (TPA) 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 terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.8 terephthalic acid (TPA)s 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 terephthalic acid (TPA) 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 terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under conditions of negative pressure, in the presence of 0.047% stabilizer triphenyl phosphate, start the polycondensation reaction in low vacuum stage, this rank
Section pressure is steadily evacuated to absolute pressure 460Pa by normal pressure, and at 267 DEG C, the reaction 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 reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 27000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- heptan
Base -1,6 hexylene glycol segment compositions, 2- heptyl -1,6 hexylene glycol 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 terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.467 terephthalic acid (TPA) and 2- hexyl -1,6 hexylene glycols are made into slurry and add in reactor,
It is 60wt% in concentration, addition is under the catalytic action of 0.47% concentrated sulfuric acid of terephthalic acid (TPA) 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 terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.89 terephthalic acid (TPA)s 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 terephthalic acid (TPA) 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 terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under conditions of negative pressure, in the presence of 0.041% stabilizer Trimethyl phosphite, start the polycondensation reaction in low vacuum stage, should
Staged pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 268 DEG C, the reaction time is 48 minutes to temperature control；Then proceed to
Vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 40Pa, reaction temperature controls 278
DEG C, 85 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 29000, own by terephthalic acid (TPA) segment, ethylene glycol segment and 2-
Base -1,6 hexylene glycol segment compositions, 2- hexyl -1,6 hexylene glycol 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 terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.48 terephthalic acid (TPA) and 2- amyl group -1,6 hexylene glycols are made into slurry and add in reactor,
Concentration is 55wt%, and addition is under the catalytic action of 0.46% concentrated sulfuric acid of terephthalic acid (TPA) 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 terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.88 terephthalic acid (TPA)s 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 terephthalic acid (TPA) 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 terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under conditions of negative pressure, in the presence of 0.047% stabilizer triphenyl phosphate, start the polycondensation reaction in low vacuum stage, this rank
Section pressure is steadily evacuated to absolute pressure 480Pa by normal pressure, and at 265 DEG C, the reaction 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 reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 28000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- penta
Base -1,6 hexylene glycol segment compositions, 2- amyl group -1,6 hexylene glycol 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 terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.46 terephthalic acid (TPA) 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 sulfuric acid of terephthalic acid (TPA) 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 terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.9 terephthalic acid (TPA)s 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 terephthalic acid (TPA) 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 terephthalic acid (TPA) weight and addition is the 0.048% of terephthalic acid (TPA) weight
Stabilizer Trimethyl phosphite in the presence of, under conditions of negative pressure start the low 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 reaction 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 reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 29000, by terephthalic acid (TPA) 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 terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.46 terephthalic acid (TPA) 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 sulfuric acid of terephthalic acid (TPA) 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 terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.89 terephthalic acid (TPA)s 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 terephthalic acid (TPA) 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 terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under conditions of negative pressure, in the presence of 0.042% stabilizer trimethyl phosphate, start the polycondensation reaction in low vacuum stage, this rank
Section pressure is steadily evacuated to absolute pressure 460Pa by normal pressure, and at 265 DEG C, the reaction 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 reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 28000, by terephthalic acid (TPA) 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 terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.43 terephthalic acid (TPA) 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 sulfuric acid of terephthalic acid (TPA) 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 terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.78 terephthalic acid (TPA)s 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 terephthalic acid (TPA) 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 terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under conditions of negative pressure, in the presence of 0.049% stabilizer triphenyl phosphate, start the polycondensation reaction in low vacuum stage, this rank
Section pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 268 DEG C, the reaction 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 reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 28000, pungent by terephthalic acid (TPA) 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 terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.43 terephthalic acid (TPA) 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 sulfuric acid of terephthalic acid (TPA) 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 terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.87 terephthalic acid (TPA)s 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 terephthalic acid (TPA) 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 terephthalic acid (TPA) weight and addition is the 0.04% of terephthalic acid (TPA) weight
Stabilizer triphenyl phosphate in the presence of, under conditions of negative pressure start the low vacuum stage polycondensation reaction, this staged pressure
Absolute pressure 470Pa is steadily evacuated to by normal pressure, at 268 DEG C, the reaction time is 45 minutes to temperature control；Then proceed to vacuumize,
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 terephthalic acid (TPA) 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 terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.457 terephthalic acid (TPA) 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 sulfuric acid of terephthalic acid (TPA) 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 terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.81 terephthalic acid (TPA)s 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 terephthalic acid (TPA) 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 terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under conditions of negative pressure, in the presence of 0.048% stabilizer Trimethyl phosphite, start the polycondensation reaction in low vacuum stage, should
Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the reaction time is 45 minutes to temperature control；Then proceed to
Vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 50Pa, reaction temperature controls 275
DEG C, 85 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 28000, own by terephthalic acid (TPA) 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 terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.47 terephthalic acid (TPA) 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 sulfuric acid of terephthalic acid (TPA) 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 terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.81 terephthalic acid (TPA)s 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 terephthalic acid (TPA) 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 terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under conditions of negative pressure, in the presence of 0.042% stabilizer triphenyl phosphate, start the polycondensation reaction in low vacuum stage, this rank
Section pressure is steadily evacuated to absolute pressure 485Pa by normal pressure, and at 268 DEG C, the reaction 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 reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 29000, by terephthalic acid (TPA) 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 terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.45 terephthalic acid (TPA) 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 sulfuric acid of terephthalic acid (TPA) 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 terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.8 terephthalic acid (TPA)s 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 terephthalic acid (TPA) 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 terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under conditions of negative pressure, in the presence of 0.047% stabilizer Trimethyl phosphite, start the polycondensation reaction in low vacuum stage, should
Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the reaction time is 49 minutes to temperature control；Then proceed to
Vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 50Pa, reaction temperature controls 278
DEG C, 88 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester be 29000, by terephthalic acid (TPA) 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 terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:2- octyl group -1,6 hexylene glycol of 1.45 terephthalic acid (TPA) sum and 2- amyl group -1,5 pentanediol
Mixture is made into slurry and adds in reactor, wherein 2- octyl group -1,6 hexylene glycols 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 sulfuric acid of terephthalic acid (TPA) 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 terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.84 terephthalic acid (TPA)s 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 terephthalic acid (TPA) 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 terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under conditions of negative pressure, in the presence of 0.045% stabilizer Trimethyl phosphite, start the polycondensation reaction in low vacuum stage, should
Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the reaction time is 45 minutes to temperature control；Then proceed to
Vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 50Pa, reaction temperature controls 278
DEG C, 85 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester be 28000, by terephthalic acid (TPA) segment, ethylene glycol segment, 2- octyl group-
1,6 hexylene glycol segment and 2- amyl group -1,5 pentanediol segment compositions, 2- octyl group -1,6 hexylene glycol 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 terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.45 terephthalic acid (TPA) 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 sulfuric acid of terephthalic acid (TPA) 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 terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.8 terephthalic acid (TPA)s 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 terephthalic acid (TPA) 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 terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under conditions of negative pressure, in the presence of 0.047% stabilizer Trimethyl phosphite, start the polycondensation reaction in low vacuum stage, should
Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the reaction time is 49 minutes to temperature control；Then proceed to
Vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 50Pa, reaction temperature controls 278
DEG C, 88 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester be 29000, by terephthalic acid (TPA) 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 terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.45 terephthalic acid (TPA) is own with 2- octyl group -1,3 propane diols, 2- amyl group -1,4 butanediol and 2-
Base -1, the mixture of 6 hexylene glycols is made into slurry and adds in reactor, wherein 2- octyl group -1,3 propane diols, 2- amyl group-Isosorbide-5-Nitrae fourth two
The mol ratio of alcohol and 2- hexyl -1,6 hexylene glycol is 3:2:1, it is 60% in concentration, addition is terephthalic acid (TPA) weight
Under the catalytic action of 0.47% concentrated sulfuric 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 terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.8 terephthalic acid (TPA)s 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 terephthalic acid (TPA) 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 terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under conditions of negative pressure, in the presence of 0.041% stabilizer Trimethyl phosphite, start the polycondensation reaction in low vacuum stage, should
Staged pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 268 DEG C, the reaction time is 49 minutes to temperature control；Then proceed to
Vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 50Pa, reaction temperature controls 277
DEG C, 84 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment, band side chain
Glycol segment composition, wherein branched glycol segment be 2- octyl group -1,3 propane diols segments, 2- amyl group-Isosorbide-5-Nitrae butanediol chain
Section and 2- hexyl -1,6 hexylene glycol segments form, and branched glycol segment with the Mole percent ratio of ethylene glycol segment is
4.71%.
Embodiment 29
A kind of preparation method of porous polyester fiber HOY silk, porous polyester fiber HOY silk adopts porous spinneret to be obtained,
On spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located at concentration ellipse
On, concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear.
As shown in figure 1, the major axis of ellipse is 1.3 with the ratio of minor axis length, the spacing of adjacent spinneret orifice is equal to spinneret orifice
Guide hole diameter add 1.5mm, spinneret is circular spinneret, the diameter of circular spinneret oval maximum long axial length with series
The difference of degree is 11mm, a diameter of 2.0mm of guide hole of spinneret orifice, and the spinneret hole count of spinneret is 374, the spinneret orifice of spinneret
Shape of cross section be circle.
The modified poly ester that embodiment 1 is obtained obtains Modified polyester chips through pelletizing；Again through measuring, extrude, cool down, oil and
High-speed winding, prepared porous polyester fiber HOY silk；The temperature of extrusion is 290 DEG C, and the wind-warm syndrome of cooling is 20 DEG C, the speed of winding
For 6000m/min.
The filament number of prepared porous polyester fiber HOY silk is 0.8dtex, and fracture strength is 4.0cN/dtex, fracture
Percentage elongation is 50.0%；At temperature is 80 DEG C, the spatial joint clearance of fibrous inside molecule interchain increases porous polyester fiber HOY silk
15v/v%；The line density deviation ratio of polyester fiber is 0.2%, and fracture strength CV value is 2.0%, and extension at break CV value is
5.0%, yarn unevenness CV value is 2.0%, and boiling water shrinkage is 5.2%, and oil content is 0.80%.
Embodiment 30
A kind of preparation method of porous polyester fiber HOY silk, porous polyester fiber HOY silk adopts porous spinneret to be obtained,
On spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located at concentration ellipse
On, concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear.
As shown in figure 3, the major axis of ellipse is 1.6 with the ratio of minor axis length, the spacing of adjacent spinneret orifice is equal to spinneret orifice
Guide hole diameter add 1.5mm, spinneret is circular spinneret, the diameter of circular spinneret oval maximum long axial length with series
The difference of degree is 11mm, a diameter of 2.0mm of guide hole of spinneret orifice, and the spinneret hole count of spinneret is 382, the spinneret orifice of spinneret
Shape of cross section be circle.
The modified poly ester that embodiment 1 is obtained obtains Modified polyester chips through pelletizing；Again through measuring, extrude, cool down, oil and
High-speed winding, prepared porous polyester fiber HOY silk；The temperature of extrusion is 290 DEG C, and the wind-warm syndrome of cooling is 20 DEG C, the speed of winding
For 6000m/min.
The filament number of prepared porous polyester fiber HOY silk is 0.5dtex, and fracture strength is 5.6cN/dtex, fracture
Percentage elongation is 54.0%, and at temperature is 80 DEG C, the spatial joint clearance of fibrous inside molecule interchain increases porous polyester fiber HOY silk
18v/v%；The line density deviation ratio of polyester fiber is 0.1%, and fracture strength CV value is 1.0%, and extension at break CV value is
4.0%, yarn unevenness CV value is 1.0%, and boiling water shrinkage is 4.5%, and oil content is 0.90%.
Comparative example 1
A kind of preparation method of porous polyester fiber HOY silk, porous polyester fiber HOY silk adopts porous spinneret to be obtained,
On spinneret, the arrangement mode of spinneret orifice is circular arrangement, and circular arrangement refers to that the hole of spinneret orifice is centrally located on concentric circles, with
Heart circle is circular for series.As shown in Fig. 2 the guide hole diameter that the spacing of adjacent spinneret orifice is equal to spinneret orifice adds 1.5mm, spinneret
For circular spinneret, the diameter of circular spinneret is 11mm with the difference of the circular maximum diameter of series, and the guide hole of spinneret orifice is straight
Footpath is 2.0mm, and the spinneret hole count of spinneret is 370, and the shape of cross section of the spinneret orifice of spinneret is circle.
The modified poly ester that embodiment 1 is obtained obtains Modified polyester chips through pelletizing；Again through measuring, extrude, cool down, oil and
High-speed winding, prepared porous polyester fiber HOY silk；The temperature of extrusion is 290 DEG C, and the wind-warm syndrome of cooling is 20 DEG C, the speed of winding
For 6000m/min.
The filament number of prepared porous polyester fiber HOY silk is 3.0dtex, and fracture strength is 2.8cN/dtex, fracture
Percentage elongation is 40.0%；At temperature is 80 DEG C, the spatial joint clearance of fibrous inside molecule interchain increases porous polyester fiber HOY silk
10v/v%；The line density deviation ratio of polyester fiber is 0.3%, and fracture strength CV value is 3.0%, and extension at break CV value is
6.0%, yarn unevenness CV value is 5.0%, and boiling water shrinkage is 6.0%, and oil content is 0.70%.
When identical with the effective area that embodiment 29 contrast can be seen that spinneret, (circular arrangement when spinneret hole count is close
Spinneret hole count is 370, and oval shaped arrangements spinneret 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 spinneret 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 fibroid of the spinneret of spinneret orifice oval shaped arrangements
Can be better than the spinneret using spinneret circular arrangement.
Embodiment 31～33
A kind of preparation method of porous polyester fiber HOY silk, porous polyester fiber HOY silk adopts porous spinneret to be obtained,
On spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located at concentration ellipse
On, concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear.
Spinneret orifice be arranged as long axial symmetry, oval major axis is 1.4 with the ratio of minor axis length, between adjacent spinneret orifice
Add 1.6mm away from the guide hole diameter equal to spinneret orifice, spinneret is circular spinneret, the diameter of circular spinneret is oval with series
The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 192 of spinneret, spinneret
The shape of cross section of the spinneret orifice of plate is square.
Modified poly ester obtains Modified polyester chips through pelletizing；Again through measuring, extruding, cool down, oil and high-speed winding, it is obtained
Porous polyester fiber HOY silk；The temperature of extrusion is 295 DEG C, and the wind-warm syndrome of cooling is 21 DEG C, and the speed of winding is 7000m/min.System
The mechanical property of the porous polyester fiber HOY silk spatial joint clearance Magnification of fibrous inside molecule interchain and the fiber at 80 DEG C that obtain
Can data such as following table.
Embodiment 34～36
A kind of preparation method of porous polyester fiber HOY silk, porous polyester fiber HOY silk adopts porous spinneret to be obtained,
On spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located at concentration ellipse
On, concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear.
Spinneret orifice be arranged as that short axle is symmetrical, oval major axis is 1.4 with the ratio of minor axis length, between adjacent spinneret orifice
Add 1.7mm away from the guide hole diameter equal to spinneret orifice, spinneret is elliptical spinneret plate, elliptical spinneret plate is with serial ellipse
The difference of big long axis length is 12mm, a diameter of 1.8mm of guide hole of spinneret orifice, and the spinneret hole count of spinneret is 200, spinneret
Spinneret orifice shape of cross section be rhombus.
Modified poly ester obtains Modified polyester chips through pelletizing；Again through measuring, extruding, cool down, oil and high-speed winding, it is obtained
Porous polyester fiber HOY silk；The temperature of extrusion is 298 DEG C, and the wind-warm syndrome of cooling is 22 DEG C, and the speed of winding is 7000m/min.System
The mechanical property of the porous polyester fiber HOY silk spatial joint clearance Magnification of fibrous inside molecule interchain and the fiber at 90 DEG C that obtain
Can data such as following table.
Embodiment 37～39
A kind of preparation method of porous polyester fiber HOY silk, porous polyester fiber HOY silk adopts porous spinneret to be obtained,
On spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located at concentration ellipse
On, concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear.
Spinneret orifice be arranged as that major axis and short axle are symmetrical, oval major axis is 1.4 with the ratio of minor axis length, adjacent spinneret
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 spinneret hole count of spinneret is
200, the shape of cross section of the spinneret orifice of spinneret is yi word pattern.
Modified poly ester obtains Modified polyester chips through pelletizing；Again through measuring, extruding, cool down, oil and high-speed winding, it is obtained
Porous polyester fiber HOY silk；The temperature of extrusion is 298 DEG C, and the wind-warm syndrome of cooling is 23 DEG C, and the speed of winding is 6500m/min.System
The mechanics of the porous polyester fiber HOY silk spatial joint clearance Magnification of fibrous inside molecule interchain and the fiber at 100 DEG C that obtain
Performance data such as following table.
Embodiment 40～42
A kind of preparation method of porous polyester fiber HOY silk, porous polyester fiber HOY silk adopts porous spinneret to be obtained,
On spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located at concentration ellipse
On, concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear.
Spinneret orifice be arranged as that major axis and short axle are symmetrical, oval major axis is 1.7 with the ratio of minor axis length, adjacent spinneret
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 spinneret hole count of spinneret is 210,
The shape of cross section of the spinneret orifice of spinneret is triangular form.
Modified poly ester obtains Modified polyester chips through pelletizing；Again through measuring, extruding, cool down, oil and high-speed winding, it is obtained
Porous polyester fiber HOY silk；The temperature of extrusion is 293 DEG C, and the wind-warm syndrome of cooling is 24 DEG C, and the speed of winding is 6200m/min.System
The mechanics of the porous polyester fiber HOY silk spatial joint clearance Magnification of fibrous inside molecule interchain and the fiber at 110 DEG C that obtain
Performance data such as following table.
Embodiment 43～45
A kind of preparation method of porous polyester fiber HOY silk, porous polyester fiber HOY silk adopts porous spinneret to be obtained,
On spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located at concentration ellipse
On, concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear.
Spinneret orifice be arranged as that short axle is symmetrical, oval major axis is 1.8 with the ratio of minor axis length, between adjacent spinneret orifice
Add 1.5mm away from the guide hole diameter equal to spinneret orifice, spinneret is circular spinneret, the diameter of circular spinneret is oval with series
The difference of maximum long axis length is 15mm, a diameter of 1.8mm of guide hole of spinneret orifice, and the spinneret hole count of spinneret is 240, spinneret
The shape of cross section of the spinneret orifice of plate is trilobal cross.
Modified poly ester obtains Modified polyester chips through pelletizing；Again through measuring, extruding, cool down, oil and high-speed winding, it is obtained
Porous polyester fiber HOY silk；The temperature of extrusion is 295 DEG C, and the wind-warm syndrome of cooling is 25 DEG C, and the speed of winding is 6800m/min.System
The mechanics of the porous polyester fiber HOY silk spatial joint clearance Magnification of fibrous inside molecule interchain and the fiber at 120 DEG C that obtain
Performance data such as following table.
Embodiment 46～49
A kind of preparation method of porous polyester fiber HOY silk, porous polyester fiber HOY silk adopts porous spinneret to be obtained,
On spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located at concentration ellipse
On, concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear.
Spinneret orifice be arranged as long axial symmetry, oval major axis is 1.8 with the ratio of minor axis length, between adjacent spinneret orifice
Add 1.6mm away from the guide hole diameter equal to spinneret orifice, spinneret is circular spinneret, the diameter of circular spinneret is oval with series
The difference of maximum long axis length is 16mm, a diameter of 2.2mm of guide hole of spinneret orifice, and the spinneret hole count of spinneret is 250, spinneret
The shape of cross section of the spinneret orifice of plate is hollow type.
Modified poly ester obtains Modified polyester chips through pelletizing；Again through measuring, extruding, cool down, oil and high-speed winding, it is obtained
Porous polyester fiber HOY silk；The temperature of extrusion is 300 DEG C, and the wind-warm syndrome of cooling is 20 DEG C, and the speed of winding is 6000m/min.System
The mechanics of the porous polyester fiber HOY silk spatial joint clearance Magnification of fibrous inside molecule interchain and the fiber at 130 DEG C that obtain
Performance data such as following table.
Embodiment 50～53
A kind of preparation method of porous polyester fiber HOY silk, porous polyester fiber HOY silk adopts porous spinneret to be obtained,
On spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located at concentration ellipse
On, concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear.
Spinneret orifice be arranged as that short axle is symmetrical, oval major axis is 1.8 with the ratio of minor axis length, between adjacent spinneret orifice
Add 1.8mm away from the guide hole diameter equal to spinneret orifice, spinneret is circular spinneret, the diameter of circular spinneret is oval with series
The difference of maximum long axis length is 15mm, a diameter of 2.5mm of guide hole of spinneret orifice, and the spinneret hole count of spinneret is 260, spinneret
The shape of cross section of the spinneret orifice of plate is platypelloid type.
Modified poly ester obtains Modified polyester chips through pelletizing；Again through measuring, extruding, cool down, oil and high-speed winding, it is obtained
Porous polyester fiber HOY silk；The temperature of extrusion is 300 DEG C, and the wind-warm syndrome of cooling is 22 DEG C, and the speed of winding is 7000m/min.System
The mechanics of the porous polyester fiber HOY silk spatial joint clearance Magnification of fibrous inside molecule interchain and the fiber at 100 DEG C that obtain
Performance data such as following table.
Embodiment 54～57
A kind of preparation method of porous polyester fiber HOY silk, porous polyester fiber HOY silk adopts porous spinneret to be obtained,
On spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located at concentration ellipse
On, concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear.
Spinneret orifice be arranged as long axial symmetry, oval major axis is 1.8 with the ratio of minor axis length, between adjacent spinneret orifice
Add 1.5mm away from the guide hole diameter equal to spinneret orifice, spinneret is circular spinneret, the diameter of circular spinneret is oval with series
The difference of maximum long axis length is 16mm, a diameter of 1.8mm of guide hole of spinneret orifice, and the spinneret hole count of spinneret is 300, spinneret
The shape of cross section of the spinneret orifice of plate is hollow type.
Modified poly ester obtains Modified polyester chips through pelletizing；Again through measuring, extruding, cool down, oil and high-speed winding, it is obtained
Porous polyester fiber HOY silk；The temperature of extrusion is 290 DEG C, and the wind-warm syndrome of cooling is 23 DEG C, and the speed of winding is 6400m/min.System
The mechanics of the porous polyester fiber HOY silk spatial joint clearance Magnification of fibrous inside molecule interchain and the fiber at 120 DEG C that obtain
Performance data such as following table.
Embodiment 58
The dyeing of modified polyester fiber：
The porous polyester fiber HOY silk of embodiment 29 preparation is dyeed in HTHP machine, actual conditions is：Dye
Before color, modified polyester fiber nonionic surfactant is processed 30 minutes at 60 DEG C, is subsequently adding in dyeing liquor, in dyeing liquor
Disperse dyes consumption be 2.0% (o.w.f)；Dispersant NNO, concentration 1.2g/L of dispersant NNO；PH value is 5, and bath raio is 1:
50, enter dye at 60 DEG C, then heat to 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C and 130 DEG C of each constant temperature dyeing 1h.
Using identical dyeing condition, general fibre is dyeed.Porous polyester fiber HOY silk after dyed upper
Dye percentage obtains by the following method：
Dye uptake adopts raffinate colorimetric method to determine, draws appropriate dyeing stoste and dyeing residual liquid, adds N, N-2 first
Base formamide (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 stoste and dyeing residual liquid.
When disperse dyes are Disperse Red 3B, disperse blue SE-2R or disperse bright blue S-GL when, porous polyester fiber HOY silk and
The dye uptake result such as following table of general fibre：
| Dyestuff | Temperature | 90℃ | 100℃ | 110℃ | 120℃ | 130℃ |
| Disperse Red 3B | Modified fibre | 60.2 | 86.0 | 86.0 | 91.7 | 93.4 |
| General fibre | 28.3 | 46.4 | 78.4 | 81.4 | 90.4 | |
| Disperse blue SE-2R | Modified fibre | 64.2 | 84.1 | 89.7 | 90.5 | 94.2 |
| General fibre | 12.6 | 35.6 | 73.5 | 88.4 | 91.7 | |
| Disperse bright blue S-GL | Modified fibre | 56.8 | 80.0 | 83.1 | 86.0 | 88.2 |
| General fibre | 11.6 | 36.2 | 70.5 | 75.4 | 82.9 |
Contrasted by Color it can be seen that the Color of modified polyester fiber is substantially better than general fibre.
Embodiment 59
The dyeing of modified polyester fiber：
Porous polyester fiber HOY silk to embodiment 35 preparation, dyeing course is identical with embodiment 58, adopts identical simultaneously
Dyeing condition general fibre is dyeed.
When disperse dyes are Disperse Red 3B, disperse blue SE-2R or disperse bright blue S-GL when, porous polyester fiber HOY silk and
The dye uptake result such as following table of general fibre：
| Dyestuff | Temperature | 90℃ | 100℃ | 110℃ | 120℃ | 130℃ |
| Disperse Red 3B | Modified fibre | 60.4 | 86.2 | 88.0 | 93.7 | 94.5 |
| General fibre | 28.3 | 46.4 | 78.4 | 81.4 | 90.4 | |
| Disperse blue SE-2R | Modified fibre | 65.3 | 85.2 | 90.9 | 91.7 | 95.3 |
| General fibre | 12.6 | 35.6 | 73.5 | 88.4 | 91.7 | |
| Disperse bright blue S-GL | Modified fibre | 57.9 | 81.1 | 84.2 | 87.2 | 90.2 |
| General fibre | 11.6 | 36.2 | 70.5 | 75.4 | 82.9 |
Contrasted by Color it can be seen that the Color of modified polyester fiber is substantially better than general fibre.
Claims (10)
1. a kind of porous polyester fiber HOY silk, is characterized in that：The material of described porous polyester fiber HOY silk is modified poly ester, institute
State modified poly ester form by terephthalic acid (TPA) segment, ethylene glycol segment and containing the dihydroxylic alcohols segment of side chain, described containing side chain two
First alcohol segment refers to that side chain is located on one of dihydroxylic alcohols segment non-end group carbon and side chain is straight containing 5-10 carbon atom
The dihydroxylic alcohols segment of chain carbochain；
The filament number of described porous polyester fiber HOY silk is 0.5～2.0dtex, fracture strength >=3.0cN/dtex, and fracture is stretched
Long rate is 50.0 ± 4.0%；Described porous polyester fiber HOY silk temperature be 80～130 DEG C at, fibrous inside molecule interchain
Spatial joint clearance increases 10～30v/v%；Line density deviation ratio≤0.2% of described porous polyester fiber HOY silk, fracture strength CV
Value≤2.5%, extension at break CV value≤5.0%, boiling water shrinkage≤5.5%.
2. a kind of preparation method of porous polyester fiber HOY silk as claimed in claim 1, is characterized in that：Modified poly ester is adopted
Porous polyester fiber HOY silk is obtained with porous spinneret spinning；On described porous spinneret, the arrangement mode of spinneret orifice is ellipse
Shape arranges, and described oval shaped arrangements refer to that the hole of spinneret orifice is centrally located on concentration ellipse, and described concentration ellipse is that series is oval,
All oval major axis are conllinear, and short axle is conllinear；
The preparation method of described porous polyester fiber HOY silk is：Modified poly ester obtains Modified polyester chips through pelletizing；Again through meter
Measure, extrude, cooling down, oiling and high-speed winding, prepared porous polyester fiber HOY silk；
The preparation process of described modified poly ester is：
(1) preparation of terephthalic acid (TPA) binary alcohol esters；
Terephthalic acid (TPA) is made into after slurry with the dihydroxylic alcohols containing side chain, under the catalytic action of the concentrated sulfuric acid, carries out esterification
Obtain terephthalic acid (TPA) binary alcohol esters；The described dihydroxylic alcohols containing side chain refers 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；
Terephthalic acid (TPA) 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 terephthalic acid (TPA) 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 low vacuum stage successively
The polycondensation reaction in empty stage, prepared modified poly ester.
3. a kind of preparation method of porous polyester fiber HOY silk according to claim 2 is it is characterised in that described modification
The concrete preparation process of polyester is：
(1) preparation of terephthalic acid (TPA) binary alcohol esters；
Terephthalic acid (TPA) is made into slurry with the dihydroxylic alcohols containing side chain, under the catalytic action of the concentrated sulfuric 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 terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate；
Terephthalic acid (TPA) 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 terephthalic acid (TPA) 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 low vacuum stage,
This staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature control at 260～270 DEG C, the reaction time be 30～
50 minutes；Then proceed to vacuumize, 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 reaction time, prepared modified poly ester；
The main spinning technology parameter of described porous polyester fiber HOY silk is：
The temperature of extrusion：290～300 DEG C；
The wind-warm syndrome of cooling：20～25 DEG C；
The speed of winding：6000～7000m/min.
4. a kind of preparation method of porous polyester fiber HOY silk according to claim 2 is it is characterised in that step (1)
In, terephthalic acid (TPA) is 1 with the mol ratio of the dihydroxylic alcohols containing side chain:1.3-1.5；Concentrated sulfuric acid addition is terephthalic acid (TPA) weight
0.3-0.5%；The concentration of the described concentrated sulfuric acid is 50-60wt%；
In step (2), terephthalic acid (TPA) is 1 with the mol ratio of ethylene glycol:1.2～2.0；
In step (3), the Mole percent ratio of described terephthalic acid (TPA) binary alcohol esters and ethylene glycol terephthalate is 2～
5%；Described catalyst is antimony oxide, antimony glycol or antimony acetate, and catalyst charge is terephthalic acid (TPA) gross weight
0.01%～0.05%；Described stabilizer is triphenyl phosphate, trimethyl phosphate or Trimethyl phosphite, and stabilizer addition is
The 0.01%～0.05% of described terephthalic acid (TPA) gross weight；
The number-average molecular weight of described modified poly ester is 15000～30000.
5. a kind of porous polyester fiber HOY silk according to claim 2 preparation method it is characterised in that described containing
The dihydroxylic alcohols of chain is 2- amyl group -1,3 propane diols, 2- hexyl -1,3 propane diols, 2- heptyl -1,3 propane diols, 2- octyl group -1,3 the third two
Alcohol, 2- nonyl -1,3 propane diols, 2- decyl -1,3 propane diols, 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 hexylene glycol, 2- hexyl -1,6 hexylene glycol, 2- heptyl -1,6 hexylene glycol, 2- octyl group -1,6 are own
One or more of glycol, 2- nonyl -1,6 hexylene glycol or 2- decyl -1,6 hexylene glycol.
6. a kind of preparation method of porous polyester fiber HOY silk according to claim 2 is it is characterised in that described spinneret
Hole be arranged as major axis and/or short axle is symmetrical.
7. a kind of preparation method of porous polyester fiber HOY silk according to claim 2 is it is characterised in that the length of ellipse
Axle is 1.3～1.8 with the ratio of minor axis length；The guide hole diameter that the spacing of adjacent spinneret orifice is more than or equal to spinneret orifice adds
1.5mm.
8. a kind of preparation method of porous polyester fiber HOY silk according to claim 2 is it is characterised in that described spinneret
Plate is circular spinneret or elliptical spinneret plate；The diameter of described circle spinneret and the difference of the oval maximum long axis length of series
Value is more than 10mm, and 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 porous polyester fiber HOY silk according to claim 2 is it is characterised in that described spinneret
A diameter of 1.5～the 2.5mm of guide hole in hole；The spinneret hole count of described spinneret is more than or equal to 192.
10. a kind of preparation method of porous polyester fiber HOY silk according to claim 2 is it is characterised in that described spinneret
The shape of cross section of the spinneret orifice of plate is circle, square, rhombus, yi word pattern, triangular form, trilobal cross, hollow type or flat
Type.
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| CN108130614A (en) * | 2017-12-14 | 2018-06-08 | 江苏恒力化纤股份有限公司 | A kind of polyester HOY fibers and preparation method thereof |
| CN108385226A (en) * | 2017-12-14 | 2018-08-10 | 江苏恒力化纤股份有限公司 | A kind of polyester imitates cotton abnormal contraction composite filament and preparation method thereof |
| CN108977976A (en) * | 2018-08-11 | 2018-12-11 | 界首市梦佳怡家居有限公司 | A kind of modified dacron mattress fabric that antibiotic property is strong |
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