CN106319675B - A kind of preparation method of porous modified polyester fiber - Google Patents
A kind of preparation method of porous modified polyester fiber Download PDFInfo
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- CN106319675B CN106319675B CN201610770147.8A CN201610770147A CN106319675B CN 106319675 B CN106319675 B CN 106319675B CN 201610770147 A CN201610770147 A CN 201610770147A CN 106319675 B CN106319675 B CN 106319675B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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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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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
- D01D5/247—Discontinuous hollow structure or microporous structure
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a kind of preparation methods of porous modified polyester fiber, and porous modified polyester fiber is made using porous spinneret spinning in modified poly ester；The arrangement mode of spinneret orifice is oval shaped arrangements on porous spinneret, i.e. the hole center of spinneret orifice is located on concentration ellipse, and concentration ellipse is that series is oval, and all elliptical long axis are conllinear, and short axle is conllinear.Porous modified polyester fiber is squeezed out through metering, porous spinneret by modified poly ester, is cooled down, oiled, stretched, thermal finalization and winding are made, and the preparation method of modified poly ester is：Ethylene glycol terephthalate is made with glycol reaction in terephthalic acid (TPA), terephthalic acid (TPA) and terephthalic acid (TPA) binary alcohol esters made from the diol reaction containing branch is added, the reaction was continued obtains modified poly ester.Fibre property produced by the present invention is excellent, fracture strength CV value≤4.0%, extension at break CV value≤8.0%, yarn unevenness CV value≤2.0%, and boiling water shrinkage is 7.5 ± 0.5%.
Description
Technical field
The invention belongs to field of polyester fiber, are related to a kind of preparation method of porous modified polyester fiber.
Background technology
Polyethylene terephthalate (PET fiber or polyester fiber) fiber since the advent of the world, have fracture strength and
Elasticity modulus 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 many advantages, such as wash and wear, stiffness is good, is widely used in the fields such as clothes, home textile.
But due to the crystallinity of PET height, compact structure, and the functional group not being combined with dyestuff on strand cause
Dye molecule hardly enters fibrous inside, and dyeing is difficult.People be cannot be satisfied to bright-coloured beautiful, unique style fabric demand.
The reason for causing PET dyeing difficult is the straight chain macromolecular that PET belongs to symmetry, and strand does not contain side chain radical
Group, regularity is very good, its main chain contains rigid phenyl ring and alkyl flexible, and the ester group being directly connected with phenyl ring with
Phenyl ring constitutes rigid conjugated system again, to constrain rotating freely for its soft segment.Such a structure increases molecules
The wall ridge of sub-chain motion, causes the glass transition temperature of PET higher, needs to promote dye molecule under very high temperature condition
Staining procedure is completed in diffusion to fibrous inside.In addition, the strand of PET is regular, good crystallinity, strand arrangement is close, and
And the polar group not having an effect with dye molecule on strand, keep the colouring of PET fiber more difficult.
Therefore, under the general high temperature and pressure of the dyeing of common PET fiber, disperse dyeing is selected, when temperature reaches PET
When fiber obtains glass transition temperature or more, gap increases between PET fiber polymer molecule, but the increased degree of its free volume is small,
Dyeing rate is not high, but it is the main problem faced now that energy consumption and dye-uptake caused by high temperature and high pressure method are low.In addition,
PET fiber melt viscosity is higher, is unfavorable for processing.
There are many method for preparing PET fiber, and wherein melt spinning method is one kind more in current industrial production application.It is molten
Melt many of spinning process parameter, these parameters determine the course of fiberizing and spin the structure and performance of fiber, production
Upper is exactly the fiber for being made by controlling these parameters required performance.The main spinning that can will be controlled in production according to technical process
Silk summary of parameters.An is melting condition, spinning conditions, condition of cure, wrapping wire condition etc., and wherein strand cools and solidifies condition to fiber
Structure has conclusive influence with performance, and the cooling velocity and its uniformity of polyester fondant thread, are generally adopted in production in order to control
Take cooling blowing.Cooling blowing can accelerate the cooling velocity of melt stream, be conducive to improve spinning speed；Reinforce empty around strand
The convection current of gas keeps the cooling of ectonexine strand uniform, to create condition using porous spinneret；Cooling blowing can make as-spun fibre
Quality advance, tensile property improve, and are conducive to the production capacity for improving equipment.
Experimental branch line all uses cross air blasting as the type of cooling for a long time, and energy consumption accounts for long filament production cost very
Most of, as people increasingly improve chemical fibre performance and quality requirements, the exploitation of chemical-fibres filaments new product is to high added value
Fibre in differentiation direction is developed, it is desirable that higher cooling blowing condition then proposes ring blowing device.Ring blowing device is not only
Have a uniform advantage of every synnema wind-engaging, and energy consumption is compared to relatively low, effective solution cross air blasting since blowing area is big and
Caused by wind energy lose problem.
In spinning process, although ring blowing has apparent advantage, the cooling of porous yarn can not be well solved
Uneven problem.Since spun silk is after round spinneret extrusion, by ring wind quenching, due to the round spinneret number of turns compared with
It is more so that ring blowing hardly enters innermost layer, leads to that the silk of innermost layer may be also uncolled after cooling in outermost silk,
There is the problems such as fiber number is irregular, and intensity is irregular, uneven dyeing to the silk of gained, the further processing subsequently to silk is caused to occur
Difficulty.
Invention content
The purpose of the present invention is overcoming the problems such as existing dyeing polyester fibers are irregular, mechanical property is poor, realize extensive
The production spinning of change provides a kind of preparation method of porous modified polyester fiber.The raw material of the polyester fiber of the present invention is to be modified
Polyester, introduces the dihydric alcohol segment containing branch in the strand of modified poly ester, modified polyester fiber prepared by modified polyester, and 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 nothing at same temperature
The conventional polyester fiber of branch is conducive to the molecules such as coloring agent and enters internal degree, improves dyeing rate；Modified poly ester
The melt viscosity of fiber reduces, and reduces processing temperature, reduces degradation rate, is conducive to process；In addition the dihydric alcohol chain containing branch
The not big destruction of structural regularity of the section to modified polyester fiber, maintains the excellent performance of polyester fiber.Spinning of the present invention
In the process use spinneret orifice oval shaped arrangements spinneret, be conducive to fiber in spinning process it is uniform, be fully cooled, fiber
Between performance and structure difference it is smaller, improve the dyeing uniformity and mechanical property of fiber.
In order to achieve the above objectives, the technical solution adopted by the present invention is：
Modified poly ester is made porous using porous spinneret spinning and changed by a kind of preparation method of porous modified polyester fiber
Property polyester fiber；The arrangement mode of spinneret orifice is oval shaped arrangements on the porous spinneret, and the oval shaped arrangements refer to spray
The hole center of wire hole is located on concentration ellipse, and the concentration ellipse is that series is oval, and all elliptical long axis are conllinear, and short axle is total
Line；
The preparation process of the porous modified polyester fiber is：Modified poly ester squeezes out through metering, porous spinneret, is cooling,
It oils, stretch, thermal finalization and winding, porous modified polyester fiber is made；The temperature of the extrusion is 280~290 DEG C, described cold
But wind-warm syndrome is 20~25 DEG C, and the speed of the winding is 4000~4200m/min；
The preparation process of the modified poly ester is：
(1) preparation of terephthalic acid (TPA) binary alcohol esters；
After terephthalic acid (TPA) and the dihydric alcohol containing branch are made into slurry, under the catalytic action of the concentrated sulfuric acid, it is esterified
Terephthalic acid (TPA) binary alcohol esters are obtained by the reaction；The dihydric alcohol segment containing branch refers to one that branch is located in dihydric alcohol segment
On a non-end group carbon and branch be the linear carbon chain containing 5-10 carbon atom dihydric alcohol segment；
For the dihydric alcohol containing branch, branch is alkyl, is electron-withdrawing group, in the presence of branch, makes strand
Spatial volume increases, and solvation becomes smaller, and proton is not easy to dissociate in dihydric alcohol so that the dihydric alcohol containing branch and terephthaldehyde
The reactivity of acid is less than ethylene glycol, mixes according to same ethylene glycol and is reacted with terephthalic acid (TPA), can cause the binary containing branch
Alcohol reaction is imperfect, to influence ratio of the dihydric alcohol containing branch in polyester macromolecule, and then influences the performance of polyester.This
Using the dihydric alcohol containing branch is first carried out esterification under the catalytic action of sulfuric acid with terephthalic acid (TPA), product exists for invention
It is added after ethylene glycol and p phthalic acid esterification, ensure that the stability of the dihydric alcohol proportioning containing branch；
(2) preparation of ethylene glycol terephthalate；
After terephthalic acid (TPA) and ethylene glycol are made into slurry, esterification is carried out, ethylene glycol terephthalate is obtained；
(3) preparation of modified poly ester；
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, stir
Mix mixing, under the action of catalyst and stabilizer, under conditions of negative pressure, successively carry out low vacuum stage polycondensation reaction and
Modified poly ester is made in the polycondensation reaction of high vacuum stage of Fig.
As preferred technical solution：
A kind of preparation method of porous modified polyester fiber as described above, the specific preparation process of the modified poly ester
For：
(1) preparation of terephthalic acid (TPA) binary alcohol esters；
Terephthalic acid (TPA) and the dihydric alcohol containing branch are made into slurry, under the catalytic action of the concentrated sulfuric acid, be esterified anti-
It answers, 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 to change when the water quantity of distillate in reaction reaches 90% of theoretical value or more, obtains terephthalic acid (TPA) dihydric alcohol
Ester；
(2) preparation of ethylene glycol terephthalate；
After terephthalic acid (TPA) and ethylene glycol are made into slurry, esterification is carried out, esterification is pressurizeed in nitrogen atmosphere
Reaction, moulding pressure are normal pressure~0.3MPa, and temperature is 250~260 DEG C, when the water quantity of distillate in esterification reaches theoretical value
90% or more when be esterification terminal, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester；
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, stir
Mixing 15-20 minutes is mixed, under the action of catalyst and stabilizer, the polycondensation for starting low vacuum stage under conditions of negative pressure is anti-
It answers, which by normal pressure is steadily evacuated to absolute pressure 500Pa hereinafter, temperature control is at 260~270 DEG C, and the reaction time is
30~50 minutes；It then proceedes to vacuumize, carries out the polycondensation reaction of high vacuum stage of Fig, so that reaction pressure is down to absolute pressure and be less than
Modified poly ester is made in 275~280 DEG C, 50~90 minutes reaction time in 100Pa, reaction temperature control.
A kind of preparation method of porous modified polyester fiber as described above, in step (1), terephthalic acid (TPA) with contain branch
Dihydric alcohol molar ratio be 1:1.3-1.5；Concentrated sulfuric acid addition is the 0.3-0.5% of terephthalic acid (TPA) weight；The dense sulphur
A concentration of 50-60wt% of acid；
In step (2), the molar ratio of terephthalic acid (TPA) and ethylene glycol is 1:1.2~2.0；
In step (3), the Mole percent ratio of the terephthalic acid (TPA) binary alcohol esters and ethylene glycol terephthalate is 2
~5%；The catalyst is antimony oxide, antimony glycol or antimony acetate, and catalyst charge is terephthalic acid (TPA) total weight
0.01%~0.05%；The stabilizer is triphenyl phosphate, trimethyl phosphate or Trimethyl phosphite, stabilizer addition
It is the 0.01%~0.05% of the terephthalic acid (TPA) total weight.
The number-average molecular weight of the modified poly ester is 15000~30000.
A kind of preparation method of porous modified polyester fiber as described above, the dihydric alcohol containing branch are 2- amyls-
1,3 propylene glycol, -1,3 propylene glycol of 2- hexyls, -1,3 propylene glycol of 2- heptyl, -1,3 propylene glycol of 2- octyls, 2- nonyls -1,3 the third two
Alcohol, -1,3 propylene glycol of 2- decyls, -1,4 butanediol of 2- amyls, -1,4 butanediol of 2- hexyls, -1,4 butanediol of 2- heptyl, 2- are pungent
- 1,4 butanediol of base, -1,4 butanediol of 2- nonyls, -1,4 butanediol of 2- decyls, -1,5 pentanediol of 2- amyls, 2- hexyls -1,5 penta
Glycol, -1,5 pentanediol of 2- heptyl, -1,5 pentanediol of 2- octyls, -1,5 pentanediol of 2- nonyls, -1,5 pentanediol of 2- decyls, 2- penta
- 1,6 hexylene glycol of base, -1,6 hexylene glycol of 2- hexyls, -1,6 hexylene glycol of 2- heptyl, -1,6 hexylene glycol of 2- octyls, 2- nonyls -1,6 oneself
One or more of -1,6 hexylene glycol of glycol or 2- decyls.
A kind of preparation method of porous modified polyester fiber as described above, the spinneret orifice be arranged as long axis and/or
Short axle is symmetrical.
The ratio of a kind of preparation method of porous modified polyester fiber as described above, elliptical long axis and minor axis length is
1.3~1.8；The guide hole diameter that the spacing of adjacent spinneret orifice is more than or equal to spinneret orifice adds 1.5mm.When the effective area of spinneret
Mutually simultaneously as the perimeter of ellipse is more than circular perimeter, the number of plies of spinneret orifice oval shaped arrangements is less than the layer of circular arrangement
Number, the hole count of spinneret orifice oval shaped arrangements are more than the hole count of circular arrangement, and therefore, spinneret orifice oval shaped arrangements are conducive to ring blowing
Cooling, improve the cooling efficiency of ring blowing, the fibre property of preparation is also more excellent.Long axis and the ratio of minor axis length more connect
It is bordering on 1, ellipse is more similar to justify, and the difference of cooling efficiency and cooling effect is little；Long axis and the ratio of minor axis length are 1.3
When, cooling effect significantly improves, and individual pen hole count accordingly increases by 16%；When long axis and the ratio of minor axis length are 1.8, cooling effect
Improve larger, individual pen hole count accordingly increases by 33%, in the case of identical hole count, and oval shaped arrangements of the invention are justified than conventional concentric arranges
The number of turns of row is reduced, and is easy to cooling wind and is blown through, makes the fiber cooling condition of Internal and external cycle evenly；The ratio of long axis and minor axis length
When more than 1.8, ellipse is partial to form flat shape, is not easy to punch, cooling no longer increases.Therefore, series is ellipse
The ratio of round long axis and minor axis length is 1.3~1.8, can reach higher cooling efficiency and preferable cooling effect.
A kind of preparation method of porous modified polyester fiber as described above, the spinneret are round spinneret or ellipse
Shape spinneret；The diameter of the circle spinneret and the difference of the oval maximum long axis length of series are more than 10mm, the ellipse
Shape spinneret and the difference of the oval maximum long axis length of series are more than 10mm.
A kind of preparation method of porous modified polyester fiber as described above, the guide hole a diameter of 1.5 of the spinneret orifice~
2.5mm；The spinneret hole count of the spinneret is more than or equal to 192.
A kind of preparation method of porous modified polyester fiber as described above, the cross section of the spinneret orifice of the spinneret
Shape is circle, square, diamond shape, "-" type, triangular form, trilobal cross, hollow type or platypelloid type.
A kind of preparation method of porous modified polyester fiber as described above, the fracture of the porous modified polyester fiber are strong
Degree >=3.8cN/dtex, elongation at break are 33.0 ± 3.0%；The porous modified polyester fiber is 80~130 DEG C in temperature
Under, the spatial joint clearance of fibrous inside molecule interchain increases 10~30v/v%, at 260~290 DEG C, melt viscosity decline 10~
20%；Line density deviation ratio≤0.5% of the porous modified polyester fiber, fracture strength CV value≤4.0%, extension at break CV
Value≤8.0%, yarn unevenness CV value≤2.0%, boiling water shrinkage are 7.5 ± 0.5%, and oil content is 0.90 ± 0.20%,
The fibrous inside molecule interchain spatial joint clearance increase refer to modified poly ester with normal polyester in mutually synthermal fiber
The comparison of spatial joint clearance between the subchain of part, melt viscosity decline refer to modified poly ester with normal polyester mutually synthermal
The comparison of melt viscosity.
The principle of the present invention is：
For unbranched polyester fiber, molecular chain structure is the linear macromolecule containing benzene ring structure, on strand
Functional group's marshalling, regularity is good, flexible poor；Its free volume increments is small when the temperature rises, the resistance of these characteristics
Dyestuff has been hindered 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 dihydric alcohol containing branch contained in modified poly ester macromolecular
Segment, when temperature is higher than glass transition temperature, branch makes the increasing degree of free volume be far longer than no branch prior to backbone motion
The characteristic of the polyester macromolecule chain of chain, the increase of free volume improves molecule and enters degree inside polyester, modified
The free volume of polyester fiber prepared by polyester is far longer than polyester fiber unbranched at same temperature, increases the diffusion of dyestuff
Degree improves the dyeability of polyester fiber.Meanwhile polyester fiber prepared by modified poly ester advantageously reduces melt viscosity, has
Conducive to its processing performance of improvement.The introducing of dihydric alcohol segment containing the branch destruction not big to polyester fiber structures regularity,
Maintain the excellent performance of polyester fiber.
When the effective area phase of spinneret is simultaneously as the perimeter of ellipse is more than circular perimeter, spinneret orifice ellipse
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 wire hole oval shaped arrangements enables to fiber quick, uniformly cooling, and the difference of structure and performance is smaller between fiber,
Be conducive to improve the performance of the even dyeing rate and fiber of fiber.
Advantageous effect：
1) arrangement mode of spinneret orifice is oval shaped arrangements on spinneret of the invention, 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 it is more preferable, the fibre property of preparation is also more excellent.
2) arrangement mode of spinneret orifice is oval shaped arrangements on spinneret of the invention, 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 can realize a greater degree of cooling,
Significantly improve cooling efficiency.
3) raw material of polyester fiber produced by the present invention is modified poly ester, contain in modified poly ester macromolecular containing branch
Dihydric alcohol segment, when temperature is higher than glass transition temperature, branch keeps the increasing degree of free volume much big prior to backbone motion
In the characteristic of unbranched polyester macromolecule chain, the increase of free volume improves molecule and enters degree inside polyester,
The free volume of polyester fiber is increased to increase the diffusion of dyestuff by branch, improves the dyeability of polyester fiber.
4) increase of polyester fiber produced by the present invention, polyester fiber free volume advantageously reduces melt viscosity, favorably
In its processing performance of improvement.
5) polyester fiber produced by the present invention, the compound with regular structure of the polyester fiber of the introducing pair of the dihydric alcohol segment containing branch
The not big destruction of property, maintains the excellent performance of polyester fiber.
6) dyeing polyester fibers performance and good mechanical performance produced by the present invention, the line density of porous modified polyester fiber
Deviation ratio≤0.5%, fracture strength CV value≤4.0%, extension at break CV value≤8.0%, yarn unevenness CV value≤2.0%,
Boiling water shrinkage is 7.5 ± 0.5%, and oil content is 0.90 ± 0.20%.
Description of the drawings
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
It is 1.3 to spend ratio；
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
It is 1.6 to spend ratio.
Specific implementation mode
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Embodiment 1
A kind of preparation method of polyester fiber, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.3 terephthalic acid (TPA) is made into slurry with 2- amyl -1,3 propylene glycol and is added in reactor,
A concentration of 50wt%, addition are to carry out esterification under the catalytic action of 0.3% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure are normal pressure, and temperature is 180 DEG C, when the water in esterification distillates
Amount is esterification terminal when reaching the 90% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.2 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, carry out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure are normal pressure, and temperature is 250 DEG C, when the water in esterification distillates
Amount is esterification terminal when reaching the 90% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 2%, is stirred 15 minutes, is being added
Amount is 0.01% the catalytic antimony trioxide of terephthalic acid (TPA) total weight and addition is terephthalic acid (TPA) total weight
Under the action of 0.01% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure
It is 500Pa that section pressure, which is steadily evacuated to absolute pressure by normal pressure, and at 260 DEG C, the reaction time is 30 minutes for temperature control；It then proceedes to
It vacuumizes, carries out the polycondensation reaction of high vacuum stage of Fig, it is 100Pa so that reaction pressure is down to absolute pressure, and reaction temperature control exists
275 DEG C, modified poly ester was made in 50 minutes reaction time.
The number-average molecular weight of modified poly ester is 15000, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- penta
Base -1,3 propylene glycol segment forms, and the Mole percent ratio of the dihydric alcohol segment containing branch and ethylene glycol segment is 2%.
Table 1：Embodiment 2-12 important technological parameters
Embodiment 2
The preparation method of the polyester fiber of embodiment 2, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly
Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 16 minutes, is in addition
0.011% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are the 0.02% of terephthalic acid (TPA) total weight
Stabilizer triphenyl phosphate under the action of, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure
Absolute pressure 490Pa is steadily evacuated to by normal pressure, at 262 DEG C, the reaction time is 31 minutes for temperature control；It then proceedes to vacuumize,
The polycondensation reaction for carrying out high vacuum stage of Fig makes reaction pressure be down to absolute pressure 90Pa, and reaction temperature is controlled at 276 DEG C, reaction
Modified poly ester was made in 51 minutes time.
The number-average molecular weight of modified poly ester be 16000, modified poly ester by terephthalic acid (TPA) segment, ethylene glycol segment and 2- oneself
Base -1,3 propylene glycol segment forms, and the Mole percent ratio of 2- hexyl -1,3 propylene glycol segments and ethylene glycol segment is 2.1%.
Embodiment 3
The preparation method of the polyester fiber of embodiment 3, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly
Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 16 minutes, is in addition
0.03% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are the 0.02% of terephthalic acid (TPA) total weight
Stabilizer triphenyl phosphate under the action of, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure
Absolute pressure 498Pa is steadily evacuated to by normal pressure, at 263 DEG C, the reaction time is 32 minutes for temperature control；It then proceedes to vacuumize,
The polycondensation reaction for carrying out high vacuum stage of Fig makes reaction pressure be down to absolute pressure 90Pa, and reaction temperature is controlled at 277 DEG C, reaction
Modified poly ester was made in 57 minutes time.
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 propylene glycol segment forms, and the Mole percent ratio of 2- heptyl -1,3 propylene glycol segments and ethylene glycol segment is 2.2%.
Embodiment 4
The preparation method of the polyester fiber of embodiment 4, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly
Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 17 minutes, is in addition
0.033% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are terephthalic acid (TPA) total weight
Under the action of 0.023% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure
It is 497Pa that section pressure, which is steadily evacuated to absolute pressure by normal pressure, and at 264 DEG C, the reaction time is 33 minutes for temperature control；It then proceedes to
It vacuumizes, carries out the polycondensation reaction of high vacuum stage of Fig, it is 80Pa so that reaction pressure is down to absolute pressure, and reaction temperature control exists
278 DEG C, modified poly ester was made in 58 minutes reaction time.
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 propylene glycol segment forms, and the Mole percent ratio of 2- octyl -1,3 propylene glycol segments and ethylene glycol segment is 2.3%.
Embodiment 5
The preparation method of the polyester fiber of embodiment 5, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly
Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 17 minutes, is in addition
0.034% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are terephthalic acid (TPA) total weight
Under the action of 0.024% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure
Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and at 265 DEG C, the reaction time is 34 minutes for temperature control；It then proceedes to take out
Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and it is 80Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled 277
DEG C, modified poly ester was made in 59 minutes reaction time.
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- nonyls
Base -1,3 propylene glycol segment forms, and the Mole percent ratio of 2- nonyl -1,3 propylene glycol segments and ethylene glycol segment is 2.4%.
Embodiment 6
The preparation method of the polyester fiber of embodiment 6, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly
Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 18 minutes, is in addition
0.035% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are terephthalic acid (TPA) total weight
Under the action of 0.025% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure
Section pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 266 DEG C, the reaction time is 35 minutes for temperature control；It then proceedes to take out
Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and it is 70Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled 278
DEG C, modified poly ester was made in 60 minutes reaction time.
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 propylene glycol segment forms, and the Mole percent ratio of 2- decyl -1,3 propylene glycol segments and ethylene glycol segment is 2.5%.
Embodiment 7
The preparation method of the polyester fiber of embodiment 7, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly
Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 19 minutes, is in addition
0.036% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are terephthalic acid (TPA) total weight
Under the action of 0.025% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure
Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and at 267 DEG C, the reaction time is 36 minutes for temperature control；It then proceedes to take out
Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and it is 70Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled 278
DEG C, modified poly ester was made in 61 minutes reaction time.
The number-average molecular weight of modified poly ester is 16000, and the number-average molecular weight of modified poly ester is 16000, and modified poly ester is by right
Phthalic acid segment, ethylene glycol segment and 2- amyls-Isosorbide-5-Nitrae butanediol segment composition, 2- amyls-Isosorbide-5-Nitrae butanediol segment and second two
The Mole percent ratio of alcohol segment is 2.6%.
Embodiment 8
The preparation method of the polyester fiber of embodiment 8, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly
Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 19 minutes, is in addition
0.036% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are terephthalic acid (TPA) total weight
Under the action of 0.025% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure
Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and at 267 DEG C, the reaction time is 36 minutes for temperature control；It then proceedes to take out
Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and it is 70Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled 278
DEG C, modified poly ester was made in 61 minutes reaction time.
The number-average molecular weight of modified poly ester be 17000, modified poly ester by terephthalic acid (TPA) segment, ethylene glycol segment and 2- oneself
The Mole percent ratio of base-Isosorbide-5-Nitrae butanediol segment composition, 2- hexyls-Isosorbide-5-Nitrae butanediol segment and ethylene glycol segment is 2.7%.
Embodiment 9
The preparation method of the polyester fiber of embodiment 9, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly
Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 16 minutes, is in addition
0.04% catalyst glycol antimony and addition of terephthalic acid (TPA) total weight are the 0.026% of terephthalic acid (TPA) total weight
Under the action of stabilizer trimethyl phosphate, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure by
Normal pressure is steadily evacuated to absolute pressure 497Pa, and at 268 DEG C, the reaction time is 38 minutes for temperature control；It then proceedes to vacuumize, into
The polycondensation reaction of row high vacuum stage of Fig, it is 60Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled at 279 DEG C, reaction
Modified poly ester was made in 62 minutes time.
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
The Mole percent ratio of base-Isosorbide-5-Nitrae butanediol segment composition, 2- heptyl-Isosorbide-5-Nitrae butanediol segment and ethylene glycol segment is 2.8%.
Embodiment 10
The preparation method of the polyester fiber of embodiment 10, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly
Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 17 minutes, is in addition
0.03% catalyst glycol antimony and addition of terephthalic acid (TPA) total weight are the 0.027% of terephthalic acid (TPA) total weight
Under the action of stabilizer trimethyl phosphate, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure by
Normal pressure is steadily evacuated to absolute pressure 498Pa, and at 269 DEG C, the reaction time is 39 minutes for temperature control；It then proceedes to vacuumize, into
The polycondensation reaction of row high vacuum stage of Fig, it is 60Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled at 278 DEG C, reaction
Modified poly ester was made in 64 minutes time.
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-
The Mole percent ratio of base-Isosorbide-5-Nitrae butanediol segment composition, 2- octyls-Isosorbide-5-Nitrae butanediol segment and ethylene glycol segment is 3%.
Embodiment 11
The preparation method of the polyester fiber of embodiment 11, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly
Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 18 minutes, is in addition
0.04% catalyst glycol antimony and addition of terephthalic acid (TPA) total weight are the 0.03% of terephthalic acid (TPA) total weight
Under the action of stabilizer trimethyl phosphate, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure by
Normal pressure is steadily evacuated to absolute pressure 497Pa, and at 260 DEG C, the reaction time is 40 minutes for temperature control；It then proceedes to vacuumize, into
The polycondensation reaction of row high vacuum stage of Fig, it is 60Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled at 277 DEG C, reaction
Modified poly ester was made in 63 minutes time.
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- nonyls
The Mole percent ratio of base-Isosorbide-5-Nitrae butanediol segment composition, 2- nonyls-Isosorbide-5-Nitrae butanediol segment and ethylene glycol segment is 4%.
Embodiment 12
The preparation method of the polyester fiber of embodiment 2, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly
Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 18 minutes, is in addition
The catalyst acetic acid antimony and addition of the 0.038% of terephthalic acid (TPA) weight are 0.03% stabilizer of terephthalic acid (TPA) weight
Under the action of Trimethyl phosphite, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, the staged pressure is by normal pressure
Steady to be evacuated to absolute pressure 497Pa, at 265 DEG C, the reaction time is 42 minutes for temperature control；It then proceedes to vacuumize, carry out high
The polycondensation reaction of vacuum stages, it is 40Pa so that reaction pressure is down to absolute pressure, and reaction temperature control is at 277 DEG C, the reaction time
70 minutes, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained is 26000, by terephthalic acid (TPA) segment, ethylene glycol segment and the 2- last of the ten Heavenly stems
The Mole percent ratio of base-Isosorbide-5-Nitrae butanediol segment composition, 2- decyls-Isosorbide-5-Nitrae butanediol segment and ethylene glycol segment is 4%.
Embodiment 13
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.5 terephthalic acid (TPA) is made into slurry with 2- decyl -1,6 hexylene glycols and is added in reactor,
A concentration of 60wt%, addition are to carry out esterification under the catalytic action of 0.5% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.3MPa, temperature is 240 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:2.0 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, carry out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.3MPa, temperature is 260 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 5%, is stirred 20 minutes, is being added
Amount be 0.05% catalyst acetic acid antimony of terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight 0.05% it is steady
Under the action of determining agent Trimethyl phosphite, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure by
It is 450Pa that normal pressure, which is steadily evacuated to absolute pressure, and at 270 DEG C, the reaction time is 50 minutes for temperature control；It then proceedes to vacuumize,
The polycondensation reaction for carrying out high vacuum stage of Fig, it is 30Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled at 280 DEG C, instead
90 minutes between seasonable, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained 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 forms, and the Mole percent ratio of 2- decyl -1,6 hexylene glycol segments and ethylene glycol segment is 5%.
Embodiment 14
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.47 terephthalic acid (TPA) is made into slurry with 2- nonyl -1,6 hexylene glycols and is added in reactor,
A concentration of 60wt%, addition are to carry out esterification under the catalytic action of 0.47% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 220 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.8 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, carry out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.27MPa, temperature is 258 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4%, is stirred 18 minutes, is being added
Amount is 0.04% catalyst glycol antimony of terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight 0.04%
Under the action of stabilizer trimethyl phosphate, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure by
Normal pressure is steadily evacuated to absolute pressure 460Pa, and at 263 DEG C, the reaction time is 47 minutes for temperature control；It then proceedes to vacuumize, into
The polycondensation reaction of row high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature is controlled at 278 DEG C, reaction
Between 85 minutes, be made modified poly ester.
The number-average molecular weight of modified poly ester obtained is 28000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- nonyls
Base -1,6 hexylene glycol segment forms, and the Mole percent ratio of 2- nonyl -1,6 hexylene glycol segments and ethylene glycol segment is 4%.
Embodiment 15
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.46 terephthalic acid (TPA) is made into slurry with 2- octyl -1,6 hexylene glycols and is added in reactor,
A concentration of 60wt%, addition are to carry out esterification under the catalytic action of 0.49% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 233 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.8 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, carry out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 259 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.5%, is stirred 19 minutes, is adding
It is terephthalic acid (TPA) weight to enter 0.044% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition
Under the action of 0.046% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure
Section pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 269 DEG C, the reaction time is 48 minutes for temperature control；It then proceedes to take out
Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be down to absolute pressure 40Pa, and reaction temperature is controlled at 279 DEG C,
Modified poly ester was made in 87 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 29000, pungent by terephthalic acid (TPA) segment, ethylene glycol segment and 2-
Base -1,6 hexylene glycol segment forms, and the Mole percent ratio of 2- octyl -1,6 hexylene glycol segments and ethylene glycol segment is 4.5%.
Embodiment 16
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.49 terephthalic acid (TPA) is made into slurry with 2- heptyl -1,6 hexylene glycols and is added in reactor,
A concentration of 60wt%, addition are to carry out esterification under the catalytic action of 0.48% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 230 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.8 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, carry out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 258 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.7%, is stirred 19 minutes, is adding
It is terephthalic acid (TPA) weight to enter 0.048% catalyst glycol antimony that amount is terephthalic acid (TPA) weight and addition
Under the action of 0.047% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure
Section pressure is steadily evacuated to absolute pressure 460Pa by normal pressure, and at 267 DEG C, the reaction time is 48 minutes for temperature control；It then proceedes to take out
Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be down to absolute pressure 40Pa, and reaction temperature is controlled at 279 DEG C,
Modified poly ester was made in 83 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 27000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- heptan
Base -1,6 hexylene glycol segment forms, and the Mole percent ratio of 2- heptyl -1,6 hexylene glycol segments and ethylene glycol segment is 4.7%.
Embodiment 17
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.467 terephthalic acid (TPA) is made into slurry with 2- hexyl -1,6 hexylene glycols and is added in reactor,
In a concentration of 60wt%, addition is be esterified anti-under the catalytic action of 0.47% concentrated sulfuric acid of terephthalic acid (TPA) weight
It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.27MPa, temperature is 236 DEG C, when in esterification
Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.89 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, be esterified anti-
It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 258 DEG C, when in esterification
Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.3%, is stirred 18 minutes, is adding
It is terephthalic acid (TPA) weight to enter 0.04% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition
Under the action of 0.041% stabilizer Trimethyl phosphite, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, it should
Staged pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 268 DEG C, the reaction time is 48 minutes for temperature control；It then proceedes to
It vacuumizes, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be down to absolute pressure 40Pa, reaction temperature is controlled 278
DEG C, modified poly ester was made in 85 minutes reaction time.
The number-average molecular weight of modified poly ester obtained be 29000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- oneself
Base -1,6 hexylene glycol segment forms, and the Mole percent ratio of 2- hexyl -1,6 hexylene glycol segments and ethylene glycol segment is 4.3%.
Embodiment 18
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.48 terephthalic acid (TPA) is made into slurry with 2- amyl -1,6 hexylene glycols and is added in reactor,
A concentration of 55wt%, addition are to carry out esterification under the catalytic action of 0.46% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 230 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.88 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, be esterified anti-
It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 256 DEG C, when in esterification
Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.7%, is stirred 18 minutes, is adding
It is terephthalic acid (TPA) weight to enter 0.047% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition
Under the action of 0.047% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure
Section pressure is steadily evacuated to absolute pressure 480Pa by normal pressure, and at 265 DEG C, the reaction time is 47 minutes for temperature control；It then proceedes to take out
Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be down to absolute pressure 40Pa, and reaction temperature is controlled at 279 DEG C,
Modified poly ester was made in 85 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 28000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- penta
Base -1,6 hexylene glycol segment forms, and the Mole percent ratio of 2- amyl -1,6 hexylene glycol segments and ethylene glycol segment is 4.7%.
Embodiment 19
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.46 terephthalic acid (TPA) is made into slurry with 2- decyl -1,5 pentanediols and is added in reactor,
A concentration of 55wt%, addition are to carry out esterification under the catalytic action of 0.47% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 238 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.9 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, carry out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 259 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching 92% of theoretical value or more, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.7%, is stirred 19 minutes, is adding
Enter the 0.046% catalyst acetic acid antimony that amount is terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight 0.048%
Stabilizer Trimethyl phosphite under the action of, under conditions of negative pressure start low vacuum stage polycondensation reaction, the stage pressure
It is 446Pa that power, which is steadily evacuated to absolute pressure by normal pressure, and at 267 DEG C, the reaction time is 49 minutes for temperature control；It then proceedes to take out true
Sky carries out the polycondensation reaction of high vacuum stage of Fig, and it is 40Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled at 278 DEG C,
Modified poly ester was made in 87 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment and the 2- last of the ten Heavenly stems
Base -1,5 pentanediol segment forms, and the Mole percent ratio of 2- decyl -1,5 pentanediol segments and ethylene glycol segment is 4.7%.
Embodiment 20
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.46 terephthalic acid (TPA) is made into slurry with 2- nonyl -1,5 pentanediols and is added in reactor,
A concentration of 60wt%, addition are to carry out esterification under the catalytic action of 0.46% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.26MPa, temperature is 221 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.89 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, be esterified anti-
It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.25MPa, temperature is 259 DEG C, when in esterification
Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.1%, is stirred 18 minutes, is adding
It is terephthalic acid (TPA) weight to enter 0.041% catalyst glycol antimony that amount is terephthalic acid (TPA) weight and addition
Under the action of 0.042% stabilizer trimethyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure
Section pressure is steadily evacuated to absolute pressure 460Pa by normal pressure, and at 265 DEG C, the reaction time is 47 minutes for temperature control；It then proceedes to take out
Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be down to absolute pressure 40Pa, and reaction temperature is controlled at 278 DEG C,
Modified poly ester was made in 85 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 28000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- nonyls
Base -1,5 pentanediol segment forms, and the Mole percent ratio of 2- nonyl -1,5 pentanediol segments and ethylene glycol segment is 4.1%.
Embodiment 21
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.43 terephthalic acid (TPA) is made into slurry with 2- octyl -1,5 pentanediols and is added in reactor,
A concentration of 60wt%, addition are to carry out esterification under the catalytic action of 0.47% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.27MPa, temperature is 235 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.78 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, be esterified anti-
It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.26MPa, temperature is 255 DEG C, when in esterification
Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.3%, is stirred 17 minutes, is adding
It is terephthalic acid (TPA) weight to enter 0.043% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition
Under the action of 0.049% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure
Section pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 268 DEG C, the reaction time is 46 minutes for temperature control；It then proceedes to take out
Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be down to absolute pressure 40Pa, and reaction temperature is controlled at 275 DEG C,
Modified poly ester was made in 85 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 28000, pungent by terephthalic acid (TPA) segment, ethylene glycol segment and 2-
Base -1,5 pentanediol segment forms, and the Mole percent ratio of 2- octyl -1,5 pentanediol segments and ethylene glycol segment is 4.3%.
Embodiment 22
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.43 terephthalic acid (TPA) is made into slurry with 2- heptyl -1,5 pentanediols and is added in reactor,
A concentration of 55wt%, addition are to carry out esterification under the catalytic action of 0.45% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.29MPa, temperature is 235 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.87 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, be esterified anti-
It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.27MPa, temperature is 255 DEG C, when in esterification
Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.6%, is stirred 18 minutes, is adding
Enter 0.047% catalyst glycol antimony that amount is terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight 0.04%
Stabilizer triphenyl phosphate under the action of, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure
Absolute pressure 470Pa is steadily evacuated to by normal pressure, at 268 DEG C, the reaction time is 45 minutes for temperature control；It then proceedes to vacuumize,
The polycondensation reaction for carrying out high vacuum stage of Fig makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature is controlled at 279 DEG C, reaction
Modified poly ester was made in 83 minutes time.
The number-average molecular weight of modified poly ester obtained is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- heptan
Base -1,5 pentanediol segment forms, and the Mole percent ratio of 2- heptyl -1,5 pentanediol segments and ethylene glycol segment is 4.6%.
Embodiment 23
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.457 terephthalic acid (TPA) is made into slurry with 2- hexyl -1,5 pentanediols and is added in reactor,
A concentration of 55%, addition is to carry out esterification under the catalytic action of 0.46% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 239 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.81 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, be esterified anti-
It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.27MPa, temperature is 255 DEG C, when in esterification
Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.41%, is stirred 19 minutes,
Addition is 0.042% the catalytic antimony trioxide of terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under the action of 0.048% stabilizer Trimethyl phosphite, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, it should
Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the reaction time is 45 minutes for temperature control；It then proceedes to
It vacuumizes, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be down to absolute pressure 50Pa, reaction temperature is controlled 275
DEG C, modified poly ester was made in 85 minutes reaction time.
The number-average molecular weight of modified poly ester obtained be 28000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- oneself
Base -1,5 pentanediol segment forms, and the Mole percent ratio of 2- hexyl -1,5 pentanediol segments and ethylene glycol segment is 4.41%.
Embodiment 24
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.47 terephthalic acid (TPA) is made into slurry with 2- amyl -1,5 pentanediols and is added in reactor,
A concentration of 55wt%, addition are to carry out esterification under the catalytic action of 0.48% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.27MPa, temperature is 245 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.81 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, be esterified anti-
It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.27MPa, temperature is 259 DEG C, when in esterification
Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.67%, is stirred 19 minutes,
Addition is 0.041% the catalytic antimony trioxide of terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under the action of 0.042% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure
Section pressure is steadily evacuated to absolute pressure 485Pa by normal pressure, and at 268 DEG C, the reaction time is 46 minutes for temperature control；It then proceedes to take out
Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be down to absolute pressure 50Pa, and reaction temperature is controlled at 275 DEG C,
Modified poly ester was made in 89 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- penta
Base -1,5 pentanediol segment forms, and the Mole percent ratio of 2- amyl -1,5 pentanediol segments and ethylene glycol segment is 4.67%.
Embodiment 25
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.45 terephthalic acid (TPA) is mixed with -1,4 butanediol of -1,5 pentanediol of 2- hexyls and 2- amyls
It closes object to be made into slurry addition reactor, wherein the molar ratio of 2- hexyls -1,5 pentanediol and 2- amyls-Isosorbide-5-Nitrae butanediol is 3:1,
A concentration of 55%, addition is to carry out esterification under the catalytic action of 0.49% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.26MPa, temperature is 236 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.8 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, carry out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 258 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.4%, is stirred 18 minutes, is adding
It is terephthalic acid (TPA) weight to enter 0.042% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition
Under the action of 0.047% stabilizer Trimethyl phosphite, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, it should
Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the reaction time is 49 minutes for temperature control；It then proceedes to
It vacuumizes, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be down to absolute pressure 50Pa, reaction temperature is controlled 278
DEG C, modified poly ester was made in 88 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment, 2- hexyls-
1,5 pentanediol segment and 2- amyls-Isosorbide-5-Nitrae butanediol segment composition, 2- hexyl -1,5 pentanediol segments and 2- amyls-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：
It is 1 by molar ratio:1.45 terephthalic acid (TPA) and -1,6 hexylene glycol of 2- octyls and -1,5 pentanediol of 2- amyls
Mixture is made into slurry and is added in reactor, and the molar ratio of wherein 2- octyls -1,6 hexylene glycol and 2- amyl -1,5 pentanediols is 3:
2, a concentration of 60%, addition is be esterified anti-under the catalytic action of 0.45% concentrated sulfuric acid of terephthalic acid (TPA) weight
It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 239 DEG C, when in esterification
Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.84 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, be esterified anti-
It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.29MPa, temperature is 255 DEG C, when in esterification
Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.6%, is stirred 18 minutes, is adding
It is terephthalic acid (TPA) weight to enter 0.0423% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition
Under the action of 0.045% stabilizer Trimethyl phosphite, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, it should
Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the reaction time is 45 minutes for temperature control；It then proceedes to
It vacuumizes, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be down to absolute pressure 50Pa, reaction temperature is controlled 278
DEG C, modified poly ester was made in 85 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 28000, by terephthalic acid (TPA) segment, ethylene glycol segment, 2- octyls-
1,6 hexylene glycol segment and 2- amyl -1,5 pentanediol segments composition, 2- octyl -1,6 hexylene glycol segments and 2- amyls -1,5 penta 2
The Mole percent ratio of alcohol segment and ethylene glycol segment is 4.6%.
Embodiment 27
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.45 terephthalic acid (TPA) is mixed with -1,4 butanediol of -1,5 pentanediol of 2- hexyls and 2- amyls
It closes object to be made into slurry addition reactor, wherein the molar ratio of 2- hexyls -1,5 pentanediol and 2- amyls-Isosorbide-5-Nitrae butanediol is 3:1,
A concentration of 55%, addition is to carry out esterification under the catalytic action of 0.49% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.26MPa, temperature is 236 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 96% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.8 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, carry out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 258 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.4%, is stirred 18 minutes, is adding
It is terephthalic acid (TPA) weight to enter 0.042% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition
Under the action of 0.047% stabilizer Trimethyl phosphite, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, it should
Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the reaction time is 49 minutes for temperature control；It then proceedes to
It vacuumizes, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be down to absolute pressure 50Pa, reaction temperature is controlled 278
DEG C, modified poly ester was made in 88 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment, 2- hexyls-
1,5 pentanediol segment and 2- amyls-Isosorbide-5-Nitrae butanediol segment composition, 2- hexyl -1,5 pentanediol segments and 2- amyls-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：
It is 1 by molar ratio:1.45 terephthalic acid (TPA) and -1,3 propylene glycol of 2- octyls, -1,4 butanediol of 2- amyls and 2- oneself
The mixture of base -1,6 hexylene glycol is made into slurry and is added in reactor, wherein 2- octyls -1,3 propylene glycol, 2- amyls-Isosorbide-5-Nitrae fourth two
The molar ratio of -1,6 hexylene glycol of alcohol and 2- hexyls is 3:2:1, a concentration of 60%, addition is terephthalic acid (TPA) weight
Under the catalytic action of 0.47% concentrated sulfuric acid, esterification, esterification compressive reaction in nitrogen atmosphere, moulding pressure are carried out
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：
It is 1 by molar ratio:1.8 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, carry out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.27MPa, temperature is 258 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.71%, is stirred 18 minutes,
Addition is 0.04% the catalytic antimony trioxide of terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under the action of 0.041% stabilizer Trimethyl phosphite, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, it should
Staged pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 268 DEG C, the reaction time is 49 minutes for temperature control；It then proceedes to
It vacuumizes, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be down to absolute pressure 50Pa, reaction temperature is controlled 277
DEG C, modified poly ester was made in 84 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment, band branch
Glycol segment composition, wherein branched glycol segment be 2- octyl -1,3 propylene glycol segment, 2- amyls-Isosorbide-5-Nitrae butanediol chain
Section and 2- hexyl -1,6 hexylene glycol segments composition, the Mole percent ratio of branched glycol segment and ethylene glycol segment are
4.71%.
Embodiment 29
A kind of preparation method of porous modified polyester fiber, porous modified polyester fiber are made using porous spinneret, spray
The arrangement mode of spinneret orifice is oval shaped arrangements on filament plate, and oval shaped arrangements refer to that the hole center of spinneret orifice is located at concentration ellipse
On, concentration ellipse is that series is oval, and all elliptical long axis are conllinear, and short axle is conllinear.
As shown in Figure 1, elliptical long axis and the ratio of minor axis length are 1.3, the spacing of adjacent spinneret orifice is equal to spinneret orifice
Guide hole diameter add 1.5mm, spinneret is round spinneret, diameter and the oval maximum long axial length of series of round spinneret
The difference of degree is 11mm, and the spinneret hole count of a diameter of 2.0mm of guide hole of spinneret orifice, spinneret are 374, the spinneret orifice of spinneret
Cross-sectional shape be circle.
Modified poly ester made from embodiment 1 squeezes out, cools down, oils, stretches through metering, porous spinneret, thermal finalization and volume
Around the temperature of obtained porous modified polyester fiber, extrusion is 280 DEG C, and cooling wind-warm syndrome is 20 DEG C, and the speed of winding is 4000m/
min。
The fracture strength of porous modified polyester fiber obtained is 4.0cN/dtex, elongation at break 31.0%；It is porous
For modified polyester fiber in the case where temperature is 80 DEG C, the spatial joint clearance of fibrous inside molecule interchain increases 15v/v%, at 289 DEG C, melts
Body viscosity declines 16%；The line density deviation ratio of polyester fiber is 0.5%, and fracture strength CV values are 4.0%, extension at break CV values
It is 8.0%, yarn unevenness CV values are 2.0%, boiling water shrinkage 7.2%, oil content 0.80%.
Embodiment 30
A kind of preparation method of porous modified polyester fiber, porous modified polyester fiber are made using porous spinneret, such as
Shown in Fig. 3, the ratio of elliptical long axis and minor axis length is 1.6, and the spacing of adjacent spinneret orifice is equal to the guide hole diameter of spinneret orifice
In addition 1.5mm, spinneret is round spinneret, and the diameter of round spinneret and the difference of serial oval maximum long axis length are
The spinneret hole count of 11mm, a diameter of 2.0mm of guide hole of spinneret orifice, spinneret are 382, the cross section shape of the spinneret orifice of spinneret
Shape is circle.
Modified poly ester made from embodiment 1 squeezes out, cools down, oils, stretches through metering, porous spinneret, thermal finalization and volume
Around the temperature of obtained porous modified polyester fiber, extrusion is 280 DEG C, and cooling wind-warm syndrome is 20 DEG C, and the speed of winding is 4000m/
min。
The fracture strength of porous modified polyester fiber obtained is 5.6cN/dtex, and elongation at break 32.0% is porous
For modified polyester fiber in the case where temperature is 80 DEG C, the spatial joint clearance of fibrous inside molecule interchain increases 18v/v%, at 289 DEG C, melts
Body viscosity declines 20%；The line density deviation ratio of polyester fiber is 0.3%, and fracture strength CV values are 2.0%, extension at break CV values
It is 6.0%, yarn unevenness CV values are 1.0%, boiling water shrinkage 7.5%, oil content 0.90%.
Comparative example 1
A kind of preparation method of porous modified polyester fiber, porous modified polyester fiber are made using porous spinneret, spray
The arrangement mode of spinneret orifice is circular arrangement on filament plate, and circular arrangement refers to that the hole center of spinneret orifice is located on concentric circles, with one heart
Circle is round 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 is
The difference of round spinneret, the diameter and the round maximum diameter of series of round spinneret is 11mm, the guide hole diameter of spinneret orifice
Spinneret hole count for 2.0mm, spinneret is 370, and the cross-sectional shape of the spinneret orifice of spinneret is circle.
Modified poly ester made from embodiment 1 squeezes out, cools down, oils, stretches through metering, porous spinneret, thermal finalization and volume
Around the temperature of obtained porous modified polyester fiber, extrusion is 280 DEG C, and cooling wind-warm syndrome is 20 DEG C, and the speed of winding is 4000m/
min。
The fracture strength of porous modified polyester fiber obtained is 3.8cN/dtex, elongation at break 30.0%；It is porous
For modified polyester fiber in the case where temperature is 80 DEG C, the spatial joint clearance of fibrous inside molecule interchain increases 10v/v%, at 289 DEG C, melts
Body viscosity declines 10%；The line density deviation ratio of polyester fiber is 0.8%, and fracture strength CV values are 7.0%, extension at break CV values
It is 10.0%, yarn unevenness CV values are 5.0%, boiling water shrinkage 7.0%, oil content 0.70%.
With embodiment 29 comparison as can be seen that the effective area of spinneret it is identical when, (circular arrangement when spinneret hole count is close
Spinneret hole count is 370, and oval shaped arrangements spinneret hole count is that 374), the spinneret orifice number of plies of oval shaped arrangements is 6, is less than circular arrangement
The spinneret orifice number of plies 8, cooling effect is more preferable；It is oval with the comparison of embodiment 30 as can be seen that when the identical effective area of spinneret
The spinneret orifice number of plies of shape arrangement is 5, is 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, cooling efficiency higher.The comparing result of fibre property shows
Fiber linear density deviation ratio made from embodiment 29 and embodiment 30, fracture strength CV values, extension at break CV values and evenness fault
Rate CV values are less than comparative example 1, under the conditions of illustrating same process, fibroid made from the spinneret using spinneret orifice oval shaped arrangements
It can be better than the spinneret using spinneret circular arrangement.
Embodiment 31~33
A kind of preparation method of porous modified polyester fiber, porous modified polyester fiber are made using porous spinneret, spray
Wire hole is arranged as long axial symmetry, and the ratio of elliptical long axis and minor axis length is 1.4, and the spacing of adjacent spinneret orifice is equal to spinneret
The guide hole diameter in hole adds 1.6mm, and spinneret is round spinneret, diameter and the oval maximum long axis of series of round spinneret
The difference of length is 12mm, and a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 192 of spinneret, the spinneret of spinneret is micro-
The cross-sectional shape in hole is square.
Modified poly ester squeezes out, cools down, oils, stretches through metering, porous spinneret, thermal finalization and winding, obtained porous to change
Property polyester fiber, the temperature of extrusion is 282 DEG C, and cooling wind-warm syndrome is 21 DEG C, and the speed of winding is 4050m/min.It is obtained more
The mechanical performance data of hole modified polyester fiber spatial joint clearance Magnification of fibrous inside molecule interchain and fiber at 80 DEG C
Such as following table.
Embodiment 34~36
A kind of preparation method of porous modified polyester fiber, porous modified polyester fiber are made using porous spinneret, spray
Wire hole is arranged as that short axle is symmetrical, and the ratio of elliptical long axis and minor axis length is 1.4, and the spacing of adjacent spinneret orifice is equal to spinneret
The guide hole diameter in hole adds 1.7mm, and spinneret is elliptical spinneret plate, elliptical spinneret plate and the oval maximum long axial length of series
The difference of degree is 12mm, and the spinneret hole count of a diameter of 1.8mm of guide hole of spinneret orifice, spinneret are 200, the spinneret orifice of spinneret
Cross-sectional shape be diamond shape.
Modified poly ester squeezes out, cools down, oils, stretches through metering, porous spinneret, thermal finalization and winding, obtained porous to change
Property polyester fiber, the temperature of extrusion is 284 DEG C, and cooling wind-warm syndrome is 22 DEG C, and the speed of winding is 4080m/min.It is obtained more
The mechanical performance data of hole modified polyester fiber spatial joint clearance Magnification of fibrous inside molecule interchain and fiber at 90 DEG C
Such as following table.
Embodiment 37~39
A kind of preparation method of porous modified polyester fiber, porous modified polyester fiber are made using porous spinneret, spray
Wire hole be arranged as long axis and short axle is symmetrical, the ratio of elliptical long axis and minor axis length is 1.4, the spacing etc. of adjacent spinneret orifice
1.8mm is added in the guide hole diameter of spinneret orifice, spinneret is round spinneret, and the diameter and series of round spinneret are oval maximum
The difference of long axis length be 13mm, a diameter of 2.5mm of guide hole of spinneret orifice, the spinneret hole count of spinneret is 200, spinneret
The cross-sectional shape of spinneret orifice is "-" type.
Modified poly ester squeezes out, cools down, oils, stretches through metering, porous spinneret, thermal finalization and winding, obtained porous to change
Property polyester fiber, the temperature of extrusion is 285 DEG C, and cooling wind-warm syndrome is 22 DEG C, and the speed of winding is 4100m/min.It is obtained more
The mechanical performance data of hole modified polyester fiber spatial joint clearance Magnification of fibrous inside molecule interchain and fiber at 100 DEG C
Such as following table.
Embodiment 40~42
A kind of preparation method of porous modified polyester fiber, porous modified polyester fiber are made using porous spinneret, spray
Wire hole be arranged as long axis and short axle is symmetrical, the ratio of elliptical long axis and minor axis length is 1.7, the spacing etc. of adjacent spinneret orifice
1.9mm is added in the guide hole diameter of spinneret orifice, spinneret is elliptical spinneret plate, and elliptical spinneret plate and serial ellipse are maximum
The difference of long axis length is 14mm, and the spinneret hole count of a diameter of 1.5mm of guide hole of spinneret orifice, spinneret are 210, the spray of spinneret
The cross-sectional shape of silk micropore is triangular form.
Modified poly ester squeezes out, cools down, oils, stretches through metering, porous spinneret, thermal finalization and winding, obtained porous to change
Property polyester fiber, the temperature of extrusion is 286 DEG C, and cooling wind-warm syndrome is 23 DEG C, and the speed of winding is 4120m/min.It is obtained more
The mechanical performance data of hole modified polyester fiber spatial joint clearance Magnification of fibrous inside molecule interchain and fiber at 110 DEG C
Such as following table.
Embodiment 43~45
A kind of preparation method of porous modified polyester fiber, porous modified polyester fiber are made using porous spinneret, spray
Wire hole is arranged as that short axle is symmetrical, and the ratio of elliptical long axis and minor axis length is 1.8, and the spacing of adjacent spinneret orifice is equal to spinneret
The guide hole diameter in hole adds 1.5mm, and spinneret is round spinneret, diameter and the oval maximum long axis of series of round spinneret
The difference of length is 15mm, and the spinneret hole count of a diameter of 1.8mm of guide hole of spinneret orifice, spinneret are 240, and the spinneret of spinneret is micro-
The cross-sectional shape in hole is trilobal cross.
Modified poly ester squeezes out, cools down, oils, stretches through metering, porous spinneret, thermal finalization and winding, obtained porous to change
Property polyester fiber, the temperature of extrusion is 287 DEG C, and cooling wind-warm syndrome is 24 DEG C, and the speed of winding is 4150m/min.It is obtained more
The mechanical performance data of hole modified polyester fiber spatial joint clearance Magnification of fibrous inside molecule interchain and fiber at 120 DEG C
Such as following table.
Embodiment 46~49
A kind of preparation method of porous modified polyester fiber, porous modified polyester fiber are made using porous spinneret, spray
Wire hole is arranged as long axial symmetry, and the ratio of elliptical long axis and minor axis length is 1.8, and the spacing of adjacent spinneret orifice is equal to spinneret
The guide hole diameter in hole adds 1.6mm, and spinneret is round spinneret, diameter and the oval maximum long axis of series of round spinneret
The difference of length is 16mm, and the spinneret hole count of a diameter of 2.2mm of guide hole of spinneret orifice, spinneret are 250, and the spinneret of spinneret is micro-
The cross-sectional shape in hole is hollow type.
Modified poly ester squeezes out, cools down, oils, stretches through metering, porous spinneret, thermal finalization and winding, obtained porous to change
Property polyester fiber, the temperature of extrusion is 288 DEG C, and cooling wind-warm syndrome is 24 DEG C, and the speed of winding is 4160m/min.It is obtained more
The mechanical performance data of hole modified polyester fiber spatial joint clearance Magnification of fibrous inside molecule interchain and fiber at 130 DEG C
Such as following table.
Embodiment 50~53
A kind of preparation method of porous modified polyester fiber, porous modified polyester fiber are made using porous spinneret, spray
Wire hole is arranged as that short axle is symmetrical, and the ratio of elliptical long axis and minor axis length is 1.8, and the spacing of adjacent spinneret orifice is equal to spinneret
The guide hole diameter in hole adds 1.8mm, and spinneret is round spinneret, diameter and the oval maximum long axis of series of round spinneret
The difference of length is 15mm, and the spinneret hole count of a diameter of 2.5mm of guide hole of spinneret orifice, spinneret are 260, and the spinneret of spinneret is micro-
The cross-sectional shape in hole is platypelloid type.
Modified poly ester squeezes out, cools down, oils, stretches through metering, porous spinneret, thermal finalization and winding, obtained porous to change
Property polyester fiber, the temperature of extrusion is 289 DEG C, and cooling wind-warm syndrome is 25 DEG C, and the speed of winding is 4180m/min.It is obtained more
The mechanical performance data of hole modified polyester fiber spatial joint clearance Magnification of fibrous inside molecule interchain and fiber at 100 DEG C
Such as following table.
Embodiment 54~57
A kind of preparation method of porous modified polyester fiber, porous modified polyester fiber are made using porous spinneret, spray
Wire hole is arranged as long axial symmetry, and the ratio of elliptical long axis and minor axis length is 1.8, and the spacing of adjacent spinneret orifice is equal to spinneret
The guide hole diameter in hole adds 1.5mm, and spinneret is round spinneret, diameter and the oval maximum long axis of series of round spinneret
The difference of length is 16mm, and the spinneret hole count of a diameter of 1.8mm of guide hole of spinneret orifice, spinneret are 300, and the spinneret of spinneret is micro-
The cross-sectional shape in hole is hollow type.
Modified poly ester squeezes out, cools down, oils, stretches through metering, porous spinneret, thermal finalization and winding, obtained porous to change
Property polyester fiber, the temperature of extrusion is 290 DEG C, and cooling wind-warm syndrome is 25 DEG C, and the speed of winding is 4200m/min.It is obtained more
The mechanical performance data of hole modified polyester fiber spatial joint clearance Magnification of fibrous inside molecule interchain and fiber at 120 DEG C
Such as following table.
Embodiment 58
The dyeing of modified polyester fiber：To embodiment 29 prepare porous modified polyester fiber in high temperature and pressure machine
It is dyed, actual conditions are：Before dyeing, modified polyester fiber nonionic surfactant handles 30 minutes at 60 DEG C, so
It is added in dyeing liquor afterwards, the disperse dyes dosage in dyeing liquor is 2.0% (o.w.f)；Dispersant NNO, the concentration of dispersant NNO
1.2g/L；PH value is 5, bath raio 1:50, it is contaminated in 60 DEG C of tripping in, then heats to 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C and 130
DEG C each constant temperature dyeing 1h.
General fibre is dyed using identical dyeing condition.The upper dye of porous modified polyester fiber after dyed
Percentage obtains by the following method：
Dye uptake is determined using raffinate colorimetric method, draws suitable dyeing stoste and dyeing residual liquid, and N, N-2 first is added
The ratio of base formamide (DMF) and distilled water, DMF and water in dye liquor to be measured is 70/30 (v/v), and dye liquor absorbance is using purple
Outside-visible spectrophotometer measures, and dye uptake is calculated with following formula.
In above formula, A0 and A1 are respectively the absorbance for dyeing stoste and dyeing residual liquid.
When disperse dyes are Disperse Red 3B, disperse blue SE-2R or when disperseing bright blue S-GL, porous modified polyester fiber and general
The dye uptake result such as following table of perforating fiber：
It is compared by the coloring of porous modified polyester fiber and general fibre, it can be seen that the dye of modified polyester fiber
Color is with obvious effects to be better than general fibre, and what is also contained from the side illustration modified poly ester macromolecular of the invention prepared contains branch
Dihydric alcohol segment, so that the increasing degree of free volume is far longer than the characteristic of unbranched polyester macromolecule chain, free volume
Increase improve molecule and enter degree inside polyester, the free volume of polyester fiber prepared by modified polyester is much
More than polyester fiber unbranched at same temperature, increase the diffusion of dyestuff, improves the dyeability of polyester fiber.
Embodiment 59
The dyeing of modified polyester fiber：
To porous modified polyester fiber prepared by embodiment 31, dyeing course is identical as embodiment 58, while using identical
Dyeing condition general fibre is dyed.
When disperse dyes are Disperse Red 3B, disperse blue SE-2R or when disperseing bright blue S-GL, porous modified polyester fiber and general
The dye uptake result such as following table of perforating fiber：
It is compared by coloring, it can be seen that the coloring of modified polyester fiber is substantially better than general fibre.
Embodiment 60
The dyeing of modified polyester fiber：It is that modified polyester fiber is former to porous modified poly ester prepared by embodiment 35
Material, by modified poly ester through metering, extrusion, cooling, oil, stretch, thermal finalization and winding, modified polyester fiber is made；
Dyeing course is identical as embodiment 58, while being dyed to general fibre using identical dyeing condition.
When disperse dyes are Disperse Red 3B, disperse blue SE-2R or when disperseing bright blue S-GL, porous modified polyester fiber and general
The dye uptake result such as following table of perforating fiber：
It is compared by coloring, it can be seen that the coloring of modified polyester fiber is substantially better than general fibre.
Claims (9)
1. a kind of preparation method of porous modified polyester fiber, it is characterized in that：Modified poly ester is used into porous spinneret spinning system
Obtain porous modified polyester fiber；The arrangement mode of spinneret orifice is oval shaped arrangements on the porous spinneret, the ellipse row
Row refer to that the hole center of spinneret orifice is located on concentration ellipse, and the concentration ellipse is that series is oval, and all elliptical long axis are conllinear,
And short axle is conllinear；
The preparation process of the porous modified polyester fiber is：Modified poly ester squeezes out, cools down, oils through metering, porous spinneret,
Stretching, thermal finalization and winding；The temperature of the extrusion is 280~290 DEG C, and the wind-warm syndrome of the cooling is 20~25 DEG C, the volume
Around speed be 4000~4200m/min；
The preparation process of the modified poly ester is：
(1) preparation of terephthalic acid (TPA) binary alcohol esters；
After terephthalic acid (TPA) and the dihydric alcohol containing branch are made into slurry, under the catalytic action of the concentrated sulfuric acid, esterification is carried out
Obtain terephthalic acid (TPA) binary alcohol esters；The dihydric alcohol containing branch be -1,3 propylene glycol of 2- amyls, -1,3 propylene glycol of 2- hexyls,
- 1,3 propylene glycol of 2- heptyl, -1,3 propylene glycol of 2- octyls, -1,3 propylene glycol of 2- nonyls, -1,3 propylene glycol of 2- decyls, amyl -1 2-,
4 butanediols, -1,4 butanediol of 2- hexyls, -1,4 butanediol of 2- heptyl, -1,4 butanediol of 2- octyls, -1,4 butanediol of 2- nonyls,
- 1,4 butanediol of 2- decyls, -1,5 pentanediol of 2- amyls, -1,5 pentanediol of 2- hexyls, -1,5 pentanediol of 2- heptyl, octyl -1 2-,
5 pentanediols, -1,5 pentanediol of 2- nonyls, -1,5 pentanediol of 2- decyls, -1,6 hexylene glycol of 2- amyls, -1,6 hexylene glycol of 2- hexyls,
One kind in -1,6 hexylene glycol of 2- heptyl, -1,6 hexylene glycol of -1,6 hexylene glycol of 2- octyls, -1,6 hexylene glycol of 2- nonyls or 2- decyls
More than；
(2) preparation of ethylene glycol terephthalate；
After terephthalic acid (TPA) and ethylene glycol are made into slurry, esterification is carried out, ethylene glycol terephthalate is obtained；
(3) preparation of modified poly ester；
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, stirring is mixed
It closes, under the action of catalyst and stabilizer, under conditions of negative pressure, carries out polycondensation reaction and the Gao Zhen of low vacuum stage successively
Modified poly ester is made in the polycondensation reaction in empty stage.
2. a kind of preparation method of porous modified polyester fiber according to claim 1, which is characterized in that the modification is poly-
The specific preparation process of ester is：
(1) preparation of terephthalic acid (TPA) binary alcohol esters；
Terephthalic acid (TPA) and the dihydric alcohol containing branch are made into slurry, under the catalytic action of the concentrated sulfuric acid, carry out esterification, ester
Change reaction compressive reaction in nitrogen atmosphere, moulding pressure is normal pressure~0.3MPa, and temperature is 180~240 DEG C, works as esterification
In water quantity of distillate be esterification terminal when reaching 90% of theoretical value or more, obtain terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate；
After terephthalic acid (TPA) and ethylene glycol are made into slurry, progress 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 90% or more, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester；
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, stirring is mixed
It closes 15-20 minutes, under the action of catalyst and stabilizer, starts the polycondensation reaction of low vacuum stage under conditions of negative pressure,
The staged pressure by normal pressure is steadily evacuated to absolute pressure 500Pa hereinafter, temperature control is at 260~270 DEG C, and the reaction time is 30~
50 minutes；It then proceedes to vacuumize, carries out the polycondensation reaction of high vacuum stage of Fig, so that reaction pressure is down to absolute pressure and be less than
Modified poly ester is made in 275~280 DEG C, 50~90 minutes reaction time in 100Pa, reaction temperature control.
3. a kind of preparation method of porous modified polyester fiber according to claim 2, which is characterized in that in step (1),
The molar ratio of terephthalic acid (TPA) and the dihydric alcohol containing branch is 1:1.3-1.5；Concentrated sulfuric acid addition is terephthalic acid (TPA) weight
0.3-0.5%；A concentration of 50-60wt% of the concentrated sulfuric acid；
In step (2), the molar ratio of terephthalic acid (TPA) and ethylene glycol is 1:1.2~2.0；
In step (3), the Mole percent ratio of the terephthalic acid (TPA) binary alcohol esters and ethylene glycol terephthalate is 2~
5%；The catalyst is antimony oxide, antimony glycol or antimony acetate, and catalyst charge is terephthalic acid (TPA) total weight
0.01%~0.05%；The stabilizer is triphenyl phosphate, trimethyl phosphate or Trimethyl phosphite, and stabilizer addition is
The 0.01%~0.05% of the terephthalic acid (TPA) total weight；
The number-average molecular weight of the modified poly ester is 15000~30000.
4. a kind of preparation method of porous modified polyester fiber according to claim 1, which is characterized in that the spinneret orifice
Be arranged as long axis and/or short axle is symmetrical.
5. a kind of preparation method of porous modified polyester fiber according to claim 1, which is characterized in that elliptical long axis
Ratio with minor axis length is 1.3~1.8；The guide hole diameter that the spacing of adjacent spinneret orifice is more than or equal to spinneret orifice adds 1.5mm.
6. a kind of preparation method of porous modified polyester fiber according to claim 1, which is characterized in that the spinneret
For round spinneret or elliptical spinneret plate；The difference of the diameter of the circle spinneret and the oval maximum long axis length of series
More than 10mm, the elliptical spinneret plate and the difference of the oval maximum long axis length of series are more than 10mm.
7. a kind of preparation method of porous modified polyester fiber according to claim 1, which is characterized in that the spinneret orifice
The a diameter of 1.5~2.5mm of guide hole；The spinneret hole count of the spinneret is more than or equal to 192.
8. a kind of preparation method of porous modified polyester fiber according to claim 1, which is characterized in that the spinneret
The cross-sectional shape of spinneret orifice be circle, square, diamond shape, "-" type, triangular form, trilobal cross, hollow type or platypelloid type.
9. a kind of preparation method of porous modified polyester fiber according to claim 1, which is characterized in that described porous to change
Property polyester fiber fracture strength >=3.8cN/dtex, elongation at break be 33.0 ± 3.0%；The porous modified polyester fiber
In the case where temperature is 80~130 DEG C, the spatial joint clearance of fibrous inside molecule interchain increases 10~30v/v%, at 260~290 DEG C,
Melt viscosity declines 10~20%；Line density deviation ratio≤0.5% of the porous modified polyester fiber, fracture strength CV values≤
4.0%, extension at break CV value≤8.0%, yarn unevenness CV value≤2.0%, boiling water shrinkage is 7.5 ± 0.5%, oil content
It is 0.90 ± 0.20%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102648231A (en) * | 2009-09-29 | 2012-08-22 | 东丽纤维研究所（中国）有限公司 | Copolyester and preparation method and use thereof |
| CN102851757A (en) * | 2011-06-30 | 2013-01-02 | 江苏华亚化纤有限公司 | Special-shaped spinneret plate for spinning heavy denier yarns |
| CN102797054B (en) * | 2012-09-03 | 2014-10-01 | 江苏恒力化纤股份有限公司 | Manufacturing method of high-strength, high-modulus and low-shrinkage polyester industrial yarn |
| JP2014189933A (en) * | 2013-03-28 | 2014-10-06 | Toray Ind Inc | Normal pressure dispersion-dyeable polyester ultra-fine fiber |
| CN104499080A (en) * | 2014-12-31 | 2015-04-08 | 江苏恒力化纤股份有限公司 | High-strength activated polyester industry yarn and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102648231A (en) * | 2009-09-29 | 2012-08-22 | 东丽纤维研究所（中国）有限公司 | Copolyester and preparation method and use thereof |
| CN102851757A (en) * | 2011-06-30 | 2013-01-02 | 江苏华亚化纤有限公司 | Special-shaped spinneret plate for spinning heavy denier yarns |
| CN102797054B (en) * | 2012-09-03 | 2014-10-01 | 江苏恒力化纤股份有限公司 | Manufacturing method of high-strength, high-modulus and low-shrinkage polyester industrial yarn |
| JP2014189933A (en) * | 2013-03-28 | 2014-10-06 | Toray Ind Inc | Normal pressure dispersion-dyeable polyester ultra-fine fiber |
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