CN106400166B - A kind of three leaf special-shaped polyester fiber of porous superbright light and preparation method thereof - Google Patents
A kind of three leaf special-shaped polyester fiber of porous superbright light and preparation method thereof Download PDFInfo
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- CN106400166B CN106400166B CN201610782670.2A CN201610782670A CN106400166B CN 106400166 B CN106400166 B CN 106400166B CN 201610782670 A CN201610782670 A CN 201610782670A CN 106400166 B CN106400166 B CN 106400166B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
Abstract
The present invention relates to a kind of three leaf special-shaped polyester fibers of porous superbright light and preparation method thereof, use the cross-sectional shape of spinneret orifice that three leaf special-shaped polyester fiber of porous superbright light is made for the porous spinneret spinning of trilobal cross 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.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, line density deviation ratio≤0.5% of three leaf special-shaped polyester fiber of porous superbright light, fracture strength CV value≤4.0%, extension at break CV value≤8.0%, yarn unevenness CV value≤2.0%.
Description
Technical field
The invention belongs to field of polyester fiber, it is related to a kind of three leaf special-shaped polyester fiber of porous superbright light and its preparation side
Method.
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, problem is still remained：Due to spun silk from
After round spinneret squeezes out, by ring wind quenching, since the round spinneret number of turns is more so that ring blowing hardly enters most interior
Layer, leads to that the silk of innermost layer may be also uncolled after cooling in outermost silk, so that fiber number occur irregular for the silk of gained,
The problems such as intensity is irregular, uneven dyeing causes the further processing subsequently to silk difficulty occur.
Superbright light trilobal terylene crimped filament is mainly shaped by melt spinning, cross section special-shapedization and Asymmetrical cooling,
The silk light sensation for assigning gloss and feel, fabric bright sense and soft elegance that polyester fiber has as silk, not only has excellent
Outside good optical characteristics, since the fibrous appearance of odd-shaped cross section is irregular, the arrangement between fiber can not be close, and gap accordingly increases
Greatly, to which fabric feeling is more thick and solid, bulkiness, good permeability have superbright flash effect.Its product is mainly used for silk like fabric and knits
The pile fabrics such as object, wool-like fabric, corduroy, knitting wool, drapery etc..Especially in clothing, decoration and fabrics for industrial use three
There are vast market prospect and economic benefit in big field.
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 three leaf special-shaped polyester fiber of porous superbright light.The polyester fiber of the present invention
Raw material is modified poly ester, and the dihydric alcohol segment containing branch, modification prepared by modified polyester are introduced in the strand of modified poly ester
Polyester fiber, under the conditions of certain temperature, the increasing degree of the spatial joint clearance of modified polyester fiber interior molecules interchain is far longer than
Unbranched conventional polyester fiber at same temperature, is conducive to the molecules such as coloring agent and enters internal degree, improve dyeing
Rate；The melt viscosity of modified polyester fiber reduces, and reduces processing temperature, reduces degradation rate, is conducive to process；In addition contain branch
The not big destruction of structural regularity of the dihydric alcohol segment to modified polyester fiber of chain, maintains the Optimality of polyester fiber
Energy.In spinning process of the present invention use spinneret orifice oval shaped arrangements spinneret, be conducive to fiber in spinning process it is uniform,
It is fully cooled, the performance and structure difference between fiber are 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：
A kind of three leaf special-shaped polyester fiber of porous superbright light, the three leaf shaped filaments of porous superbright light are by modified poly ester through spray
Wire hole obtains for three leaf profile spinneret spinning of Y-shaped structure, and the material of the three leaf special-shaped polyester fiber of porous superbright light is
Modified poly ester, the modified poly ester is made of terephthalic acid (TPA) segment, ethylene glycol segment and dihydric alcohol segment containing branch, described
Dihydric alcohol segment containing branch refers on a non-end group carbon that branch is located in dihydric alcohol segment and branch is containing 5-10
The dihydric alcohol segment of the linear carbon chain of carbon atom；
The filament number of the three leaf special-shaped polyester fiber of porous superbright light be 0.3~2.0dtex, fracture strength >=
3.8cN/dtex, elongation at break are 33.0 ± 3.0%；The three leaf special-shaped polyester fiber of porous superbright light temperature be 80~
At 130 DEG C, the spatial joint clearance of fibrous inside molecule interchain increases 10~30v/v%；Three leaf abnormal shape polyester of the porous superbright light
Line density deviation ratio≤0.5% of 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 space of the molecule interchain
Gap increase refer to modified poly ester with normal polyester the spatial joint clearance of mutually synthermal molecule interchain comparison.
The present invention also provides a kind of preparation methods of three leaf special-shaped polyester fiber of porous superbright light, and modified poly ester is used
The cross-sectional shape of spinneret orifice is that three leaf special-shaped polyester fiber of porous superbright light is made in the porous spinneret spinning of trilobal cross；Institute
The arrangement mode for stating spinneret orifice on porous spinneret is oval shaped arrangements, and the oval shaped arrangements refer to the hole centre bit of spinneret orifice
In on concentration ellipse, the concentration ellipse is that series is oval, and all elliptical long axis are conllinear, and short axle is conllinear；
The preparation method of the three leaf special-shaped polyester fiber of porous superbright light is：Modified poly ester obtains modified poly ester through pelletizing
Slice；Squeezes out, cool down, oil, stretch through metering, porous spinneret orifice again, thermal finalization and winding, obtained porous three leaf of superbright light it is different
Type polyester fiber；
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 containing branch refers to that be located in dihydric alcohol segment one of branch is non-
On end group carbon and branch be the linear carbon chain containing 5-10 carbon atom dihydric alcohol；
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 three leaf special-shaped polyester fiber of porous superbright light as described above, the modified poly ester it is specific
Preparation process 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, 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；
The main spinning technology parameter of the three leaf special-shaped polyester fiber of porous superbright light is：
The temperature of extrusion：280~290 DEG C；
Cooling wind-warm syndrome：20~25 DEG C；
The speed of winding：4000~4600m/min.
A kind of preparation method of three leaf special-shaped polyester fiber of porous superbright light as described above, in step (1), terephthaldehyde
The molar ratio of acid and the dihydric alcohol containing branch is 1:1.3-1.5；Concentrated sulfuric acid addition is the 0.3- of terephthalic acid (TPA) weight
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, 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 three leaf special-shaped polyester fiber of porous superbright light as described above, the dihydric alcohol containing branch
For -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, 2- nonyls -
1,3 propylene glycol, -1,3 propylene glycol of 2- decyls, -1,4 butanediol of 2- amyls, -1,4 butanediol of 2- hexyls, -1,4 fourth two of 2- heptyl
Alcohol, -1,4 butanediol of 2- octyls, -1,4 butanediol of 2- nonyls, -1,4 butanediol of 2- decyls, -1,5 pentanediol of 2- amyls, 2- oneself
- 1,5 pentanediol of base, -1,5 pentanediol of 2- heptyl, -1,5 pentanediol of 2- octyls, -1,5 pentanediol of 2- nonyls, 2- decyls -1,5 penta
Glycol, -1,6 hexylene glycol of 2- amyls, -1,6 hexylene glycol of 2- hexyls, -1,6 hexylene glycol of 2- heptyl, -1,6 hexylene glycol of 2- octyls, 2- nonyls
One or more of -1,6 hexylene glycol of -1,6 hexylene glycol of base or 2- decyls.
A kind of preparation method of three leaf special-shaped polyester fiber of porous superbright light as described above, the spinneret orifice are arranged as
Long axis and/or short axle are symmetrical.
A kind of preparation method of three leaf special-shaped polyester fiber of porous superbright light as described above, elliptical long axis and short axle are long
The ratio of degree 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.Work as spinneret
Effective area phase simultaneously as the perimeter of ellipse is more than circular perimeter, the numbers of plies of spinneret orifice oval shaped arrangements is less than circle
The number of plies of shape arrangement, 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 have
Conducive to the cooling of ring blowing, the cooling efficiency of ring blowing is improved, the fibre property of preparation is also more excellent.Long axis and minor axis length
Ratio closer to 1, ellipse is more similar to justify, and the difference of cooling efficiency and cooling effect is little；Long axis and minor axis length
When ratio is 1.3, cooling effect significantly improves, and individual pen hole count accordingly increases by 16%；Long axis and the ratio of minor axis length are 1.8
When, cooling effect raising is larger, the accordingly increase by 33% of individual pen hole count, in the case of identical hole count, oval shaped arrangements of the invention ratio
The number of turns of conventional concentric circle best-fit is reduced, and is easy to cooling wind and is blown through, makes the fiber cooling condition of Internal and external cycle evenly；Long axis with it is short
When the ratio of shaft length is more than 1.8, ellipse is partial to form flat shape, is not easy to punch, cooling no longer increases.
Therefore, the elliptical long axis of series and the ratio of minor axis length are 1.3~1.8, can reach higher cooling efficiency and preferable
Cooling effect.
A kind of preparation method of three leaf special-shaped polyester fiber of porous superbright light as described above, the spinneret are circular jetting
Filament plate or elliptical spinneret plate；The diameter of the circle spinneret and the difference of serial oval maximum long axis length are more than
10mm, the elliptical spinneret plate and the difference of the oval maximum long axis length of series are more than 10mm.
A kind of preparation method of three leaf special-shaped polyester fiber of porous superbright light as described above, the guide hole of the spinneret orifice are straight
Diameter is 1.5~2.5mm；The spinneret hole count of the spinneret is more than or equal to 192.
A kind of preparation method of three leaf special-shaped polyester fiber of porous superbright light as described above, three leaves of the spinneret orifice
Three leaves are mutually 120 degree of angles in type cross section, and it is 2~5 that leaf, which is grown with the ratio of leaf width,:1.
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 polyester fiber of the present invention is modified poly ester, the dihydric alcohol chain containing branch contained in modified poly ester macromolecular
Section, when temperature is higher than glass transition temperature, branch makes the increasing degree of free volume be far longer than unbranched prior to backbone motion
Polyester macromolecule chain characteristic, the increase of free volume improves molecule and enters degree inside polyester, modified poly-
The free volume of polyester fiber prepared by ester is far longer than polyester fiber unbranched at same temperature, increases the diffusion path of dyestuff
Degree, improves the dyeability of polyester fiber.Meanwhile polyester fiber prepared by modified poly ester advantageously reduces melt viscosity, favorably
In its processing performance of improvement.The introducing of dihydric alcohol segment containing the branch destruction not big to polyester fiber structures regularity, is protected
The excellent performance of polyester fiber is held.
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) material of three leaf special-shaped polyester fiber of porous superbright light produced by the present invention is modified poly ester, and modified poly ester divides greatly
The dihydric alcohol segment containing branch contained in son, when temperature is higher than glass transition temperature, branch makes free body prior to backbone motion
Long-pending increasing degree is far longer than the characteristic of unbranched polyester macromolecule chain, the increase of free volume improve molecule into
Enter the degree inside polyester, the free volume of polyester fiber is increased by branch to increase the diffusion of dyestuff, improves poly-
The dyeability of ester fiber.
4) three leaf special-shaped polyester fiber of porous superbright light produced by the present invention, the increase of polyester fiber free volume are conducive to
Melt viscosity is reduced, is conducive to improve its processing performance.
5) three leaf special-shaped polyester fiber of porous superbright light produced by the present invention, the introducing pair of the dihydric alcohol segment containing branch
The not big destruction of the structural regularity of polyester fiber, maintains the excellent performance of polyester fiber.
6) three leaf special-shaped polyester fiber dyeability of porous superbright light and good mechanical performance produced by the present invention are porous super
Line density deviation ratio≤0.5% of three leaf special-shaped polyester fiber of light, fracture strength CV value≤4.0%, extension at break CV values≤
8.0%, yarn unevenness CV value≤2.0%.
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 modified poly ester, 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) weight and addition is terephthalic acid (TPA) weight 0.01%
Stabilizer triphenyl phosphate under the action of, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure
It is 500Pa that absolute pressure is steadily evacuated to by normal pressure, and at 260 DEG C, the reaction time is 30 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 100Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled 275
DEG C, modified poly ester was made in 50 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 15000, 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 process of the modified poly ester of embodiment 2 is with embodiment 1, wherein main technical parameter is referring to table 1；In step
(3) it after terephthalic acid (TPA) binary alcohol esters being added, is stirred 16 minutes, is terephthalic acid (TPA) total weight in addition
0.011% the catalytic antimony trioxide and addition is 0.02% stabilizer triphenyl phosphate of terephthalic acid (TPA) total weight
Under the action of, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, which is steadily evacuated to absolutely by normal pressure
Pressure 490Pa, at 262 DEG C, the reaction time is 31 minutes for temperature control；It then proceedes to vacuumize, carries out the contracting of high vacuum stage of Fig
Poly- reaction, makes reaction pressure be down to absolute pressure 90Pa, and reaction temperature control is made and is modified in 276 DEG C, 51 minutes reaction time
Polyester.
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 process of the modified poly ester of embodiment 3 is with embodiment 1, wherein main technical parameter is referring to table 1；In step
(3) it after terephthalic acid (TPA) binary alcohol esters being added, is stirred 16 minutes, in 0.03% that addition is terephthalic acid (TPA) total weight
The catalytic antimony trioxide and addition be terephthalic acid (TPA) total weight 0.02% stabilizer triphenyl phosphate effect
Under, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, which is steadily evacuated to absolute pressure by normal pressure
498Pa, at 263 DEG C, the reaction time is 32 minutes for temperature control；It then proceedes to vacuumize, the polycondensation for carrying out high vacuum stage of Fig is anti-
It answers, reaction pressure is made to be down to absolute pressure 90Pa, reaction temperature control is made modified poly- in 277 DEG C, 57 minutes reaction time
Ester.
The number-average molecular weight of modified poly ester is 15900, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- heptan
Base -1,3 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 process of the modified poly ester of embodiment 4 is with embodiment 1, wherein main technical parameter is referring to table 1；In step
(3) it after terephthalic acid (TPA) binary alcohol esters being added, is stirred 17 minutes, is terephthalic acid (TPA) total weight in addition
0.033% the catalytic antimony trioxide and addition is 0.023% stabilizer phosphoric acid triphen of terephthalic acid (TPA) total weight
Under the action of ester, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, which is steadily evacuated to absolutely by normal pressure
It is 497Pa to pressure, at 264 DEG C, the reaction time is 33 minutes for temperature control；It then proceedes to vacuumize, carries out high vacuum stage of Fig
Polycondensation reaction, it is 80Pa so that reaction pressure is down to absolute pressure, and reaction temperature control is at 278 DEG C, 58 minutes reaction time, system
Obtain modified poly ester.
The number-average molecular weight of modified poly ester is 15800, and modified poly ester is pungent by terephthalic acid (TPA) segment, ethylene glycol segment and 2-
Base -1,3 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 process of the modified poly ester of embodiment 5 is with embodiment 1, wherein main technical parameter is referring to table 1；In step
(3) it after terephthalic acid (TPA) binary alcohol esters being added, is stirred 17 minutes, is terephthalic acid (TPA) total weight in addition
0.034% the catalytic antimony trioxide and addition is 0.024% stabilizer phosphoric acid triphen of terephthalic acid (TPA) total weight
Under the action of ester, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, which is steadily evacuated to absolutely by normal pressure
To pressure 496Pa, at 265 DEG C, the reaction time is 34 minutes for temperature control；It then proceedes to vacuumize, carries out high vacuum stage of Fig
Polycondensation reaction, it is 80Pa so that reaction pressure is down to absolute pressure, and reaction temperature control is made in 277 DEG C, 59 minutes reaction time
Modified poly ester.
The number-average molecular weight of modified poly ester is 15900, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- 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 process of the modified poly ester of embodiment 6 is with embodiment 1, wherein main technical parameter is referring to table 1；In step
(3) it after terephthalic acid (TPA) binary alcohol esters being added, is stirred 18 minutes, is terephthalic acid (TPA) total weight in addition
0.035% the catalytic antimony trioxide and addition is 0.025% stabilizer phosphoric acid triphen of terephthalic acid (TPA) total weight
Under the action of ester, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, which is steadily evacuated to absolutely by normal pressure
To pressure 495Pa, at 266 DEG C, the reaction time is 35 minutes for temperature control；It then proceedes to vacuumize, carries out high vacuum stage of Fig
Polycondensation reaction, it is 70Pa so that reaction pressure is down to absolute pressure, and reaction temperature control is made in 278 DEG C, 60 minutes reaction time
Modified poly ester.
The number-average molecular weight of modified poly ester is 16000, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and the 2- last of the ten Heavenly stems
Base -1,3 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 process of the modified poly ester of embodiment 7 is with embodiment 1, wherein main technical parameter is referring to table 1；In step
(3) it after terephthalic acid (TPA) binary alcohol esters being added, is stirred 19 minutes, is terephthalic acid (TPA) total weight in addition
0.036% the catalytic antimony trioxide and addition is 0.025% stabilizer phosphoric acid triphen of terephthalic acid (TPA) total weight
Under the action of ester, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, which is steadily evacuated to absolutely by normal pressure
To pressure 496Pa, at 267 DEG C, the reaction time is 36 minutes for temperature control；It then proceedes to vacuumize, carries out high vacuum stage of Fig
Polycondensation reaction, it is 70Pa so that reaction pressure is down to absolute pressure, and reaction temperature control is made in 278 DEG C, 61 minutes reaction time
Modified poly ester.
The number-average molecular weight of modified poly ester is 16000, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- penta
The Mole percent ratio of base-Isosorbide-5-Nitrae butanediol segment composition, 2- amyls-Isosorbide-5-Nitrae butanediol segment and ethylene glycol segment is 2.6%.
Embodiment 8
The preparation process of the modified poly ester of embodiment 8 is with embodiment 1, wherein main technical parameter is referring to table 1；In step
(3) it after terephthalic acid (TPA) binary alcohol esters being added, is stirred 19 minutes, is terephthalic acid (TPA) total weight in addition
0.036% the catalytic antimony trioxide and addition is 0.025% stabilizer phosphoric acid triphen of terephthalic acid (TPA) total weight
Under the action of ester, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, which is steadily evacuated to absolutely by normal pressure
To pressure 496Pa, at 267 DEG C, the reaction time is 36 minutes for temperature control；It then proceedes to vacuumize, carries out high vacuum stage of Fig
Polycondensation reaction, it is 70Pa so that reaction pressure is down to absolute pressure, and reaction temperature control is made in 278 DEG C, 61 minutes reaction time
Modified poly ester.
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 process of the modified poly ester of embodiment 9 is with embodiment 1, wherein main technical parameter is referring to table 1；In step
(3) it after terephthalic acid (TPA) binary alcohol esters being added, is stirred 16 minutes, in 0.04% that addition is terephthalic acid (TPA) total weight
Catalyst glycol antimony and addition be terephthalic acid (TPA) total weight 0.026% stabilizer trimethyl phosphate effect
Under, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, which is steadily evacuated to absolute pressure by normal pressure
497Pa, at 268 DEG C, the reaction time is 38 minutes for temperature control；It then proceedes to vacuumize, the polycondensation for carrying out high vacuum stage of Fig is anti-
It answers, it is 60Pa so that reaction pressure is down to absolute pressure, and reaction temperature control is made modified poly- in 279 DEG C, 62 minutes reaction time
Ester.
The number-average molecular weight of modified poly ester is 17000, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- heptan
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 process of the modified poly ester of embodiment 10 is with embodiment 1, wherein main technical parameter is referring to table 1；In step
Suddenly it after terephthalic acid (TPA) binary alcohol esters are added in (3), is stirred 17 minutes, is terephthalic acid (TPA) total weight in addition
0.03% catalyst glycol antimony and addition is 0.027% stabilizer trimethyl phosphate of terephthalic acid (TPA) total weight
Under effect, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, which is steadily evacuated to absolute pressure by normal pressure
Power 498Pa, at 269 DEG C, the reaction time is 39 minutes for temperature control；It then proceedes to vacuumize, carries out the polycondensation of high vacuum stage of Fig
Reaction, it is 60Pa so that reaction pressure is down to absolute pressure, and reaction temperature control is made and is modified in 278 DEG C, 64 minutes reaction time
Polyester.
The number-average molecular weight of modified poly ester is 17000, and modified poly ester is pungent by terephthalic acid (TPA) segment, ethylene glycol segment and 2-
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 process of the modified poly ester of embodiment 11 is with embodiment 1, wherein main technical parameter is referring to table 1；In step
Suddenly it after terephthalic acid (TPA) binary alcohol esters are added in (3), is stirred 18 minutes, is terephthalic acid (TPA) total weight in addition
0.04% catalyst glycol antimony and addition is 0.03% stabilizer trimethyl phosphate of terephthalic acid (TPA) total weight
Under effect, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, which is steadily evacuated to absolute pressure by normal pressure
Power 497Pa, at 260 DEG C, the reaction time is 40 minutes for temperature control；It then proceedes to vacuumize, carries out the polycondensation of high vacuum stage of Fig
Reaction, it is 60Pa so that reaction pressure is down to absolute pressure, and reaction temperature control is made and is modified in 277 DEG C, 63 minutes reaction time
Polyester.
The number-average molecular weight of modified poly ester is 18000, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- 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 process of the modified poly ester of embodiment 2 is with embodiment 1, wherein main technical parameter is referring to table 1；In step
(3) it after terephthalic acid (TPA) binary alcohol esters being added, is stirred 18 minutes, in 0.038% that addition is terephthalic acid (TPA) weight
Catalyst acetic acid antimony and addition be terephthalic acid (TPA) weight 0.03% stabilizer Trimethyl phosphite under the action of,
Start the polycondensation reaction of low vacuum stage under conditions of negative pressure, which is steadily evacuated to absolute pressure 497Pa by normal pressure, temperature
At 265 DEG C, the reaction time is 42 minutes for degree control；It then proceedes to vacuumize, carries out the polycondensation reaction of high vacuum stage of Fig, make reaction
It is 40Pa that pressure, which is down to absolute pressure, and modified poly ester is made in 277 DEG C, 70 minutes reaction time in reaction temperature control.
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 three leaf special-shaped polyester fiber of porous superbright light, three leaf special-shaped polyester fiber of porous superbright light are adopted
It is made with the porous spinneret that the cross-sectional shape of spinneret orifice is trilobal cross, three leaves are mutual in the trilobal cross cross section of spinneret orifice
At 120 degree of angles, the ratio of leaf length and leaf width is 2:1, the arrangement mode of spinneret orifice is oval shaped arrangements, ellipse on spinneret
Arrangement refers to that 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.
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.
Modified poly ester obtains Modified polyester chips through pelletizing made from embodiment 1；Squeezed out again through metering, porous spinneret orifice,
It cools down, oil, stretching, thermal finalization and winding, three leaf special-shaped polyester fiber of porous superbright light is made；The temperature of extrusion is 280 DEG C,
Cooling wind-warm syndrome is 25 DEG C, and the speed of winding is 4000m/min.
The filament number of three leaf special-shaped polyester fiber of porous superbright light obtained is 0.5dtex, fracture strength 4.0cN/
Dtex, elongation at break 31.0%；Three leaf special-shaped polyester fiber of porous superbright light is in the case where temperature is 80 DEG C, fibrous inside molecule
The spatial joint clearance of interchain increases 15v/v%；The line density deviation ratio of polyester fiber is 0.5%, and fracture strength CV values are 4.0%,
Extension at break CV values are 8.0%, and yarn unevenness CV values are 2.0%, boiling water shrinkage 7.2%, oil content 0.80%.
Embodiment 30
A kind of preparation method of three leaf special-shaped polyester fiber of porous superbright light, three leaf special-shaped polyester fiber of porous superbright light are adopted
It is made with the porous spinneret that the cross-sectional shape of spinneret orifice is trilobal cross, three leaves are mutual in the trilobal cross cross section of spinneret orifice
At 120 degree of angles, the ratio of leaf length and leaf width is 2:1, the arrangement mode of spinneret orifice is oval shaped arrangements, ellipse on spinneret
Arrangement refers to that 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.
As shown in figure 3, elliptical long axis and the ratio of minor axis length are 1.6, 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 382.
Modified poly ester obtains Modified polyester chips through pelletizing made from embodiment 1；Squeezed out again through metering, porous spinneret orifice,
It cools down, oil, stretching, thermal finalization and winding, three leaf special-shaped polyester fiber of porous superbright light is made；The temperature of extrusion is 280 DEG C,
Cooling wind-warm syndrome is 25 DEG C, and the speed of winding is 4000m/min.
The filament number of three leaf special-shaped polyester fiber of porous superbright light obtained is 0.3dtex, fracture strength 5.6cN/
Dtex, elongation at break 32.0%, three leaf special-shaped polyester fiber of porous superbright light is in the case where temperature is 80 DEG C, fibrous inside molecule
The spatial joint clearance of interchain increases 18v/v%；The line density deviation ratio of polyester fiber is 0.3%, and fracture strength CV values are 2.0%,
Extension at break CV values are 6.0%, and 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 three leaf special-shaped polyester fiber of porous superbright light, three leaf special-shaped polyester fiber of porous superbright light are adopted
It is made with the porous spinneret that the cross-sectional shape of spinneret orifice is trilobal cross, three leaves are mutual in the trilobal cross cross section of spinneret orifice
At 120 degree of angles, the ratio of leaf length and leaf width is 2:1, the arrangement mode of spinneret orifice is circular arrangement, circular arrangement on spinneret
Refer to that the hole center of spinneret orifice is located on concentric circles, concentric circles is that series is round.As shown in Fig. 2, the spacing etc. of adjacent spinneret orifice
1.5mm is added in the guide hole diameter of spinneret orifice, spinneret is round spinneret, and the diameter and series of round spinneret are round maximum
The difference of diameter be 11mm, a diameter of 2.0mm of guide hole of spinneret orifice, the spinneret hole count of spinneret is 370.
Modified poly ester obtains Modified polyester chips through pelletizing made from embodiment 1；Squeezed out again through metering, porous spinneret orifice,
It cools down, oil, stretching, thermal finalization and winding, three leaf special-shaped polyester fiber of porous superbright light is made；The temperature of extrusion is 280 DEG C,
Cooling wind-warm syndrome is 25 DEG C, and the speed of winding is 4000m/min.
The filament number of three leaf special-shaped polyester fiber of porous superbright light obtained is 2.0dtex, fracture strength 3.8cN/
Dtex, elongation at break 30.0%；Three leaf special-shaped polyester fiber of porous superbright light is in the case where temperature is 80 DEG C, fibrous inside molecule
The spatial joint clearance of interchain increases 10v/v%；The line density deviation ratio of polyester fiber is 0.8%, and fracture strength CV values are 7.0%,
Extension at break CV values are 10.0%, and 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 three leaf special-shaped polyester fiber of porous superbright light, three leaf special-shaped polyester fiber of porous superbright light are adopted
It is made with the porous spinneret that the cross-sectional shape of spinneret orifice is trilobal cross, three leaves are mutual in the trilobal cross cross section of spinneret orifice
At 120 degree of angles, the ratio of leaf length and leaf width is 3:1, the arrangement mode of spinneret orifice is oval shaped arrangements on spinneret.Spinneret orifice
Be arranged as long axial symmetry, the ratio of elliptical long axis and minor axis length is 1.4, and the spacing of adjacent spinneret orifice is equal to spinneret orifice
Guide hole diameter adds 1.6mm, and spinneret is round spinneret, diameter and the oval maximum long axis length of series of round spinneret
Difference be 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 192 of spinneret.
Modified poly ester obtains Modified polyester chips through pelletizing；It squeezes out, cool down, oil, draw through metering, porous spinneret orifice again
It stretches, thermal finalization and winding, three leaf special-shaped polyester fiber of porous superbright light is made；The temperature of extrusion is 290 DEG C, and cooling wind-warm syndrome is
22 DEG C, the speed of winding is 6000m/min.Three leaf special-shaped polyester fiber filament number of porous superbright light obtained be 0.3~
0.5dtex, the mechanical performance data such as following table of the spatial joint clearance Magnification of fibrous inside molecule interchain and fiber at 80 DEG C.
Embodiment 34~36
A kind of preparation method of three leaf special-shaped polyester fiber of porous superbright light, three leaf special-shaped polyester fiber of porous superbright light are adopted
It is made with the porous spinneret that the cross-sectional shape of spinneret orifice is trilobal cross, three leaves are mutual in the trilobal cross cross section of spinneret orifice
At 120 degree of angles, the ratio of leaf length and leaf width is 3:1, the arrangement mode of spinneret orifice is oval shaped arrangements on spinneret.Spinneret orifice
Be arranged as that short axle is symmetrical, the ratio of elliptical long axis and minor axis length is 1.4, and the spacing of adjacent spinneret orifice is equal to spinneret orifice
Guide hole diameter adds 1.7mm, and spinneret is elliptical spinneret plate, elliptical spinneret plate and the oval maximum long axis length of series
Difference is 12mm, and the spinneret hole count of a diameter of 1.8mm of guide hole of spinneret orifice, spinneret are 200.
Modified poly ester obtains Modified polyester chips through pelletizing；It squeezes out, cool down, oil, draw through metering, porous spinneret orifice again
It stretches, thermal finalization and winding, three leaf special-shaped polyester fiber of porous superbright light is made；The temperature of extrusion is 290 DEG C, and cooling wind-warm syndrome is
22 DEG C, the speed of winding is 6000m/min.Three leaf special-shaped polyester fiber filament number of porous superbright light obtained be 0.6~
0.9dtex, the mechanical performance data such as following table of the spatial joint clearance Magnification of fibrous inside molecule interchain and fiber at 90 DEG C.
Embodiment 37~39
A kind of preparation method of three leaf special-shaped polyester fiber of porous superbright light, three leaf special-shaped polyester fiber of porous superbright light are adopted
It is made with the porous spinneret that the cross-sectional shape of spinneret orifice is trilobal cross, three leaves are mutual in the trilobal cross cross section of spinneret orifice
At 120 degree of angles, the ratio of leaf length and leaf width is 4:1, the arrangement mode of spinneret orifice is oval shaped arrangements on spinneret.Spinneret orifice
Be arranged as long axis and short axle is symmetrical, the ratio of elliptical long axis and minor axis length is 1.4, and the spacing of adjacent spinneret orifice is equal to spray
The guide hole diameter of wire hole adds 1.8mm, and spinneret is round spinneret, diameter and the oval maximum length of series of round spinneret
The difference of shaft length is 13mm, and the spinneret hole count of a diameter of 2.5mm of guide hole of spinneret orifice, spinneret are 200.
Modified poly ester obtains Modified polyester chips through pelletizing；It squeezes out, cool down, oil, draw through metering, porous spinneret orifice again
It stretches, thermal finalization and winding, three leaf special-shaped polyester fiber of porous superbright light is made；The temperature of extrusion is 285 DEG C, and cooling wind-warm syndrome is
24 DEG C, the speed of winding is 5000m/min.Three leaf special-shaped polyester fiber filament number of porous superbright light obtained be 0.5~
0.7dtex, the spatial joint clearance Magnification of fibrous inside molecule interchain and the mechanical performance data of fiber are as follows at 100 DEG C
Table.
Embodiment 40~42
A kind of preparation method of three leaf special-shaped polyester fiber of porous superbright light, three leaf special-shaped polyester fiber of porous superbright light are adopted
It is made with the porous spinneret that the cross-sectional shape of spinneret orifice is trilobal cross, three leaves are mutual in the trilobal cross cross section of spinneret orifice
At 120 degree of angles, the ratio of leaf length and leaf width is 5:1, the arrangement mode of spinneret orifice is oval shaped arrangements on spinneret.Spinneret orifice
Be arranged as long axis and short axle is symmetrical, the ratio of elliptical long axis and minor axis length is 1.7, and the spacing of adjacent spinneret orifice is equal to spray
The guide hole diameter of wire hole adds 1.9mm, and spinneret is elliptical spinneret plate, elliptical spinneret plate and the oval maximum long axis of series
The difference of length is 14mm, and the spinneret hole count of a diameter of 1.5mm of guide hole of spinneret orifice, spinneret are 210.
Modified poly ester obtains Modified polyester chips through pelletizing；It squeezes out, cool down, oil, draw through metering, porous spinneret orifice again
It stretches, thermal finalization and winding, three leaf special-shaped polyester fiber of porous superbright light is made；The temperature of extrusion is 285 DEG C, and cooling wind-warm syndrome is
25 DEG C, the speed of winding is 5000m/min.Three leaf special-shaped polyester fiber filament number of porous superbright light obtained be 0.8~
1.0dtex, the spatial joint clearance Magnification of fibrous inside molecule interchain and the mechanical performance data of fiber are as follows at 110 DEG C
Table.
Embodiment 43~45
A kind of preparation method of three leaf special-shaped polyester fiber of porous superbright light, three leaf special-shaped polyester fiber of porous superbright light are adopted
It is made with the porous spinneret that the cross-sectional shape of spinneret orifice is trilobal cross, three leaves are mutual in the trilobal cross cross section of spinneret orifice
At 120 degree of angles, the ratio of leaf length and leaf width is 2:1, the arrangement mode of spinneret orifice is oval shaped arrangements on spinneret.Spinneret orifice
Be arranged as that short axle is symmetrical, the ratio of elliptical long axis and minor axis length is 1.8, and the spacing of adjacent spinneret orifice is equal to spinneret orifice
Guide hole diameter adds 1.5mm, and spinneret is round spinneret, diameter and the oval maximum long axis length of series of round spinneret
Difference be 15mm, a diameter of 1.8mm of guide hole of spinneret orifice, the spinneret hole count of spinneret is 240.
Modified poly ester obtains Modified polyester chips through pelletizing；It squeezes out, cool down, oil, draw through metering, porous spinneret orifice again
It stretches, thermal finalization and winding, three leaf special-shaped polyester fiber of porous superbright light is made；The temperature of extrusion is 285 DEG C, and cooling wind-warm syndrome is
20 DEG C, the speed of winding is 5500m/min.Three leaf special-shaped polyester fiber filament number of porous superbright light obtained be 1.3~
2.0dtex, the spatial joint clearance Magnification of fibrous inside molecule interchain and the mechanical performance data of fiber are as follows at 120 DEG C
Table.
Embodiment 46~49
A kind of preparation method of three leaf special-shaped polyester fiber of porous superbright light, three leaf special-shaped polyester fiber of porous superbright light are adopted
It is made with the porous spinneret that the cross-sectional shape of spinneret orifice is trilobal cross, three leaves are mutual in the trilobal cross cross section of spinneret orifice
At 120 degree of angles, the ratio of leaf length and leaf width is 5:1, the arrangement mode of spinneret orifice is oval shaped arrangements on spinneret.Spinneret orifice
Be arranged as long axial symmetry, the ratio of elliptical long axis and minor axis length is 1.8, and the spacing of adjacent spinneret orifice is equal to spinneret orifice
Guide hole diameter adds 1.6mm, and spinneret is round spinneret, diameter and the oval maximum long axis length of series of round spinneret
Difference be 16mm, a diameter of 2.2mm of guide hole of spinneret orifice, the spinneret hole count of spinneret is 250.
Modified poly ester obtains Modified polyester chips through pelletizing；It squeezes out, cool down, oil, draw through metering, porous spinneret orifice again
It stretches, thermal finalization and winding, three leaf special-shaped polyester fiber of porous superbright light is made；The temperature of extrusion is 288 DEG C, and cooling wind-warm syndrome is
23 DEG C, the speed of winding is 5500m/min.Three leaf special-shaped polyester fiber filament number of porous superbright light obtained be 1.7~
2.0dtex, the spatial joint clearance Magnification of fibrous inside molecule interchain and the mechanical performance data of fiber are as follows at 130 DEG C
Table.
Embodiment 50~53
A kind of preparation method of three leaf special-shaped polyester fiber of porous superbright light, three leaf special-shaped polyester fiber of porous superbright light are adopted
It is made with the porous spinneret that the cross-sectional shape of spinneret orifice is trilobal cross, three leaves are mutual in the trilobal cross cross section of spinneret orifice
At 120 degree of angles, the ratio of leaf length and leaf width is 4:1, the arrangement mode of spinneret orifice is oval shaped arrangements on spinneret.Spinneret orifice
Be arranged as that short axle is symmetrical, the ratio of elliptical long axis and minor axis length is 1.8, and the spacing of adjacent spinneret orifice is equal to spinneret orifice
Guide hole diameter adds 1.8mm, and spinneret is round spinneret, diameter and the oval maximum long axis length of series of round spinneret
Difference be 15mm, a diameter of 2.5mm of guide hole of spinneret orifice, the spinneret hole count of spinneret is 260.
Modified poly ester obtains Modified polyester chips through pelletizing；It squeezes out, cool down, oil, draw through metering, porous spinneret orifice again
It stretches, thermal finalization and winding, three leaf special-shaped polyester fiber of porous superbright light is made；The temperature of extrusion is 288 DEG C, and cooling wind-warm syndrome is
24 DEG C, the speed of winding is 5500m/min.Three leaf special-shaped polyester fiber filament number of porous superbright light obtained be 0.3~
0.5dtex, the spatial joint clearance Magnification of fibrous inside molecule interchain and the mechanical performance data of fiber are as follows at 100 DEG C
Table.
Embodiment 54~57
A kind of preparation method of three leaf special-shaped polyester fiber of porous superbright light, three leaf special-shaped polyester fiber of porous superbright light are adopted
It is made with the porous spinneret that the cross-sectional shape of spinneret orifice is trilobal cross, three leaves are mutual in the trilobal cross cross section of spinneret orifice
At 120 degree of angles, the ratio of leaf length and leaf width is 2:1, the arrangement mode of spinneret orifice is oval shaped arrangements on spinneret.Spinneret orifice
Be arranged as long axial symmetry, the ratio of elliptical long axis and minor axis length is 1.8, and the spacing of adjacent spinneret orifice is equal to spinneret orifice
Guide hole diameter adds 1.5mm, and spinneret is round spinneret, diameter and the oval maximum long axis length of series of round spinneret
Difference be 16mm, a diameter of 1.8mm of guide hole of spinneret orifice, the spinneret hole count of spinneret is 300.
Modified poly ester obtains Modified polyester chips through pelletizing；It squeezes out, cool down, oil, draw through metering, porous spinneret orifice again
It stretches, thermal finalization and winding, three leaf special-shaped polyester fiber of porous superbright light is made；The temperature of extrusion is 288 DEG C, and cooling wind-warm syndrome is
24 DEG C, the speed of winding is 5800m/min.Three leaf special-shaped polyester fiber filament number of porous superbright light obtained be 1.7~
2.0dtex, the spatial joint clearance Magnification of fibrous inside molecule interchain and the mechanical performance data of fiber are as follows at 120 DEG C
Table.
Embodiment 58
The dyeing of three leaf special-shaped polyester fiber of porous superbright light：
The three leaf special-shaped polyester fiber of porous superbright light prepared to embodiment 29 dyes in high temperature and pressure machine, specifically
Condition is：Before dyeing, three leaf special-shaped polyester fiber nonionic surfactant of porous superbright light 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.Three leaf abnormal shape polyester of porous superbright light after dyed
The dye uptake of fiber 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 the bright blue S-GL of dispersion, three leaf abnormal shape of porous superbright light is poly-
The dye uptake result such as following table of ester fiber and general fibre：
It is compared by the coloring of three leaf special-shaped polyester fiber of porous superbright light and general fibre, it can be seen that porous super
The coloring of three leaf special-shaped polyester fiber of light is substantially better than general fibre, also from the side illustration modification of the invention prepared
The dihydric alcohol segment containing branch contained in polyester macromolecule, makes the increasing degree of free volume be far longer than unbranched polyester
The characteristic of macromolecular chain, the increase of free volume improve molecule and enter degree inside polyester, prepared by modified polyester
The free volume of polyester fiber be far longer than polyester fiber unbranched at same temperature, increase the diffusion of dyestuff, carry
The dyeability of superpolyester fiber.
Embodiment 59
The dyeing of three leaf special-shaped polyester fiber of porous superbright light：
To three leaf special-shaped polyester fiber of porous superbright light prepared by embodiment 31, dyeing course is identical as embodiment 58, together
The identical dyeing conditions of Shi Caiyong dye general fibre.
When disperse dyes are Disperse Red 3B, disperse blue SE-2R or the bright blue S-GL of dispersion, three leaf abnormal shape of porous superbright light is poly-
The dye uptake result such as following table of ester fiber and general fibre：
It is compared by coloring, it can be seen that the coloring of three leaf special-shaped polyester fiber of porous superbright light is substantially better than
General fibre.
Claims (9)
1. a kind of three leaf special-shaped polyester fiber of porous superbright light, it is characterized in that：The three leaf shaped filaments of porous superbright light are by being modified
Polyester is obtained through spinneret orifice for three leaf profile spinneret spinning of Y-shaped structure, the three leaf special-shaped polyester fiber of porous superbright light
Material be modified poly ester, the modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and dihydric alcohol segment containing branch
Composition；
The filament number of the three leaf special-shaped polyester fiber of porous superbright light is 0.3~2.0dtex, fracture strength >=3.8cN/
Dtex, elongation at break are 33.0 ± 3.0%；The three leaf special-shaped polyester fiber of porous superbright light is 80~130 DEG C in temperature
Under, the spatial joint clearance of fibrous inside molecule interchain increases 10~30v/v%；The three leaf special-shaped polyester fiber of porous superbright light
Line density deviation ratio≤0.5%, fracture strength CV value≤4.0%, extension at break CV value≤8.0%, yarn unevenness CV values≤
2.0%, boiling water shrinkage is 7.5 ± 0.5%, and oil content is 0.90 ± 0.20%；
Dihydric alcohol containing branch is -1,3 propylene glycol of 2- amyls, -1,3 propylene glycol of 2- hexyls, -1,3 propylene glycol of 2- heptyl, 2- pungent
- 1,3 propylene glycol of base, -1,3 propylene glycol of 2- nonyls, -1,3 propylene glycol of 2- decyls, -1,4 butanediol of 2- amyls, -1,4 fourth of 2- hexyls
Glycol, -1,4 butanediol of 2- heptyl, -1,4 butanediol of 2- octyls, -1,4 butanediol of 2- nonyls, -1,4 butanediol of 2- decyls, 2- penta
- 1,5 pentanediol of base, -1,5 pentanediol of 2- hexyls, -1,5 pentanediol of 2- heptyl, -1,5 pentanediol of 2- octyls, 2- nonyls -1,5 penta
Glycol, -1,5 pentanediol of 2- decyls, -1,6 hexylene glycol of 2- amyls, -1,6 hexylene glycol of 2- hexyls, -1,6 hexylene glycol of 2- heptyl, 2- are pungent
One or more of -1,6 hexylene glycol of -1,6 hexylene glycol of base, -1,6 hexylene glycol of 2- nonyls or 2- decyls.
2. a kind of preparation method of three leaf special-shaped polyester fiber of porous superbright light as described in claim 1, it is characterized in that：It will change
Property polyester to use the cross-sectional shape of spinneret orifice for the porous spinneret spinning of trilobal cross porous three leaf of superbright light to be made special-shaped
Polyester fiber；The arrangement mode of spinneret orifice is oval shaped arrangements on the porous spinneret, and the oval shaped arrangements refer to spinneret
The hole center in 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 method of the three leaf special-shaped polyester fiber of porous superbright light is：Modified poly ester obtains modified poly ester through pelletizing and cuts
Piece；Squeezes out, cool down, oil, stretch through metering, porous spinneret orifice again, thermal finalization and winding, obtained porous three leaf of superbright light abnormal shape
Polyester fiber；
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；
(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.
3. a kind of preparation method of three leaf special-shaped polyester fiber of porous superbright light according to claim 2, which is characterized in that
The specific preparation process of the modified poly 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；
The main spinning technology parameter of the three leaf special-shaped polyester fiber of porous superbright light is：
The temperature of extrusion：280~290 DEG C；
Cooling wind-warm syndrome：20~25 DEG C；
The speed of winding：4000~4600m/min.
4. a kind of preparation method of three leaf special-shaped polyester fiber of porous superbright light 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 to benzene two
The 0.3-0.5% of formic acid weight；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.
5. a kind of preparation method of three leaf special-shaped polyester fiber of porous superbright light according to claim 2, which is characterized in that
The spinneret orifice be arranged as long axis and/or short axle is symmetrical.
6. a kind of preparation method of three leaf special-shaped polyester fiber of porous superbright light according to claim 2, which is characterized in that
Elliptical long axis and the ratio of minor axis length are 1.3~1.8；The spacing of adjacent spinneret orifice is more than or equal to the guide hole diameter of spinneret orifice
In addition 1.5mm.
7. a kind of preparation method of three leaf special-shaped polyester fiber of porous superbright light according to claim 2, which is characterized in that
The spinneret is round spinneret or elliptical spinneret plate；The diameter of the circle spinneret and the oval maximum long axis of series
The difference of length is more than 10mm, and the elliptical spinneret plate and the difference of the oval maximum long axis length of series are more than 10mm.
8. a kind of preparation method of three leaf special-shaped polyester fiber of porous superbright light according to claim 2, which is characterized in that
A diameter of 1.5~the 2.5mm of guide hole of the spinneret orifice；The spinneret hole count of the spinneret is more than or equal to 192.
9. a kind of preparation method of three leaf special-shaped polyester fiber of porous superbright light according to claim 2, which is characterized in that
Three leaves are mutually 120 degree of angles in the trilobal cross cross section of the spinneret orifice, and it is 2~5 that leaf, which is grown with the ratio of leaf width,:1.
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| CN106283261B (en) * | 2016-08-31 | 2018-10-30 | 江苏恒力化纤股份有限公司 | Porous super soft super fine denier polyester fiber of one kind and preparation method thereof |
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