CN106283263B - Porous soft super fine denier polyester fiber of one kind and preparation method thereof - Google Patents

Porous soft super fine denier polyester fiber of one kind and preparation method thereof Download PDF

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Publication number
CN106283263B
CN106283263B CN201610785296.1A CN201610785296A CN106283263B CN 106283263 B CN106283263 B CN 106283263B CN 201610785296 A CN201610785296 A CN 201610785296A CN 106283263 B CN106283263 B CN 106283263B
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tpa
terephthalic acid
spinneret
preparation
polyester fiber
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CN106283263A (en
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李文刚
汤方明
王彦芳
尹立新
邓丽娜
孙晓华
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Jiangsu Hengli Chemical Fiber Co Ltd
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Jiangsu Hengli Chemical Fiber Co Ltd
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D13/00—Complete machines for producing artificial threads
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
    • D01D5/092—Cooling filaments, threads or the like, leaving the spinnerettes in shafts or chimneys
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor

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

Abstract

The present invention relates to a kind of porous soft super fine denier polyester fibers and preparation method thereof, and porous soft super fine denier polyester fiber is made using porous spinneret spinning in modified poly ester；The arrangement mode of spinneret orifice is oval shaped arrangements on porous spinneret, i.e. the hole center of spinneret orifice is located on concentration ellipse, and concentration ellipse is that series is oval, and all elliptical long axis are conllinear, and short axle is conllinear.It is porous softness super fine denier polyester fiber by Modified polyester chips through metering, extrusion, cooling, oiling is made with high-speed winding, 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%, fracture strength CV value≤4.0%, extension at break CV value≤8.0%, yarn unevenness CV value≤2.0%.

Description

Porous soft super fine denier polyester fiber of one kind and preparation method thereof
Technical field
The invention belongs to field of polyester fiber, are related to porous soft super fine denier polyester fiber of one kind and preparation method thereof.
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.
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 porous soft super fine denier polyester fiber of one kind and preparation method thereof.The original of the polyester fiber of the present invention Material is modified poly ester, and the dihydric alcohol segment containing branch is introduced in the strand of modified poly ester, and modified polyester is prepared porous soft Soft super fine denier polyester fiber, under the conditions of certain temperature, the spatial joint clearance of porous softness super fine denier polyester fiber interior molecules interchain Increasing degree be far longer than conventional polyester fiber unbranched at same temperature, be conducive to the molecules such as coloring agent enter in The degree in portion improves dyeing rate；The melt viscosity of porous softness super fine denier polyester fiber reduces, and reduces processing temperature, reduces Degradation rate is conducive to process；In addition compound with regular structure of the dihydric alcohol segment containing branch to porous soft super fine denier polyester fiber The not big destruction of property, maintains the excellent performance of polyester fiber.Spinneret orifice oval shaped arrangements are used in spinning process of the present invention Spinneret, be conducive to fiber in spinning process it is uniform, be fully cooled, performance between fiber and structure difference 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：
The material of a kind of porous soft super fine denier polyester fiber, the porous soft super fine denier polyester fiber is modified poly- Ester, the modified poly ester are made of terephthalic acid (TPA) segment, ethylene glycol segment and dihydric alcohol segment containing branch, described to contain branch Dihydric alcohol segment refer on a non-end group carbon that branch is located in dihydric alcohol segment and branch is containing 5-10 carbon atom Linear carbon chain dihydric alcohol segment；
The filament number of the porous soft super fine denier polyester fiber is 0.20~0.50dtex, initial modulus≤70cN/ Dtex, fracture strength >=3.8cN/dtex, elongation at break are 35.0 ± 3.0%；The porous soft super fine denier polyester fiber In the case where temperature is 80~130 DEG C, the spatial joint clearance of fibrous inside molecule interchain increases 10~30v/v%, at 260~290 DEG C, Melt viscosity declines 10~20%；Line density deviation ratio≤0.5% of the porous soft super fine denier polyester fiber, fracture strength CV value≤4.0%, extension at break CV value≤8.0%, yarn unevenness CV value≤2.0%.
The present invention also provides a kind of preparation methods of porous soft super fine denier polyester fiber, by modified poly ester using porous Porous soft super fine denier polyester fiber is made in spinneret spinning；The arrangement mode of spinneret orifice is ellipse on the porous spinneret Arrangement, the oval shaped arrangements refer to that the hole center of spinneret orifice is located on concentration ellipse, and the concentration ellipse is that series is oval, institute There is elliptical long axis conllinear, and short axle is conllinear；
The preparation method of the porous soft super fine denier polyester fiber is：Modified poly ester is obtained modified poly ester through pelletizing to cut Piece, then by Modified polyester chips through metering, extrusion, cooling, oil and high-speed winding, it is fine to obtain porous soft super fine denier polyester Dimension；
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 porous soft super fine denier polyester fiber as described above, the specific preparation of the modified poly ester Step 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 porous soft super fine denier polyester fiber is：
The temperature of extrusion：290~295 DEG C；
Cooling wind-warm syndrome：20~25 DEG C；
HT1：75-95℃；
HT2：120-130℃；
High-speed winding speed：4000~5000m/min.
A kind of preparation method of porous soft super fine denier polyester fiber as described above, in step (1), terephthalic acid (TPA) with The molar ratio of dihydric alcohol containing branch is 1:1.3-1.5；Concentrated sulfuric acid addition is the 0.3-0.5% of terephthalic acid (TPA) weight；Institute State 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 porous soft super fine denier polyester fiber as described above, the dihydric alcohol containing branch is 2- - 1,4 butanediol of amyl, -1,4 butanediol of 2- hexyls, -1,4 butanediol of 2- heptyl, -1,4 butanediol of 2- octyls, 2- nonyls -1,4 Butanediol, -1,4 butanediol of 2- decyls, -1,5 pentanediol of 2- amyls, -1,5 pentanediol of 2- hexyls, -1,5 pentanediol of 2- heptyl, 2- One or more of -1,5 pentanediol of -1,5 pentanediol of octyl, -1,5 pentanediol of 2- nonyls or 2- decyls.
A kind of preparation method of porous soft super fine denier polyester fiber as described above, the spinneret orifice are arranged as long axis And/or short axle is symmetrical.
A kind of preparation method of porous soft super fine denier polyester fiber as described above, elliptical long axis and minor axis length Ratio is 1.3~1.8；The guide hole diameter that the spacing of adjacent spinneret orifice is more than or equal to spinneret orifice adds 1.5mm.When having for spinneret Area phase is imitated simultaneously as the perimeter of ellipse is more than circular perimeter, the number of plies of spinneret orifice oval shaped arrangements is less than circular row The number of plies of row, the hole count of spinneret orifice oval shaped arrangements are more than the hole count of circular arrangement, and therefore, spinneret orifice oval shaped arrangements are conducive to The cooling of ring blowing, improves the cooling efficiency of ring blowing, and the fibre property of preparation is also more excellent.The ratio of long axis and minor axis length Value is closer to 1, and ellipse is more similar to justify, and the difference of cooling efficiency and cooling effect is little；The ratio of long axis and minor axis length When being 1.3, cooling effect significantly improves, and individual pen hole count accordingly increases by 16%；It is cold when long axis and the ratio of minor axis length are 1.8 But effect improves larger, the accordingly increase by 33% of individual pen hole count, and in the case of identical hole count, oval shaped arrangements of the invention are more same than conventional The number of turns of heart 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 and minor axis length Ratio be more than 1.8 when, ellipse be partial to form flat shape, be 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 is imitated Fruit.
A kind of preparation method of porous soft super fine denier polyester fiber as described above, the spinneret is round spinneret Or elliptical spinneret plate；The diameter of the circle spinneret and the difference of the oval maximum long axis length of series are more than 10mm, institute It states elliptical spinneret plate and the difference of the oval maximum long axis length of series is more than 10mm.
A kind of preparation method of porous soft super fine denier polyester fiber as described above, the guide hole of the spinneret orifice are a diameter of 1.5~2.5mm；The spinneret hole count of the spinneret is more than or equal to 192.
A kind of preparation method of porous soft super fine denier polyester fiber as described above, the spinneret orifice of the spinneret Cross-sectional shape is circle, square, diamond shape, "-" type, triangular form, trilobal cross, hollow type or platypelloid type.
The principle of the present invention is：
For unbranched polyester fiber, molecular chain structure is the linear macromolecule containing benzene ring structure, on strand Functional group's marshalling, regularity is good, flexible poor；Its free volume increments is small when the temperature rises, the resistance of these characteristics Dyestuff has been hindered to enter inside polyester fiber, thus dyeability is poor.
The raw material of the polyester fiber of the present invention is modified poly ester, the dihydric alcohol containing branch contained in modified poly ester macromolecular Segment, when temperature is higher than glass transition temperature, branch makes the increasing degree of free volume be far longer than no branch prior to backbone motion The characteristic of the polyester macromolecule chain of chain, the increase of free volume improves molecule and enters degree inside polyester, modified The free volume of polyester fiber prepared by polyester is far longer than polyester fiber unbranched at same temperature, increases the diffusion of dyestuff Degree improves the dyeability of polyester fiber.Meanwhile polyester fiber prepared by modified poly ester advantageously reduces melt viscosity, has Conducive to its processing performance of improvement.The introducing of dihydric alcohol segment containing the branch destruction not big to polyester fiber structures regularity, Maintain the excellent performance of polyester fiber.
When the effective area phase of spinneret is simultaneously as the perimeter of ellipse is more than circular perimeter, spinneret orifice ellipse The number of plies of arrangement is less than the number of plies of circular arrangement, and the hole count of spinneret orifice oval shaped arrangements is more than the hole count of circular arrangement, using spray The spinneret of wire hole oval shaped arrangements enables to fiber quick, uniformly cooling, and the difference of structure and performance is smaller between fiber, Be conducive to improve the performance of the even dyeing rate and fiber of fiber.
Advantageous effect：
1) arrangement mode of spinneret orifice is oval shaped arrangements on spinneret of the invention, and the effective area of spinneret is identical When, the number of plies of spinneret orifice oval shaped arrangements is less than the number of plies of circular arrangement, and ring blowing is easier to blow through dynamic analysis of spinning, dynamic analysis of spinning Cooling effect it is more preferable, the fibre property of preparation is also more excellent.
2) arrangement mode of spinneret orifice is oval shaped arrangements on spinneret of the invention, and the effective area of spinneret is identical When, the hole count of spinneret orifice oval shaped arrangements is more than the hole count of circular arrangement, and oval shaped arrangements can realize a greater degree of cooling, Significantly improve cooling efficiency.
3) material of porous soft super fine denier polyester fiber produced by the present invention is modified poly ester, in modified poly ester macromolecular The dihydric alcohol segment containing branch contained, when temperature is higher than glass transition temperature, branch makes free volume prior to backbone motion Increasing degree is far longer than the characteristic of unbranched polyester macromolecule chain, and the increase of free volume improves molecule entrance and gathers Degree inside ester increases the free volume of polyester fiber by branch to increase the diffusion of dyestuff, it is fine to improve polyester The dyeability of dimension.
4) porous soft super fine denier polyester fiber produced by the present invention, the increase of polyester fiber free volume advantageously reduce Melt viscosity is conducive to improve its processing performance.
5) porous soft super fine denier polyester fiber produced by the present invention, the polyester of the introducing pair of the dihydric alcohol segment containing branch The not big destruction of the structural regularity of fiber, maintains the excellent performance of polyester fiber.
6) porous soft super fine denier dyeing polyester fibers performance and good mechanical performance produced by the present invention, initial modulus≤ 70cN/dtex, line density deviation ratio≤0.5% of porous softness super fine denier polyester fiber, fracture strength CV value≤4.0% break Split elongation CV value≤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) total weight and addition is terephthalic acid (TPA) total weight Under the action of 0.01% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure It is 500Pa that section pressure, which is steadily evacuated to absolute pressure by normal pressure, and at 260 DEG C, the reaction time is 30 minutes for temperature control；It then proceedes to It vacuumizes, carries out the polycondensation reaction of high vacuum stage of Fig, it is 100Pa so that reaction pressure is down to absolute pressure, and reaction temperature control exists 275 DEG C, modified poly ester was made in 50 minutes reaction time.
The number-average molecular weight of modified poly ester is 15000, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- penta Base -1,3 propylene glycol segment forms, and the Mole percent ratio of the dihydric alcohol segment containing branch and ethylene glycol segment is 2%.
Table 1：Embodiment 2-12 important technological parameters
Embodiment 2
The preparation method of the modified poly ester of embodiment 2, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 16 minutes, is in addition 0.011% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are the 0.02% of terephthalic acid (TPA) total weight Stabilizer triphenyl phosphate under the action of, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure Absolute pressure 490Pa is steadily evacuated to by normal pressure, at 262 DEG C, the reaction time is 31 minutes for temperature control；It then proceedes to vacuumize, The polycondensation reaction for carrying out high vacuum stage of Fig makes reaction pressure be down to absolute pressure 90Pa, and reaction temperature is controlled at 276 DEG C, reaction Modified poly ester was made in 51 minutes time.
The number-average molecular weight of modified poly ester be 16000, modified poly ester by terephthalic acid (TPA) segment, ethylene glycol segment and 2- oneself Base -1,3 propylene glycol segment forms, and the Mole percent ratio of 2- hexyl -1,3 propylene glycol segments and ethylene glycol segment is 2.1%.
Embodiment 3
The preparation method of the modified poly ester of embodiment 3, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 16 minutes, is in addition 0.03% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are the 0.02% of terephthalic acid (TPA) total weight Stabilizer triphenyl phosphate under the action of, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure Absolute pressure 498Pa is steadily evacuated to by normal pressure, at 263 DEG C, the reaction time is 32 minutes for temperature control；It then proceedes to vacuumize, The polycondensation reaction for carrying out high vacuum stage of Fig makes reaction pressure be down to absolute pressure 90Pa, and reaction temperature is controlled at 277 DEG C, reaction Modified poly ester was made in 57 minutes time.
The number-average molecular weight of modified poly ester is 15900, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- heptan Base -1,3 propylene glycol segment forms, and the Mole percent ratio of 2- heptyl -1,3 propylene glycol segments and ethylene glycol segment is 2.2%.
Embodiment 4
The preparation method of the modified poly ester of embodiment 4, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 17 minutes, is in addition 0.033% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are terephthalic acid (TPA) total weight Under the action of 0.023% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure It is 497Pa that section pressure, which is steadily evacuated to absolute pressure by normal pressure, and at 264 DEG C, the reaction time is 33 minutes for temperature control；It then proceedes to It vacuumizes, carries out the polycondensation reaction of high vacuum stage of Fig, it is 80Pa so that reaction pressure is down to absolute pressure, and reaction temperature control exists 278 DEG C, modified poly ester was made in 58 minutes reaction time.
The number-average molecular weight of modified poly ester is 15800, and modified poly ester is pungent by terephthalic acid (TPA) segment, ethylene glycol segment and 2- Base -1,3 propylene glycol segment forms, and the Mole percent ratio of 2- octyl -1,3 propylene glycol segments and ethylene glycol segment is 2.3%.
Embodiment 5
The preparation method of the modified poly ester of embodiment 5, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 17 minutes, is in addition 0.034% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are terephthalic acid (TPA) total weight Under the action of 0.024% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and at 265 DEG C, the reaction time is 34 minutes for temperature control；It then proceedes to take out Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and it is 80Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled 277 DEG C, modified poly ester was made in 59 minutes reaction time.
The number-average molecular weight of modified poly ester is 15900, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- nonyls Base -1,3 propylene glycol segment forms, and the Mole percent ratio of 2- nonyl -1,3 propylene glycol segments and ethylene glycol segment is 2.4%.
Embodiment 6
The preparation method of the modified poly ester of embodiment 6, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 18 minutes, is in addition 0.035% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are terephthalic acid (TPA) total weight Under the action of 0.025% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure Section pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 266 DEG C, the reaction time is 35 minutes for temperature control；It then proceedes to take out Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and it is 70Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled 278 DEG C, modified poly ester was made in 60 minutes reaction time.
The number-average molecular weight of modified poly ester is 16000, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and the 2- last of the ten Heavenly stems Base -1,3 propylene glycol segment forms, and the Mole percent ratio of 2- decyl -1,3 propylene glycol segments and ethylene glycol segment is 2.5%.
Embodiment 7
The preparation method of the modified poly ester of embodiment 7, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 19 minutes, is in addition 0.036% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are terephthalic acid (TPA) total weight Under the action of 0.025% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and at 267 DEG C, the reaction time is 36 minutes for temperature control；It then proceedes to take out Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and it is 70Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled 278 DEG C, modified poly ester was made in 61 minutes reaction time.
The number-average molecular weight of modified poly ester is 16000, and the number-average molecular weight of modified poly ester is 16000, and modified poly ester is by right Phthalic acid segment, ethylene glycol segment and 2- amyls-Isosorbide-5-Nitrae butanediol segment composition, 2- amyls-Isosorbide-5-Nitrae butanediol segment and second two The Mole percent ratio of alcohol segment is 2.6%.
Embodiment 8
The preparation method of the modified poly ester of embodiment 8, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 19 minutes, is in addition 0.036% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are terephthalic acid (TPA) total weight Under the action of 0.025% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and at 267 DEG C, the reaction time is 36 minutes for temperature control；It then proceedes to take out Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and it is 70Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled 278 DEG C, modified poly ester was made in 61 minutes reaction time.
The number-average molecular weight of modified poly ester be 17000, modified poly ester by terephthalic acid (TPA) segment, ethylene glycol segment and 2- oneself The Mole percent ratio of base-Isosorbide-5-Nitrae butanediol segment composition, 2- hexyls-Isosorbide-5-Nitrae butanediol segment and ethylene glycol segment is 2.7%.
Embodiment 9
The preparation method of the modified poly ester of embodiment 9, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 16 minutes, is in addition 0.04% catalyst glycol antimony and addition of terephthalic acid (TPA) total weight are the 0.026% of terephthalic acid (TPA) total weight Under the action of stabilizer trimethyl phosphate, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure by Normal pressure is steadily evacuated to absolute pressure 497Pa, and at 268 DEG C, the reaction time is 38 minutes for temperature control；It then proceedes to vacuumize, into The polycondensation reaction of row high vacuum stage of Fig, it is 60Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled at 279 DEG C, reaction Modified poly ester was made in 62 minutes time.
The number-average molecular weight of modified poly ester is 17000, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- heptan The Mole percent ratio of base-Isosorbide-5-Nitrae butanediol segment composition, 2- heptyl-Isosorbide-5-Nitrae butanediol segment and ethylene glycol segment is 2.8%.
Embodiment 10
The preparation method of the modified poly ester of embodiment 10, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 17 minutes, is in addition 0.03% catalyst glycol antimony and addition of terephthalic acid (TPA) total weight are the 0.027% of terephthalic acid (TPA) total weight Under the action of stabilizer trimethyl phosphate, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure by Normal pressure is steadily evacuated to absolute pressure 498Pa, and at 269 DEG C, the reaction time is 39 minutes for temperature control；It then proceedes to vacuumize, into The polycondensation reaction of row high vacuum stage of Fig, it is 60Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled at 278 DEG C, reaction Modified poly ester was made in 64 minutes time.
The number-average molecular weight of modified poly ester is 17000, and modified poly ester is pungent by terephthalic acid (TPA) segment, ethylene glycol segment and 2- The Mole percent ratio of base-Isosorbide-5-Nitrae butanediol segment composition, 2- octyls-Isosorbide-5-Nitrae butanediol segment and ethylene glycol segment is 3%.
Embodiment 11
The preparation method of the modified poly ester of embodiment 11, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 18 minutes, is in addition 0.04% catalyst glycol antimony and addition of terephthalic acid (TPA) total weight are the 0.03% of terephthalic acid (TPA) total weight Under the action of stabilizer trimethyl phosphate, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure by Normal pressure is steadily evacuated to absolute pressure 497Pa, and at 260 DEG C, the reaction time is 40 minutes for temperature control；It then proceedes to vacuumize, into The polycondensation reaction of row high vacuum stage of Fig, it is 60Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled at 277 DEG C, reaction Modified poly ester was made in 63 minutes time.
The number-average molecular weight of modified poly ester is 18000, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- nonyls The Mole percent ratio of base-Isosorbide-5-Nitrae butanediol segment composition, 2- nonyls-Isosorbide-5-Nitrae butanediol segment and ethylene glycol segment is 4%.
Embodiment 12
The preparation method of the modified poly ester of embodiment 12, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 18 minutes, is in addition The catalyst acetic acid antimony and addition of the 0.038% of terephthalic acid (TPA) weight are 0.03% stabilizer of terephthalic acid (TPA) weight Under the action of Trimethyl phosphite, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, the staged pressure is by normal pressure Steady to be evacuated to absolute pressure 497Pa, at 265 DEG C, the reaction time is 42 minutes for temperature control；It then proceedes to vacuumize, carry out high The polycondensation reaction of vacuum stages, it is 40Pa so that reaction pressure is down to absolute pressure, and reaction temperature control is at 277 DEG C, the reaction time 70 minutes, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained is 26000, by terephthalic acid (TPA) segment, ethylene glycol segment and the 2- last of the ten Heavenly stems The Mole percent ratio of base-Isosorbide-5-Nitrae butanediol segment composition, 2- decyls-Isosorbide-5-Nitrae butanediol segment and ethylene glycol segment is 4%.
Embodiment 13
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.5 terephthalic acid (TPA) is made into slurry with 2- decyl -1,5 pentanediols 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 -1,5 pentanediol segment forms, and the Mole percent ratio of 2- decyl -1,5 pentanediol 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 -1,5 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 0.28MPa, 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 -1,5 pentanediol segment forms, and the Mole percent ratio of 2- nonyl -1,5 pentanediol 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 -1,5 pentanediols 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 -1,5 pentanediol segment forms, and the Mole percent ratio of 2- octyl -1,5 pentanediol 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 -1,5 pentanediols 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 -1,5 pentanediol segment forms, and the Mole percent ratio of 2- heptyl -1,5 pentanediol 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 -1,5 pentanediols 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 -1,5 pentanediol segment forms, and the Mole percent ratio of 2- hexyl -1,5 pentanediol 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 -1,5 pentanediols 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 -1,5 pentanediol segment forms, and the Mole percent ratio of 2- amyl -1,5 pentanediol 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 -1,5 pentanediol 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- 1,5 pentanediol segment and 2- amyl -1,5 pentanediol segments composition, 2- octyl -1,5 pentanediol 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 -1,5 pentanediol of 2- octyls, -1,4 butanediol of 2- amyls and 2- oneself The mixture of base -1,5 pentanediol is made into slurry and is added in reactor, wherein 2- octyls -1,5 pentanediol, 2- amyls-Isosorbide-5-Nitrae fourth two The molar ratio of -1,5 pentanediol 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 -1,5 pentanediols segment, 2- amyls-Isosorbide-5-Nitrae butanediol chain Section and 2- hexyl -1,5 pentanediol segments composition, the Mole percent ratio of branched glycol segment and ethylene glycol segment are 4.71%.
Embodiment 29
A kind of preparation method of porous soft super fine denier polyester fiber, porous softness super fine denier polyester fiber use porous spray Filament plate is made, and the arrangement mode of spinneret orifice is oval shaped arrangements on spinneret, and oval shaped arrangements refer to the hole centre bit of spinneret orifice In on concentration ellipse, concentration ellipse is that series is oval, and all elliptical long axis are conllinear, and short axle is conllinear.
As shown in Figure 1, elliptical long axis and the ratio of minor axis length are 1.3, the spacing of adjacent spinneret orifice is equal to spinneret orifice Guide hole diameter add 1.5mm, spinneret is round spinneret, diameter and the oval maximum long axial length of series of round spinneret The difference of degree is 11mm, and the spinneret hole count of a diameter of 2.0mm of guide hole of spinneret orifice, spinneret are 374, the spinneret orifice of spinneret Cross-sectional shape be circle.
By modified poly ester made from embodiment 1, Modified polyester chips are obtained through pelletizing；Again through metering, extrusion, cooling, on Oil and high-speed winding, are made porous soft super fine denier polyester fiber, and the temperature of the extrusion of porous softness super fine denier polyester fiber is 295 DEG C, cooling wind-warm syndrome is 25 DEG C, and the speed of high-speed winding is 4500m/min；HT1 is 75 DEG C；HT2 is 125 DEG C.
The filament number of porous soft super fine denier polyester fiber obtained is 0.42dtex, initial modulus 68cN/dtex, is broken Resistance to spalling is 4.7cN/dtex, elongation at break 34.7%；Porous softness super fine denier polyester fiber is fine in the case where temperature is 80 DEG C The spatial joint clearance for tieing up interior molecules interchain increases 15v/v%, and at 289 DEG C, melt viscosity declines 16%；Porous softness super fine denier The line density deviation ratio of polyester fiber is 0.4%, and fracture strength CV values are 3.2%, and extension at break CV values are 6.9%, and item is dry not Even rate CV values are 1.8%.
Embodiment 30
A kind of preparation method of porous soft super fine denier polyester fiber, porous softness super fine denier polyester fiber use porous spray Filament plate is made, and the arrangement mode of spinneret orifice is oval shaped arrangements on spinneret, and oval shaped arrangements refer to the hole centre bit of spinneret orifice In on concentration ellipse, 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, the spinneret orifice of spinneret Cross-sectional shape be circle.
By modified poly ester made from embodiment 1, Modified polyester chips are obtained through pelletizing；Again through metering, extrusion, cooling, on Oil and high-speed winding, are made porous soft super fine denier polyester fiber, and the temperature of the extrusion of porous softness super fine denier polyester fiber is 295 DEG C, cooling wind-warm syndrome is 25 DEG C, and the speed of high-speed winding is 4500m/min；HT1 is 75 DEG C；HT2 is 125 DEG C.
The filament number of porous polyester fiber multihole softness super fine denier polyester fiber obtained is 0.50dtex, initial modulus 70cN/dtex, fracture strength 5.4cN/dtex, elongation at break 35.2%；Porous polyester fiber multihole softness super fine denier For polyester fiber in the case where temperature is 80 DEG C, the spatial joint clearance of fibrous inside molecule interchain increases 15v/v%, and at 289 DEG C, melt is viscous Degree declines 16%；The line density deviation ratio of porous polyester fiber multihole softness super fine denier polyester fiber is 0.2%, fracture strength CV Value is 2.2%, and extension at break CV values are 5.9%, and yarn unevenness CV values are 1.4%.
Comparative example 1
A kind of preparation method of porous soft super fine denier polyester fiber, porous softness super fine denier polyester fiber use porous spray Filament plate is made, and the arrangement mode of spinneret orifice is circular arrangement on spinneret, and circular arrangement refers to that the hole center of spinneret orifice is located at together On heart circle, concentric circles is that series is round.As shown in Fig. 2, the guide hole diameter that the spacing of adjacent spinneret orifice is equal to spinneret orifice adds 1.5mm, spinneret are round spinneret, and the diameter of round spinneret and the difference of the round maximum diameter of series are 11mm, spray The spinneret hole count of a diameter of 2.0mm of guide hole of wire hole, spinneret are 370, and the cross-sectional shape of the spinneret orifice of spinneret is circle Shape.
By modified poly ester made from embodiment 1, Modified polyester chips are obtained through pelletizing；Again through metering, extrusion, cooling, on Oil and high-speed winding, are made porous soft super fine denier polyester fiber, and the temperature of the extrusion of porous softness super fine denier polyester fiber is 295 DEG C, cooling wind-warm syndrome is 25 DEG C, and the speed of high-speed winding is 4500m/min；HT1 is 75 DEG C；HT2 is 125 DEG C.
The filament number of porous polyester fiber multihole softness super fine denier polyester fiber obtained is 0.12dtex, initial modulus 65cN/dtex, fracture strength 3.8cN/dtex, elongation at break 36.0%；Porous polyester fiber multihole softness super fine denier For polyester fiber in the case where temperature is 80 DEG C, the spatial joint clearance of fibrous inside molecule interchain increases 15v/v%, and at 289 DEG C, melt is viscous Degree declines 16%；The line density deviation ratio of porous polyester fiber multihole softness super fine denier polyester fiber is 0.7%, fracture strength CV Value is 5.2%, and extension at break CV values are 9.1%, and yarn unevenness CV values are 2.8%.
With embodiment 29 comparison as can be seen that the effective area of spinneret it is identical when, (circular arrangement when spinneret hole count is close Spinneret hole count is 370, and oval shaped arrangements spinneret hole count is that 374), the spinneret orifice number of plies of oval shaped arrangements is 6, is less than circular arrangement The spinneret orifice number of plies 8, cooling effect is more preferable；It is oval with the comparison of embodiment 30 as can be seen that when the identical effective area of spinneret The spinneret orifice number of plies of shape arrangement is 5, is less than the spinneret orifice number of plies 8 of circular arrangement, cooling effect is more preferable, the spinneret of oval shaped arrangements The hole count 382 in hole is more than the hole count 370 of the spinneret orifice of circular arrangement, cooling efficiency higher.The comparing result of fibre property shows Fiber linear density deviation ratio made from embodiment 29 and embodiment 30, fracture strength CV values, extension at break CV values and evenness fault Rate CV values are less than comparative example 1, under the conditions of illustrating same process, fibroid made from the spinneret using spinneret orifice oval shaped arrangements It can be better than the spinneret using spinneret circular arrangement.
Embodiment 31~33
A kind of preparation method of porous soft super fine denier polyester fiber, porous softness super fine denier polyester fiber use porous spray Filament plate is made, and the arrangement mode of spinneret orifice is oval shaped arrangements on spinneret, and oval shaped arrangements refer to the hole centre bit of spinneret orifice In on concentration ellipse, concentration ellipse is that series is oval, and all elliptical long axis are conllinear, and short axle is conllinear.
Spinneret orifice is arranged as long axial symmetry, and the ratio of elliptical long axis and minor axis length is 1.4, between adjacent spinneret orifice 1.6mm is added away from the guide hole diameter equal to spinneret orifice, spinneret is round spinneret, and the diameter and series of round spinneret are oval The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 192 of spinneret, spinneret The cross-sectional shape of the spinneret orifice of plate is square.
Modified poly ester obtains Modified polyester chips through pelletizing；Again through metering, extrusion, cooling, oil and high-speed winding, system Porous soft super fine denier polyester fiber is obtained, the temperature of the extrusion of porous softness super fine denier polyester fiber is 290 DEG C, cooling wind-warm syndrome It it is 20 DEG C, the speed of high-speed winding is 4000m/min；HT1 is 95 DEG C；HT2 is 130 DEG C.Porous soft super fine denier obtained is poly- Ester fiber the spatial joint clearance Magnification of fibrous inside molecule interchain, melt viscosity rate of descent and fibre at 260 DEG C at 80 DEG C The mechanical performance data of dimension such as following table.
Embodiment 34~36
A kind of preparation method of porous soft super fine denier polyester fiber, porous softness super fine denier polyester fiber use porous spray Filament plate is made, and the arrangement mode of spinneret orifice is oval shaped arrangements on spinneret, and oval shaped arrangements refer to the hole centre bit of spinneret orifice In on concentration ellipse, concentration ellipse is that series is oval, and all elliptical long axis are conllinear, and short axle is conllinear.
Spinneret orifice is arranged as that short axle is symmetrical, and the ratio of elliptical long axis and minor axis length is 1.4, between adjacent spinneret orifice 1.7mm is added away from the guide hole diameter equal to spinneret orifice, spinneret is elliptical spinneret plate, and elliptical spinneret plate is oval most with series The difference of big long axis length is 12mm, and the spinneret hole count of a diameter of 1.8mm of guide hole of spinneret orifice, spinneret are 200, spinneret Spinneret orifice cross-sectional shape be diamond shape.
Modified poly ester obtains Modified polyester chips through pelletizing；Again through metering, extrusion, cooling, oil and high-speed winding, system Porous soft super fine denier polyester fiber is obtained, the temperature of the extrusion of porous softness super fine denier polyester fiber is 295 DEG C, cooling wind-warm syndrome It it is 25 DEG C, the speed of high-speed winding is 5000m/min；HT1 is 75 DEG C；HT2 is 120 DEG C.Porous soft super fine denier obtained is poly- Ester fiber the spatial joint clearance Magnification of fibrous inside molecule interchain, melt viscosity rate of descent and fibre at 289 DEG C at 130 DEG C The mechanical performance data of dimension such as following table.
Embodiment 37~39
A kind of preparation method of porous soft super fine denier polyester fiber, porous softness super fine denier polyester fiber use porous spray Filament plate is made, and the arrangement mode of spinneret orifice is oval shaped arrangements on spinneret, and oval shaped arrangements refer to the hole centre bit of spinneret orifice In on concentration ellipse, concentration ellipse is that series is oval, and all elliptical long axis are conllinear, and short axle is conllinear.
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, adjacent spinneret The guide hole diameter that the spacing in hole is equal to spinneret orifice adds 1.8mm, and spinneret is round spinneret, the diameter of round spinneret be The difference of the oval maximum long axis length of row is 13mm, a diameter of 2.5mm of guide hole of spinneret orifice, and the spinneret hole count of spinneret is 200, the cross-sectional shape of the spinneret orifice of spinneret is "-" type.
Modified poly ester obtains Modified polyester chips through pelletizing；Again through metering, extrusion, cooling, oil and high-speed winding, system Porous soft super fine denier polyester fiber is obtained, the temperature of the extrusion of porous softness super fine denier polyester fiber is 291 DEG C, cooling wind-warm syndrome It it is 21 DEG C, the speed of winding is 4400m/min；HT1 is 75 DEG C；HT2 is 125 DEG C.Porous soft super fine denier polyester obtained is fine Dimension the spatial joint clearance Magnification of fibrous inside molecule interchain, melt viscosity rate of descent and fiber at 290 DEG C at 100 DEG C Mechanical performance data such as following table.
Embodiment 40~42
A kind of preparation method of porous soft super fine denier polyester fiber, porous softness super fine denier polyester fiber use porous spray Filament plate is made, and the arrangement mode of spinneret orifice is oval shaped arrangements on spinneret, and oval shaped arrangements refer to the hole centre bit of spinneret orifice In on concentration ellipse, concentration ellipse is that series is oval, and all elliptical long axis are conllinear, and short axle is conllinear.
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, adjacent spinneret The guide hole diameter that the spacing in hole is equal to spinneret orifice adds 1.9mm, and spinneret is elliptical spinneret plate, elliptical spinneret plate and series The difference of oval maximum long axis length is 14mm, and the spinneret hole count of a diameter of 1.5mm of guide hole of spinneret orifice, spinneret are 210, The cross-sectional shape of the spinneret orifice of spinneret is triangular form.
Modified poly ester obtains Modified polyester chips through pelletizing；Again through metering, extrusion, cooling, oil and high-speed winding, system Porous soft super fine denier polyester fiber is obtained, the temperature of the extrusion of porous softness super fine denier polyester fiber is 291 DEG C, cooling wind-warm syndrome It it is 24 DEG C, the speed of winding is 4340m/min；HT1 is 85 DEG C；HT2 is 122 DEG C.Porous soft super fine denier polyester obtained is fine Dimension the spatial joint clearance Magnification of fibrous inside molecule interchain, melt viscosity rate of descent and fiber at 289 DEG C at 110 DEG C Mechanical performance data such as following table.
Embodiment 43~45
A kind of preparation method of porous soft super fine denier polyester fiber, porous softness super fine denier polyester fiber use porous spray Filament plate is made, and the arrangement mode of spinneret orifice is oval shaped arrangements on spinneret, and oval shaped arrangements refer to the hole centre bit of spinneret orifice In on concentration ellipse, concentration ellipse is that series is oval, and all elliptical long axis are conllinear, and short axle is conllinear.
Spinneret orifice is arranged as that short axle is symmetrical, and the ratio of elliptical long axis and minor axis length is 1.8, between adjacent spinneret orifice 1.5mm is added away from the guide hole diameter equal to spinneret orifice, spinneret is round spinneret, and the diameter and series of round spinneret are oval The difference of maximum long axis length is 15mm, and the spinneret hole count of a diameter of 1.8mm of guide hole of spinneret orifice, spinneret are 240, spinneret The cross-sectional shape of the spinneret orifice of plate is trilobal cross.
Modified poly ester obtains Modified polyester chips through pelletizing；Again through metering, extrusion, cooling, oil and high-speed winding, system Porous soft super fine denier polyester fiber is obtained, the temperature of the extrusion of porous softness super fine denier polyester fiber is 294 DEG C, cooling wind-warm syndrome It it is 23 DEG C, the speed of winding is 4390m/min；HT1 is 78 DEG C；HT2 is 122 DEG C.Porous soft super fine denier polyester obtained is fine Dimension the spatial joint clearance Magnification of fibrous inside molecule interchain, melt viscosity rate of descent and fiber at 270 DEG C at 120 DEG C Mechanical performance data such as following table.
Embodiment 46~49
A kind of preparation method of porous soft super fine denier polyester fiber, porous softness super fine denier polyester fiber use porous spray Filament plate is made, and the arrangement mode of spinneret orifice is oval shaped arrangements on spinneret, and oval shaped arrangements refer to the hole centre bit of spinneret orifice In on concentration ellipse, concentration ellipse is that series is oval, and all elliptical long axis are conllinear, and short axle is conllinear.
Spinneret orifice is arranged as long axial symmetry, and the ratio of elliptical long axis and minor axis length is 1.8, between adjacent spinneret orifice 1.6mm is added away from the guide hole diameter equal to spinneret orifice, spinneret is round spinneret, and the diameter and series of round spinneret are oval The difference of maximum long axis length is 16mm, and the spinneret hole count of a diameter of 2.2mm of guide hole of spinneret orifice, spinneret are 250, spinneret The cross-sectional shape of the spinneret orifice of plate is hollow type.
Modified poly ester obtains Modified polyester chips through pelletizing；Again through metering, extrusion, cooling, oil and high-speed winding, system Porous soft super fine denier polyester fiber is obtained, the temperature of the extrusion of porous softness super fine denier polyester fiber is 291 DEG C, cooling wind-warm syndrome It it is 25 DEG C, the speed of winding is 4600m/min；HT1 is 79 DEG C；HT2 is 129 DEG C.Porous soft super fine denier polyester obtained is fine Dimension the spatial joint clearance Magnification of fibrous inside molecule interchain, melt viscosity rate of descent and fiber at 275 DEG C at 80 DEG C Mechanical performance data such as following table.
Embodiment 50~53
A kind of preparation method of porous soft super fine denier polyester fiber, porous softness super fine denier polyester fiber use porous spray Filament plate is made, and the arrangement mode of spinneret orifice is oval shaped arrangements on spinneret, and oval shaped arrangements refer to the hole centre bit of spinneret orifice In on concentration ellipse, concentration ellipse is that series is oval, and all elliptical long axis are conllinear, and short axle is conllinear.
Spinneret orifice is arranged as that short axle is symmetrical, and the ratio of elliptical long axis and minor axis length is 1.8, between adjacent spinneret orifice 1.8mm is added away from the guide hole diameter equal to spinneret orifice, spinneret is round spinneret, and the diameter and series of round spinneret are oval The difference of maximum long axis length is 15mm, and the spinneret hole count of a diameter of 2.5mm of guide hole of spinneret orifice, spinneret are 260, spinneret The cross-sectional shape of the spinneret orifice of plate is platypelloid type.
Modified poly ester obtains Modified polyester chips through pelletizing；Again through metering, extrusion, cooling, oil and high-speed winding, system Porous soft super fine denier polyester fiber is obtained, the temperature of the extrusion of porous softness super fine denier polyester fiber is 295 DEG C, cooling wind-warm syndrome It it is 23 DEG C, the speed of winding is 4950m/min；HT1 is 75 DEG C；HT2 is 125 DEG C.Porous soft super fine denier polyester obtained is fine Dimension the spatial joint clearance Magnification of fibrous inside molecule interchain, melt viscosity rate of descent and fiber at 289 DEG C at 80 DEG C Mechanical performance data such as following table.
Embodiment 54~57
A kind of preparation method of porous soft super fine denier polyester fiber, porous softness super fine denier polyester fiber use porous spray Filament plate is made, and the arrangement mode of spinneret orifice is oval shaped arrangements on spinneret, and oval shaped arrangements refer to the hole centre bit of spinneret orifice In on concentration ellipse, concentration ellipse is that series is oval, and all elliptical long axis are conllinear, and short axle is conllinear.
Spinneret orifice is arranged as long axial symmetry, and the ratio of elliptical long axis and minor axis length is 1.8, between adjacent spinneret orifice 1.5mm is added away from the guide hole diameter equal to spinneret orifice, spinneret is round spinneret, and the diameter and series of round spinneret are oval The difference of maximum long axis length is 16mm, and the spinneret hole count of a diameter of 1.8mm of guide hole of spinneret orifice, spinneret are 300, spinneret The cross-sectional shape of the spinneret orifice of plate is hollow type.
Modified poly ester obtains Modified polyester chips through pelletizing；Again through metering, extrusion, cooling, oil and high-speed winding, system Porous soft super fine denier polyester fiber is obtained, the temperature of the extrusion of porous softness super fine denier polyester fiber is 290 DEG C, cooling wind-warm syndrome It it is 25 DEG C, the speed of winding is 4600m/min；HT1 is 85 DEG C；HT2 is 127 DEG C.Porous soft super fine denier polyester obtained is fine Dimension the spatial joint clearance Magnification of fibrous inside molecule interchain, melt viscosity rate of descent and fiber at 260 DEG C at 130 DEG C Mechanical performance data such as following table.
Embodiment 58
The dyeing of porous softness super fine denier polyester fiber：
Porous soft super fine denier polyester fiber prepared by embodiment 29 is dyed in high temperature and pressure machine, actual conditions For：Before dyeing, porous softness super fine denier polyester fiber nonionic surfactant is handled 30 minutes at 60 DEG C, and dye is then added In color liquid, the disperse dyes dosage in dyeing liquor is 2.0% (o.w.f)；The concentration 1.2g/L of dispersant NNO, dispersant NNO； 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 Dye 1h.
General fibre is dyed using identical dyeing condition.Porous soft super fine denier polyester fiber after dyed Dye uptake obtain 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, porous softness super fine denier polyester is fine The dye uptake result such as following table of peacekeeping general fibre：
It is compared by the coloring of porous soft super fine denier polyester fiber and general fibre, it can be seen that porous soft super The coloring of microdenier polyester fibers is substantially better than general fibre, also divides greatly from the side illustration modified poly ester of the invention prepared The dihydric alcohol segment containing branch contained in son, makes the increasing degree of free volume be far longer than unbranched polyester macromolecule chain Characteristic, the increase of free volume improves molecule and enters degree inside polyester, and polyester prepared by modified polyester is fine The free volume of dimension is far longer than polyester fiber unbranched at same temperature, increases the diffusion of dyestuff, and it is fine to improve polyester The dyeability of dimension.
Embodiment 59
The dyeing of porous softness super fine denier polyester fiber：
Porous soft super fine denier polyester fiber prepared by embodiment 31 is dyed in high temperature and pressure machine, actual conditions For：Before dyeing, porous softness super fine denier polyester fiber nonionic surfactant is handled 30 minutes at 60 DEG C, and dye is then added In color liquid, the disperse dyes dosage in dyeing liquor is 2.0% (o.w.f)；The concentration 1.2g/L of dispersant NNO, dispersant NNO； 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 Dye 1h.
General fibre is dyed using identical dyeing condition.Porous soft super fine denier polyester fiber after dyed Dye uptake obtain 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, porous softness super fine denier polyester is fine The dye uptake result such as following table of peacekeeping general fibre：
It is compared by the coloring of porous soft super fine denier polyester fiber and general fibre, it can be seen that porous soft super The coloring of microdenier polyester fibers is substantially better than general fibre, also divides greatly from the side illustration modified poly ester of the invention prepared The dihydric alcohol segment containing branch contained in son, makes the increasing degree of free volume be far longer than unbranched polyester macromolecule chain Characteristic, the increase of free volume improves molecule and enters degree inside polyester, and polyester prepared by modified polyester is fine The free volume of dimension is far longer than polyester fiber unbranched at same temperature, increases the diffusion of dyestuff, and it is fine to improve polyester The dyeability of dimension.

Claims (9)

1. a kind of porous soft super fine denier polyester fiber, it is characterized in that：The material of the porous soft super fine denier polyester fiber is Modified poly ester, the modified poly ester are made of terephthalic acid (TPA) segment, ethylene glycol segment and dihydric alcohol segment containing branch；
The filament number of the porous soft super fine denier polyester fiber is 0.20~0.50dtex, initial modulus≤70cN/dtex, Fracture strength >=3.8cN/dtex, elongation at break are 35.0 ± 3.0%；The porous soft super fine denier polyester fiber is in temperature For at 80~130 DEG C, the spatial joint clearance of fibrous inside molecule interchain increases 10~30v/v%, at 260~290 DEG C, melt is viscous Degree declines 10~20%；Line density deviation ratio≤0.5% of the porous soft super fine denier polyester fiber, fracture strength CV values≤ 4.0%, extension at break CV value≤8.0%, yarn unevenness CV value≤2.0%；The spatial joint clearance of the molecule interchain increases Refer to modified poly ester with normal polyester the spatial joint clearance of mutually synthermal molecule interchain comparison；
Dihydric alcohol containing branch is -1,4 butanediol of 2- amyls, -1,4 butanediol of 2- hexyls, -1,4 butanediol of 2- heptyl, 2- pungent - 1,4 butanediol of base, -1,4 butanediol of 2- nonyls, -1,4 butanediol of 2- decyls, -1,5 pentanediol of 2- amyls, 2- hexyls -1,5 penta In glycol, -1,5 pentanediol of 2- heptyl, -1,5 pentanediol of -1,5 pentanediol of 2- octyls, -1,5 pentanediol of 2- nonyls or 2- decyls More than one.
2. a kind of preparation method of porous soft super fine denier polyester fiber as described in claim 1, it is characterized in that：It will be modified poly- Porous soft super fine denier polyester fiber is made using porous spinneret spinning in ester；The arrangement side of spinneret orifice on the porous spinneret Formula is oval shaped arrangements, and the oval shaped arrangements refer to that the hole center of spinneret orifice is located on concentration ellipse, and the concentration ellipse is Serial oval, all elliptical long axis are conllinear, and short axle is conllinear；
The preparation method of the porous soft super fine denier polyester fiber is：Modified poly ester is obtained into Modified polyester chips through pelletizing, Then by Modified polyester chips through metering, extrusion, cooling, oil and high-speed winding, obtain porous soft super fine denier 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 porous soft super fine denier polyester fiber according to claim 2, which is characterized in that described The specific preparation process of 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 porous soft super fine denier polyester fiber is：
The temperature of extrusion：290~295 DEG C；
Cooling wind-warm syndrome：20~25 DEG C；
HT1：75-95℃；
HT2：120-130℃；
High-speed winding speed：4000~5000m/min.
4. a kind of preparation method of porous soft super fine denier polyester fiber according to claim 2, which is characterized in that step (1) in, the molar ratio of terephthalic acid (TPA) and the dihydric alcohol containing branch is 1:1.3-1.5；Concentrated sulfuric acid addition is terephthalic acid (TPA) The 0.3-0.5% of 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 porous soft super fine denier polyester fiber according to claim 2, which is characterized in that described Spinneret orifice be arranged as long axis and/or short axle is symmetrical.
6. a kind of preparation method of porous soft super fine denier polyester fiber according to claim 2, which is characterized in that oval Long axis and minor axis length ratio be 1.3~1.8；The guide hole diameter that the spacing of adjacent spinneret orifice is more than or equal to spinneret orifice adds 1.5mm。
7. a kind of preparation method of porous soft super fine denier polyester fiber according to claim 2, which is characterized in that described Spinneret is round spinneret or elliptical spinneret plate；The diameter of the circle spinneret and the oval maximum long axis length of series Difference be more than 10mm, 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 porous soft super fine denier polyester fiber according to claim 2, which is characterized in that described A diameter of 1.5~the 2.5mm of guide hole of spinneret orifice；The spinneret hole count of the spinneret is more than or equal to 192.
9. a kind of preparation method of porous soft super fine denier polyester fiber according to claim 2, which is characterized in that described The cross-sectional shape of the spinneret orifice of spinneret be circle, square, diamond shape, "-" type, triangular form, trilobal cross, hollow type or Platypelloid type.
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Publication number Priority date Publication date Assignee Title
CN1298460A (en) * 1998-04-23 2001-06-06 纳幕尔杜邦公司 Polyester fiber and methods for making same
CN101063236A (en) * 2007-05-11 2007-10-31 东华大学 Modified copolyester slicer or fabric and method for making same
CN102030893A (en) * 2009-09-29 2011-04-27 东丽纤维研究所（中国）有限公司 Copolyester as well as preparation method and application thereof
CN102535199A (en) * 2010-12-13 2012-07-04 东丽纤维研究所（中国）有限公司 Method for dyeing copolyester-fiber-containing textile
CN102851757A (en) * 2011-06-30 2013-01-02 江苏华亚化纤有限公司 Special-shaped spinneret plate for spinning heavy denier yarns

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US7468335B2 (en) * 2006-03-31 2008-12-23 Imes Robert H High-strength meltblown polyester webs

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1298460A (en) * 1998-04-23 2001-06-06 纳幕尔杜邦公司 Polyester fiber and methods for making same
CN101063236A (en) * 2007-05-11 2007-10-31 东华大学 Modified copolyester slicer or fabric and method for making same
CN102030893A (en) * 2009-09-29 2011-04-27 东丽纤维研究所（中国）有限公司 Copolyester as well as preparation method and application thereof
CN102535199A (en) * 2010-12-13 2012-07-04 东丽纤维研究所（中国）有限公司 Method for dyeing copolyester-fiber-containing textile
CN102851757A (en) * 2011-06-30 2013-01-02 江苏华亚化纤有限公司 Special-shaped spinneret plate for spinning heavy denier yarns

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