CN106350889B - A kind of high-strength middle shrinkage type polyester industrial fiber of high uniformity and preparation method thereof - Google Patents

A kind of high-strength middle shrinkage type polyester industrial fiber of high uniformity and preparation method thereof Download PDF

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CN106350889B
CN106350889B CN201610778339.3A CN201610778339A CN106350889B CN 106350889 B CN106350889 B CN 106350889B CN 201610778339 A CN201610778339 A CN 201610778339A CN 106350889 B CN106350889 B CN 106350889B
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tpa
terephthalic acid
segment
esterification
temperature
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CN106350889A (en
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李文刚
王山水
邓丽娜
杨大矛
王彦芳
赵慧荣
范晓兵
宋光坤
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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
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • 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
    • 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
    • D01D7/00—Collecting the newly-spun products

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

Abstract

The present invention relates to high-strength middle shrinkage type polyester industrial fiber of a kind of high uniformity and preparation method thereof, the raw material of the high-strength middle shrinkage type polyester industrial fiber of high uniformity is the modified poly ester being made of terephthalic acid (TPA) segment, ethylene glycol segment and dihydric alcohol segment containing branch.The preparation method of the high-strength middle shrinkage type polyester industrial fiber of high uniformity is to carry out esterification and obtain phthalic acid binary alcohol esters terephthalic acid (TPA) in the catalysis of the concentrated sulfuric acid with containing the dihydric alcohol of branch；Then phthalic acid and ethylene glycol are made into carry out esterification, obtain ethylene glycol terephthalate；Finally the two is stirred, under the action of catalyst and stabilizer, carry out the polycondensation reaction of low vacuum stage and high vacuum stage of Fig, modified poly ester is made, modified poly ester squeezes out, cools down, oils, stretches through metering, porous spinneret, thermal finalization and winding, the obtained high-strength middle shrinkage type polyester industrial fiber of high uniformity.

Description

A kind of high-strength middle shrinkage type polyester industrial fiber of high uniformity and preparation method thereof
Technical field
The invention belongs to polyester fiber technical field, it is related to a kind of high-strength middle shrinkage type polyester industrial fiber of high uniformity and its system Preparation Method.
Background technique
Polyethylene terephthalate (PET fiber or polyester fiber) fiber since the advent of the world, have breaking 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 have many advantages, such as it is crease-resistant exempt to provide, stiffness is good, is widely used in the fields such as clothes, home textile.
Pet Industrial Fiber is primarily referred to as mostly being applied to industry, national defence, medical treatment, environmental protection and most advanced branches of science each side Face is that have relatively special physicalchemical structure, performance and purposes, or the chemical fibre with specific function, major embodiment Be able to bear strong corrosion, low abrasion, high temperature resistant, radiation hardness, fire-retardant, fire-resistant, high voltage withstanding, high strength and modulus and plurality of medical function Energy.The PVC shelter cloth produced using high-strength low-shrinkage polyester industrial filament yarn as raw material, peel strength with higher and tearing are strong Degree makes shelter cloth be suitable for various uses, flexible body advertising lamp box material, inflatable structure material, fluffy lid architectural fabrics sunshade account Paulin etc..It is that main textile material obtains in terms of the military supplies such as special protective garment, camouflage, covering, knapsack with high-strength low-shrinkage industrial yarn To application.One kind as earth working material has many advantages, such as light, soft, high-strength, wear-resisting, anticorrosive, non-conductive, damping.Make It is used time safe ready, high-efficient, and lifting object will not be damaged.The application field of Pet Industrial Fiber, which is expanded, drives application The whole competitiveness in field is promoted, and no matter in the weight for mitigating composite material, cost is raised in the durability used and reduction maintenance Etc. all various aspects, polyesters high-performance fiber increasingly plays its synthetic competitive advantages.Following many decades, high-performance polyester The development of fiber not only has a considerable progress in quantity, more mentioning in the expansion of application field and industrial chain whole competitiveness It goes up and obtains substantive effect.
It is high-intensitive, middle shrink by be Pet Industrial Fiber development Main way, and influence fiber quality is polyester High molecular collection state structure, the active force being mainly concerned between polyester molecule, the form and structure of crystallization, orientation structure etc., And the form and structure crystallized is emphasis therein.
There are many parameter during melt spinning, these parameters determine the course of fiberizing and spin fiber structure and Performance is exactly the fiber of performance needed for being made by controlling these parameters in production.Experimental branch line all uses side for a long time Blowing is used as the type of cooling, and energy consumption accounts for the significant portion of long filament production cost, as people are to chemical fibre performance and quality It is required that increasingly improving, the exploitation of chemical-fibres filaments new product develops to the fibre in differentiation direction of high added value, it is desirable that higher cold But it dries condition, then proposes circular blow wind apparatus.Circular blow wind apparatus not only has the uniform advantage of every synnema wind-engaging, Er Qieneng Consumption compared to lower, effective solution cross air blasting as blowing area it is big and caused by wind energy lose problem.
During the spinning process, although circular blow wind has apparent advantage, the cooling of porous yarn can not be well solved Uneven problem: since spun silk is after round spinneret extrusion, by ring wind quenching, due to round spinneret circle number compared with It is more, so that circular blow wind hardly enters innermost layer, lead to that the silk of innermost layer may be also uncolled after cooling in outermost silk, To which the problems such as fiber number is irregular, and intensity is irregular occurs in resulting silk, the subsequent further processing to silk is caused difficulty occur.
Summary of the invention
The technical problem to be solved by the present invention is in view of the deficiencies of the prior art, provide a kind of high-strength middle contraction of high uniformity Type polyester industrial fiber and preparation method thereof, the raw material of the high-strength middle shrinkage type polyester industrial fiber of high uniformity of the present invention are modified poly- Ester, the dihydric alcohol segment containing branch is introduced in the strand of modified poly ester, and the modification high uniformity of modified polyester preparation is high-strength Middle shrinkage type polyester industrial fiber, under the conditions of certain temperature, the high-strength middle shrinkage type polyester industrial fiber interior molecules interchain of high uniformity The increasing degree of spatial joint clearance be far longer than the high-strength middle shrinkage type polyester industrial fiber of high uniformity unbranched at same temperature, The melt viscosity of the high-strength middle shrinkage type polyester industrial fiber of high uniformity reduces, and reduces processing temperature, reduces degradation rate, is conducive to Processing.In addition on the porous spinneret of the high-strength middle shrinkage type polyester industrial fiber of high uniformity of the invention spinneret orifice arrangement mode For oval shaped arrangements, oval shaped arrangements refer to that the hole center of spinneret orifice is located on concentration ellipse, and concentration ellipse is that series is oval, institute There is elliptical long axis conllinear, and short axle is conllinear；Higher cooling efficiency and preferable cooling effect can be reached.
A kind of high-strength middle shrinkage type polyester industrial fiber of high uniformity, the high-strength middle shrinkage type polyester industrial fiber of high uniformity By modified poly ester, spinning is obtained after solid-phase tack producing；The material of the high-strength middle shrinkage type polyester industrial fiber of high uniformity 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 one that branch is located in dihydric alcohol segment non-end group carbon and branch be containing 5-10 carbon atom Linear carbon chain dihydric alcohol segment；The high-strength middle shrinkage type polyester industrial fiber of high uniformity is at 260~290 DEG C, melt Viscosity declines 10-20%, in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, dry-hot shrinkage 6.0 ± 0.5%, breaking strength >=8.1cN/dtex of the high-strength middle shrinkage type polyester industrial fiber of high uniformity, line density deviation ratio ≤ 1.0%, breaking strength CV value≤2.0%, extension at break CV value≤5.5%.
A kind of high-strength middle shrinkage type polyester industrial fiber of high uniformity is modified poly ester, is drawn on modified poly ester macromolecular long-chain Enter the dihydric alcohol segment containing branch, and influence of the length and quantity of branch to the crystal property and flow behavior of modified poly ester compared with Greatly, the too short purpose that polyester modification is not achieved of branch lengths, length is too long to cause new entanglement, influence its flow behavior, when When branch is located on a non-end group carbon in dihydric alcohol segment and branch is the linear carbon chain containing 5-10 carbon atom, through changing Property polyester preparation a kind of high-strength middle shrinkage type polyester industrial fiber of high uniformity, under the conditions of certain temperature, industrial yarn inner part The increasing degree of spatial joint clearance between subchain is far longer than industrial yarn unbranched at same temperature, and it is viscous to be conducive to industrial yarn melt Degree reduces, convenient for further processing.
As a preferred technical scheme:
A kind of high-strength middle shrinkage type polyester industrial fiber of high uniformity as described above, the high-strength middle shrinkage type of high uniformity The extension at break of polyester industrial fiber is 13.0 ± 1.5%, network 6 ± 2；The number-average molecular weight of the modified poly ester is 15000- 30000。
A kind of high-strength middle shrinkage type polyester industrial fiber of high uniformity as described above, the dihydric alcohol segment containing branch are - 1,3 propylene glycol segment of 2- amyl, -1,3 propylene glycol segment of 2- hexyl, -1,3 propylene glycol segment of 2- heptyl, 2- octyl -1,3 the third two Alcohol segment, -1,3 propylene glycol segment of 2- nonyl, -1,3 propylene glycol segment of 2- decyl, -1,4 butanediol segment of 2- amyl, 2- hexyl - 1,4 butanediol segments, -1,4 butanediol segment of 2- heptyl, -1,4 butanediol segment of 2- octyl, -1,4 butanediol segment of 2- nonyl, - 1,4 butanediol segment of 2- decyl, -1,5 pentanediol segment of 2- amyl, -1,5 pentanediol segment of 2- hexyl, 2- heptyl -1,5 penta 2 Alcohol segment, -1,5 pentanediol segment of 2- octyl, -1,5 pentanediol segment of 2- nonyl, -1,5 pentanediol segment of 2- decyl, 2- amyl - 1,6 hexylene glycol segments, -1,6 hexylene glycol segment of 2- hexyl, -1,6 hexylene glycol segment of 2- heptyl, -1,6 hexylene glycol segment of 2- octyl, One or more of -1,6 hexylene glycol segment of -1,6 hexylene glycol segment of 2- nonyl or 2- decyl；The dihydric alcohol segment containing branch Mole percent ratio with ethylene glycol segment is 2~5%.
The preparation method of the high-strength middle shrinkage type polyester industrial fiber of a kind of high uniformity of the invention, by modified poly ester through solid phase Condensation viscosity enhancing, metering, porous spinneret squeeze out, cool down, oil, stretching, thermal finalization and winding, and the high-strength middle receipts of high uniformity are made Miniature polyester industrial fiber；
The arrangement mode of spinneret orifice is oval shaped arrangements on the porous spinneret, and the oval shaped arrangements refer to spinneret orifice Hole center be located on concentration ellipse, the concentration ellipse is that series is oval, and all elliptical long axis are conllinear, and short axle is conllinear；
The preparation process of modified poly ester the following steps are included:
(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 Reaction, obtains terephthalic acid (TPA) binary alcohol esters；The dihydric alcohol containing branch is that be located in dihydric alcohol segment one of branch is non- On end group carbon and branch is the dihydric alcohol of the linear carbon chain containing 5-10 carbon atom；
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 dihydric alcohol and terephthaldehyde containing branch The reactivity of acid is less than ethylene glycol, mixes according to same ethylene glycol and reacts with terephthalic acid (TPA), will 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 with terephthalic acid (TPA) under the catalytic action of sulfuric acid, product exists for invention It is added after ethylene glycol and p phthalic acid esterification, ensure that the stability of the dihydric alcohol proportion 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.
A kind of preparation method of the high-strength middle shrinkage type polyester industrial fiber of high uniformity as described above, the modified poly ester system Standby specific steps are as follows:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
Terephthalic acid (TPA) and the dihydric alcohol containing branch are made into slurry to be added in reactor, in the catalytic action of the concentrated sulfuric acid Under, esterification, esterification compressive reaction in nitrogen atmosphere are carried out, moulding pressure is normal pressure~0.3MPa, temperature 180 ~240 DEG C, be esterification terminal when the water quantity of distillate in esterification reaches 90% or more of theoretical value；It obtains to benzene two Formic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
It is added in reactor after terephthalic acid (TPA) and ethylene glycol are made into slurry, carries out esterification, esterification is in nitrogen Atmosphere encloses middle compressive reaction, and moulding pressure is normal pressure~0.3MPa, and temperature is 250~260 DEG C, when the water in esterification distillates Amount is esterification terminal when reaching 90% 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, 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 100Pa, reaction temperature are controlled at 275~280 DEG C, the reaction time 50~90 minutes, and modified poly ester is made；
Modified poly ester is obtained into Modified polyester chips through pelletizing again, acquired polyester slice is viscosified by solid phase polycondensation, made The inherent viscosity of polyester slice is increased to 1.0~1.2dL/g, as high-viscosity slicing；It is squeezed out again through metering, porous spinneret, is cold But, oil, stretch, thermal finalization and winding, the high-strength middle shrinkage type polyester industrial fiber of high uniformity is made；
Spinning main technologic parameters are as follows:
The temperature of the extrusion is 290~320 DEG C；
The wind-warm syndrome of the cooling is 20~30 DEG C；
The stretching, heat setting process:
480~600m/min of GR-1 speed；Temperature is room temperature；
500~1000m/min of GR-2 speed；80~100 DEG C of temperature；
1800~2500m/min of GR-3 speed；100~150 DEG C of temperature；
2800~3500m/min of GR-4 speed；200~250 DEG C of temperature；
2800~3500m/min of GR-5 speed；200~250 DEG C of temperature；
2600~3400m/min of GR-6 speed；150~220 DEG C of temperature；
The speed of the winding is 2600~3400m/min.
A kind of preparation method of the high-strength middle shrinkage type polyester industrial fiber of high uniformity as described above, in the step (1), The molar ratio of terephthalic acid (TPA) and the dihydric alcohol containing branch is 1:1.3-1.5；Concentrated sulfuric acid additional amount is terephthalic acid (TPA) weight 0.3-0.5%；The concentration of the concentrated sulfuric acid is 50-60wt%；In the step (2), mole of terephthalic acid (TPA) and ethylene glycol Than for 1:1.2~2.0；In the step (3), mole of the terephthalic acid (TPA) binary alcohol esters and ethylene glycol terephthalate Percent value is 2~5%；The catalyst is antimony oxide, antimony glycol or antimony acetate, and catalyst charge is to benzene two The 0.01%~0.05% of formic acid total weight；The stabilizer be triphenyl phosphate, trimethyl phosphate or Trimethyl phosphite, surely Determine 0.01%~0.05% that agent additional amount is the terephthalic acid (TPA) total weight.
A kind of preparation method of the high-strength middle shrinkage type polyester industrial fiber of high uniformity as described above, two containing branch First alcohol is -1,3 propylene glycol of 2- amyl, -1,3 propylene glycol of 2- hexyl, -1,3 propylene glycol of 2- heptyl, -1,3 propylene glycol of 2- octyl, 2- - 1,3 propylene glycol of nonyl, -1,3 propylene glycol of 2- decyl, -1,4 butanediol of 2- amyl, -1,4 butanediol of 2- hexyl, 2- heptyl -1,4 Butanediol, -1,4 butanediol of 2- octyl, -1,4 butanediol of 2- nonyl, -1,4 butanediol of 2- decyl, -1,5 pentanediol of 2- amyl, 2- - 1,5 pentanediol of hexyl, -1,5 pentanediol of 2- heptyl, -1,5 pentanediol of 2- octyl, -1,5 pentanediol of 2- nonyl, 2- decyl -1,5 Pentanediol, 2- amyl -1,6 hexylene glycol, 2- hexyl -1,6 hexylene glycol, 2- heptyl -1,6 hexylene glycol, 2- octyl -1,6 hexylene glycol, 2- One or more of -1,6 hexylene glycol of -1,6 hexylene glycol of nonyl or 2- decyl.
A kind of preparation method of the high-strength middle shrinkage type polyester industrial fiber of high uniformity as described above, the porous spinneret For round spinneret or elliptical spinneret plate；The diameter of the circle spinneret and the difference of the oval maximum long axis length of series Greater than 10mm, the difference of the elliptical spinneret plate and the oval maximum long axis length of series is greater than 10mm.
A kind of preparation method of the high-strength middle shrinkage type polyester industrial fiber of high uniformity as described above, the porous spinneret Upper spinneret orifice be arranged as long axis and/or short axle is symmetrical, the guide hole diameter that the spacing of adjacent spinneret orifice is more than or equal to spinneret orifice adds Upper 1.5mm；Elliptical long axis and the ratio of minor axis length are 1.3~1.8.
When the effective area phase of spinneret is simultaneously as the perimeter of ellipse is greater 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 greater than the hole count of circular arrangement, therefore, spray Wire hole oval shaped arrangements are conducive to the cooling of circular blow wind, improve the cooling efficiency of circular blow wind, and the fibre property of preparation is also more excellent It is good.Long axis and the ratio of minor axis length are closer to 1, and ellipse is more similar to justify, and the difference of cooling efficiency and cooling effect is little； When long axis and the ratio of minor axis length are 1.3, cooling effect is significantly improved, and individual pen hole count increase accordingly 16%；Long axis and short axle When the ratio of length is 1.8, cooling effect improves larger, and individual pen hole count increase accordingly 33%, in the case of identical hole count, the present invention Oval shaped arrangements than conventional concentric circle best-fit circle number reduce, be easy to cooling wind and blow through, make the fiber cooling condition of Internal and external cycle More evenly；When long axis and the ratio of minor axis length are greater than 1.8, ellipse is partial to form flat shape, is not easy to punch, while cold But effect 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 cold But efficiency and preferable cooling effect.
A kind of preparation method of the high-strength middle shrinkage type polyester industrial fiber of high uniformity as described above, the spinneret orifice are led Bore dia is 1.5~2.5mm；The spinneret hole count of the spinneret be more than or equal to 192, the spinneret orifice of the spinneret it is transversal Face shape is circle, square, diamond shape, "-" type, triangular form, trilobal cross, hollow type or platypelloid type
The principle of the present invention are as follows:
The raw material of the high-strength middle shrinkage type polyester industrial fiber of high uniformity of the invention is modified poly ester, modified poly ester macromolecular In the dihydric alcohol segment containing branch that contains, when temperature is higher than glass transition temperature, branch makes free volume prior to backbone motion Increasing degree be far longer than the characteristic of unbranched polyester macromolecule chain, the free volume of the industrial yarn of modified polyester preparation It is far longer than industrial yarn unbranched at same temperature, advantageously reduces its melt viscosity.
The arrangement mode of spinneret orifice is oval shaped arrangements on spinneret of the invention, when the effective area of spinneret is identical, The number of plies of spinneret orifice oval shaped arrangements is less than the number of plies of circular arrangement, and circular blow wind is easier to blow through dynamic analysis of spinning, dynamic analysis of spinning Cooling effect is more preferable, and the industrial yarn of preparation is also more excellent.When the effective area of spinneret is identical, spinneret orifice oval shaped arrangements Hole count is greater than the hole count of circular arrangement, and oval shaped arrangements can be realized a greater degree of cooling, significantly improve cooling efficiency.
The utility model has the advantages that
The raw material of the resulting high-strength middle shrinkage type polyester industrial fiber of high uniformity of the present invention is modified poly ester, and modified poly ester is big The dihydric alcohol segment containing branch contained in molecule, when temperature is higher than glass transition temperature, branch makes freedom prior to backbone motion The increasing degree of volume is far longer than the characteristic of unbranched polyester macromolecule chain, and the increase of free volume advantageously reduces melt Viscosity improves its processing performance.
The raw material of the resulting high-strength middle shrinkage type polyester industrial fiber of high uniformity of the present invention is modified poly ester, two containing branch The not big destruction of the structural regularity of the modified poly ester of the introducing pair of first alcohol segment, maintains the excellent performance of polyester fiber.
The arrangement mode of spinneret orifice is ellipse on the high-strength middle shrinkage type polyester industrial fiber spinneret of high uniformity of the invention Shape arrangement, when the effective area of spinneret is identical, the number of plies of spinneret orifice oval shaped arrangements is less than the number of plies of circular arrangement, circular blow wind It is easier to blow through dynamic analysis of spinning, the cooling effect of dynamic analysis of spinning is more preferable, and the fibre property of preparation is also more excellent.
The arrangement mode of spinneret orifice is ellipse on the high-strength middle shrinkage type polyester industrial fiber spinneret of high uniformity of the invention Shape arrangement, when the effective area of spinneret is identical, the hole count of spinneret orifice oval shaped arrangements is greater than the hole count of circular arrangement, ellipse Arrangement can be realized a greater degree of cooling, significantly improve cooling efficiency.
Detailed description of the invention
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 Spending ratio is 1.3；
Fig. 2 is the circular arrangement figure of 370 spinneret orifices, and the aperture of spinneret orifice is 2.0mm；
Fig. 3 is the oval shaped arrangements figure of 382 spinneret orifices, and the aperture of spinneret orifice is 2.0mm, the length of transverse and short axle Spending ratio is 1.6.
Specific embodiment
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 the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
Terephthalic acid (TPA) and 2- amyl -1,3 propylene glycol that molar ratio is 1:1.3 are made into slurry to be added in reactor, Concentration is 50wt%, and additional amount is 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 to be added in reactor after 1:1.2 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, carries 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 It measures 0.01% the catalytic antimony trioxide for being terephthalic acid (TPA) weight and additional amount is the 0.01% of terephthalic acid (TPA) weight Stabilizer triphenyl phosphate under the action of, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure It is 500Pa that absolute pressure is steadily evacuated to by normal pressure, and at 260 DEG C, the reaction time is 30 minutes for temperature control；It then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be down to absolute pressure 100Pa, and reaction temperature is controlled 275 DEG C, the reaction time 50 minutes, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained is 15000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- penta Base -1,3 propylene glycol segment composition, the Mole percent ratio of dihydric alcohol segment and ethylene glycol segment containing branch are 2%.
Embodiment 2
A kind of preparation method of modified poly ester, specifically includes the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
Terephthalic acid (TPA) and 2- hexyl -1,3 propylene glycol that molar ratio is 1:1.38 are made into slurry to be added in reactor, Concentration is 55wt%, and additional amount is to carry out esterification under the catalytic action of 0.32% concentrated sulfuric acid of terephthalic acid (TPA) weight, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.13MPa, temperature is 181 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 91% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
It is to be added in reactor after 1:1.3 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.12MPa, temperature is 251 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 91% 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 2.1%, is stirred 16 minutes, is adding Entering 0.011% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and additional amount is terephthalic acid (TPA) weight Under the action of 0.02% 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 262 DEG C, the reaction time is 31 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 99Pa, and reaction temperature is controlled at 276 DEG C, Reaction time 51 minutes, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained be 16000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- oneself The Mole percent ratio of base -1,3 propylene glycol segment composition, 2- hexyl -1,3 propylene glycol segment and ethylene glycol segment is 2.1%.
Embodiment 3
A kind of preparation method of modified poly ester, specifically includes the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
Terephthalic acid (TPA) and 2- heptyl -1,3 propylene glycol that molar ratio is 1:1.33 are made into slurry to be added in reactor, Concentration is 55wt%, and additional amount is to carry out esterification under the catalytic action of 0.33% concentrated sulfuric acid of terephthalic acid (TPA) weight, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.12MPa, temperature is 183 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 to be added in reactor after 1:1.31 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, be esterified anti- It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.31MPa, temperature is 252 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 2.2%, is stirred 16 minutes, is adding Entering 0.03% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and additional amount is terephthalic acid (TPA) weight Under the action of 0.02% 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 498Pa by normal pressure, and at 263 DEG C, the reaction time is 32 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 80Pa, and reaction temperature is controlled at 277 DEG C, Reaction time 57 minutes, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained is 15900, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- heptan The Mole percent ratio of base -1,3 propylene glycol segment composition, 2- heptyl -1,3 propylene glycol segment and ethylene glycol segment is 2.2%.
Embodiment 4
A kind of preparation method of modified poly ester, specifically includes the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
Terephthalic acid (TPA) and 2- octyl -1,3 propylene glycol that molar ratio is 1:1.34 are made into slurry to be added in reactor, Concentration is 60wt%, and additional amount is to carry out esterification under the catalytic action of 0.34% concentrated sulfuric acid of terephthalic acid (TPA) weight, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.13MPa, temperature is 184 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 93% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
It is to be added in reactor after 1:1.32 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, be esterified anti- It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.33MPa, temperature is 253 DEG C, when in esterification Water quantity of distillate is esterification terminal when reaching the 93% 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 2.3%, is stirred 17 minutes, is adding Entering 0.033% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and additional amount is terephthalic acid (TPA) 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, reaction pressure is made to be down to absolute pressure 80Pa, reaction temperature control exists 278 DEG C, the reaction time 58 minutes, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained is 15800, pungent by terephthalic acid (TPA) segment, ethylene glycol segment and 2- The Mole percent ratio of base -1,3 propylene glycol segment composition, 2- octyl -1,3 propylene glycol segment and ethylene glycol segment is 2.3%.
Embodiment 5
A kind of preparation method of modified poly ester, specifically includes the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
Terephthalic acid (TPA) and 2- nonyl -1,3 propylene glycol that molar ratio is 1:1.35 are made into slurry to be added in reactor, Concentration is 55wt%, and additional amount is to carry out esterification under the catalytic action of 0.36% concentrated sulfuric acid of terephthalic acid (TPA) weight, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.14MPa, temperature is 185 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 93.2% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
It is to be added in reactor after 1:1.33 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, be esterified anti- It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.14MPa, temperature is 254 DEG C, when in esterification Water quantity of distillate is esterification terminal when reaching the 93.2% 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 2.4%, is stirred 17 minutes, is adding Entering 0.034% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and additional amount is terephthalic acid (TPA) 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 reaction pressure is made to be down to absolute pressure 70Pa, and reaction temperature is controlled 277 DEG C, the reaction time 59 minutes, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained is 15900, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- nonyl The Mole percent ratio of base -1,3 propylene glycol segment composition, 2- nonyl -1,3 propylene glycol segment and ethylene glycol segment is 2.4%.
Embodiment 6
A kind of preparation method of modified poly ester, specifically includes the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
Terephthalic acid (TPA) and 2- decyl -1,3 propylene glycol that molar ratio is 1:1.36 are made into slurry to be added in reactor, Concentration is 50wt%, and additional amount is to carry out esterification under the catalytic action of 0.37% concentrated sulfuric acid of terephthalic acid (TPA) weight, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.15MPa, temperature is 186 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 93.3% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
It is to be added in reactor after 1:1.34 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, be esterified anti- It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.15MPa, temperature is 255 DEG C, when in esterification Water quantity of distillate is esterification terminal when reaching the 93.3% 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 2.5%, is stirred 18 minutes, is adding Entering 0.035% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and additional amount is terephthalic acid (TPA) 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 reaction pressure is made to be down to absolute pressure 70Pa, and reaction temperature is controlled 278 DEG C, the reaction time 60 minutes, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained is 16000, by terephthalic acid (TPA) segment, ethylene glycol segment and the 2- last of the ten Heavenly stems The Mole percent ratio of base -1,3 propylene glycol segment composition, 2- decyl -1,3 propylene glycol segment and ethylene glycol segment is 2.5%.
Embodiment 7
A kind of preparation method of modified poly ester, specifically includes the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
Terephthalic acid (TPA) and 2- amyl-Isosorbide-5-Nitrae butanediol that molar ratio is 1:1.37 are made into slurry to be added in reactor, Concentration is 60wt%, and additional amount is to carry out esterification under the catalytic action of 0.38% concentrated sulfuric acid of terephthalic acid (TPA) weight, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.16MPa, temperature is 187 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 93.4% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
It is to be added in reactor after 1:1.36 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, be esterified anti- It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.16MPa, temperature is 256 DEG C, when in esterification Water quantity of distillate is esterification terminal when reaching the 93.4% 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 2.6%, is stirred 19 minutes, is adding Entering 0.036% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and additional amount is terephthalic acid (TPA) 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 reaction pressure is made to be down to absolute pressure 70Pa, and reaction temperature is controlled 278 DEG C, the reaction time 61 minutes, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained is 16000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- penta The Mole percent ratio of base-Isosorbide-5-Nitrae butanediol segment composition, 2- amyl-Isosorbide-5-Nitrae butanediol segment and ethylene glycol segment is 2.6%.
Embodiment 8
A kind of preparation method of modified poly ester, specifically includes the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
Terephthalic acid (TPA) and 2- hexyl-Isosorbide-5-Nitrae butanediol that molar ratio is 1:1.38 are made into slurry to be added in reactor, Concentration is 55wt%, and additional amount is to carry out esterification under the catalytic action of 0.39% concentrated sulfuric acid of terephthalic acid (TPA) weight, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.17MPa, temperature is 188 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 93.5% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
It is to be added in reactor after 1:1.37 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, be esterified anti- It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.17MPa, temperature is 257 DEG C, when in esterification Water quantity of distillate is esterification terminal when reaching the 93.5% 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 2.7%, is stirred 19 minutes, is adding Entering 0.036% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and additional amount is terephthalic acid (TPA) 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 reaction pressure is made to be down to absolute pressure 60Pa, and reaction temperature is controlled 278 DEG C, the reaction time 61 minutes, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained be 17000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- oneself The Mole percent ratio of base-Isosorbide-5-Nitrae butanediol segment composition, 2- hexyl-Isosorbide-5-Nitrae butanediol segment and ethylene glycol segment is 2.7%.
Embodiment 9
A kind of preparation method of modified poly ester, specifically includes the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
Terephthalic acid (TPA) and 2- heptyl-Isosorbide-5-Nitrae butanediol that molar ratio is 1:1.39 are made into slurry to be added in reactor, Concentration is 50wt%, and additional amount is to carry out esterification under the catalytic action of 0.4% concentrated sulfuric acid of terephthalic acid (TPA) weight, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.17MPa, temperature is 188 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 93.5% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
It is to be added in reactor after 1:1.37 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, be esterified anti- It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.17MPa, temperature is 257 DEG C, when in esterification Water quantity of distillate is esterification terminal when reaching the 93.5% 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 2.8%, is stirred 16 minutes, is adding Entering 0.04% catalyst glycol antimony that amount is terephthalic acid (TPA) weight and additional amount is the 0.026% of terephthalic acid (TPA) weight Stabilizer trimethyl phosphate under the action of, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure Absolute pressure 497Pa is steadily evacuated to by normal pressure, at 268 DEG C, the reaction time is 38 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 50Pa, and reaction temperature is controlled at 279 DEG C, instead 62 minutes between seasonable, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained is 18000, 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
A kind of preparation method of modified poly ester, specifically includes the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
Terephthalic acid (TPA) and 2- octyl-Isosorbide-5-Nitrae butanediol that molar ratio is 1:1.4 are made into slurry to be added in reactor, Concentration is 55wt%, and additional amount is to carry out esterification under the catalytic action of 0.4% concentrated sulfuric acid of terephthalic acid (TPA) weight, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.17MPa, temperature is 188 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 93.5% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
It is to be added in reactor after 1:1.38 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, be esterified anti- It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.18MPa, temperature is 257.8 DEG C, when in esterification Water quantity of distillate be esterification terminal when reaching the 93.6% of theoretical value, 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, it is right The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 3%, is stirred 17 minutes, is being added It measures 0.03% catalyst glycol antimony for being terephthalic acid (TPA) weight and additional amount is the 0.027% of terephthalic acid (TPA) 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, makes reaction pressure be down to absolute pressure 50Pa, and reaction temperature controls the reaction at 278 DEG C Time 64 minutes, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained is 19000, pungent by terephthalic acid (TPA) segment, ethylene glycol segment and 2- The Mole percent ratio of base-Isosorbide-5-Nitrae butanediol segment composition, 2- octyl-Isosorbide-5-Nitrae butanediol segment and ethylene glycol segment is 3%.
Embodiment 11
A kind of preparation method of modified poly ester, specifically includes the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
Terephthalic acid (TPA) and 2- nonyl-Isosorbide-5-Nitrae butanediol that molar ratio is 1:1.4 are made into slurry to be added in reactor, Concentration is 55wt%, and additional amount is to carry out esterification under the catalytic action of 0.4% concentrated sulfuric acid of terephthalic acid (TPA) weight, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.18MPa, temperature is 189 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 93.6% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
It is to be added in reactor after 1:1.39 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, be esterified anti- It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.19MPa, temperature is 258.8 DEG C, when in esterification Water quantity of distillate be esterification terminal when reaching the 94% of theoretical value, 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, 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 It measures 0.04% catalyst glycol antimony for being terephthalic acid (TPA) weight and additional amount is the 0.03% of terephthalic acid (TPA) 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, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls the reaction at 277 DEG C Time 63 minutes, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained is 20000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- nonyl The Mole percent ratio of base-Isosorbide-5-Nitrae butanediol segment composition, 2- nonyl-Isosorbide-5-Nitrae butanediol segment and ethylene glycol segment is 4%.
Embodiment 12
A kind of preparation method of modified poly ester, specifically includes the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
Terephthalic acid (TPA) and 2- nonyl-Isosorbide-5-Nitrae butanediol that molar ratio is 1:1.4 are made into slurry to be added in reactor, Concentration is 55wt%, and additional amount is to carry out esterification under the catalytic action of 0.4% concentrated sulfuric acid of terephthalic acid (TPA) weight, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.2MPa, temperature is 200 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 94% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
It is to be added in reactor after 1:1.6 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.2MPa, temperature is 256 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 94% 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 18 minutes, is adding Entering 0.038% catalyst acetic acid antimony that amount is terephthalic acid (TPA) weight and additional amount is the 0.03% of terephthalic acid (TPA) weight Under the action of stabilizer Trimethyl phosphite, start the polycondensation reaction of low vacuum stage, the staged pressure under conditions of negative pressure Absolute pressure 497Pa is steadily evacuated to by normal pressure, at 265 DEG C, the reaction time is 42 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 277 DEG C, instead 70 minutes between seasonable, 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- decyl-Isosorbide-5-Nitrae butanediol segment and ethylene glycol segment is 4%.
Embodiment 13
A kind of preparation method of modified poly ester, specifically includes the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
Terephthalic acid (TPA) and 2- decyl -1,6 hexylene glycol that molar ratio is 1:1.5 are made into slurry to be added in reactor, Concentration is 60wt%, and additional amount is 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 to be added in reactor after 1:2.0 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, carries 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 terephthalic acid (TPA) weight 0.05% catalyst acetic acid antimony and additional amount be 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, makes reaction pressure be down to absolute pressure 30Pa, 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 The Mole percent ratio of base -1,6 hexylene glycol segment composition, 2- decyl -1,6 hexylene glycol segment and ethylene glycol segment is 5%.
Embodiment 14
A kind of preparation method of modified poly ester, specifically includes the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
Terephthalic acid (TPA) and 2- nonyl -1,6 hexylene glycol that molar ratio is 1:1.47 are made into slurry to be added in reactor, Concentration is 60wt%, and additional amount is 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 to be added in reactor after 1:1.8 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, carries 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 It measures 0.04% catalyst glycol antimony for being terephthalic acid (TPA) weight and additional amount is the 0.04% of terephthalic acid (TPA) 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 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- nonyl The Mole percent ratio of base -1,6 hexylene glycol segment composition, 2- nonyl -1,6 hexylene glycol segment and ethylene glycol segment is 4%.
Embodiment 15
A kind of preparation method of modified poly ester, specifically includes the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
Terephthalic acid (TPA) and 2- octyl -1,6 hexylene glycol that molar ratio is 1:1.46 are made into slurry to be added in reactor, Concentration is 60wt%, and additional amount 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 0.28MPa, 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 to be added in reactor after 1:1.8 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, carries 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 Entering 0.044% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and additional amount is terephthalic acid (TPA) weight 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, Reaction time 87 minutes, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained is 29000, pungent by terephthalic acid (TPA) segment, ethylene glycol segment and 2- The Mole percent ratio of base -1,6 hexylene glycol segment composition, 2- octyl -1,6 hexylene glycol segment and ethylene glycol segment is 4.5%.
Embodiment 16
A kind of preparation method of modified poly ester, specifically includes the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
Terephthalic acid (TPA) and 2- heptyl -1,6 hexylene glycol that molar ratio is 1:1.49 are made into slurry to be added in reactor, Concentration is 60wt%, and additional amount is 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 to be added in reactor after 1:1.8 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, carries 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 Entering 0.048% catalyst glycol antimony that amount is terephthalic acid (TPA) weight and additional amount is terephthalic acid (TPA) weight 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, Reaction time 83 minutes, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained is 27000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- heptan The Mole percent ratio of base -1,6 hexylene glycol segment composition, 2- heptyl -1,6 hexylene glycol segment and ethylene glycol segment is 4.7%.
Embodiment 17
A kind of preparation method of modified poly ester, specifically includes the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
Terephthalic acid (TPA) and 2- hexyl -1,6 hexylene glycol that molar ratio is 1:1.467 are made into slurry to be added in reactor, It is 60wt% in concentration, additional amount 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 to be added in reactor after 1:1.89 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, 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 Entering 0.04% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and additional amount 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 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, the reaction time 85 minutes, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained be 29000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- oneself The Mole percent ratio of base -1,6 hexylene glycol segment composition, 2- hexyl -1,6 hexylene glycol segment and ethylene glycol segment is 4.3%.
Embodiment 18
A kind of preparation method of modified poly ester, specifically includes the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
Terephthalic acid (TPA) and 2- amyl -1,6 hexylene glycol that molar ratio is 1:1.48 are made into slurry to be added in reactor, Concentration is 55wt%, and additional amount 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 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 to be added in reactor after 1:1.88 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, 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 Entering 0.047% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and additional amount is terephthalic acid (TPA) weight 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, Reaction time 85 minutes, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained is 28000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- penta The Mole percent ratio of base -1,6 hexylene glycol segment composition, 2- amyl -1,6 hexylene glycol segment and ethylene glycol segment is 4.7%.
Embodiment 19
A kind of preparation method of modified poly ester, specifically includes the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
Terephthalic acid (TPA) and 2- decyl -1,5 pentanediol that molar ratio is 1:1.46 are made into slurry to be added in reactor, Concentration is 55wt%, and additional amount is 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 to be added in reactor after 1:1.9 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, carries 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 Entering 0.046% catalyst acetic acid antimony that amount is terephthalic acid (TPA) weight and additional amount is the 0.048% of terephthalic acid (TPA) weight 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 reaction pressure is made to be down to absolute pressure 40Pa, and reaction temperature is controlled at 278 DEG C, Reaction time 87 minutes, modified poly ester is made.
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 The Mole percent ratio of base -1,5 pentanediol segment composition, 2- decyl -1,5 pentanediol segment and ethylene glycol segment is 4.7%.
Embodiment 20
A kind of preparation method of modified poly ester, specifically includes the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
Terephthalic acid (TPA) and 2- nonyl -1,5 pentanediol that molar ratio is 1:1.46 are made into slurry to be added in reactor, Concentration is 60wt%, and additional amount 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 0.26MPa, 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 to be added in reactor after 1:1.89 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, 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 Entering 0.041% catalyst glycol antimony that amount is terephthalic acid (TPA) weight and additional amount is terephthalic acid (TPA) weight 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, Reaction time 85 minutes, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained is 28000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- nonyl The Mole percent ratio of base -1,5 pentanediol segment composition, 2- nonyl -1,5 pentanediol segment and ethylene glycol segment is 4.1%.
Embodiment 21
A kind of preparation method of modified poly ester, specifically includes the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
Terephthalic acid (TPA) and 2- octyl -1,5 pentanediol that molar ratio is 1:1.43 are made into slurry to be added in reactor, Concentration is 60wt%, and additional amount is 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 to be added in reactor after 1:1.78 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, 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 Entering 0.043% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and additional amount is terephthalic acid (TPA) weight 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, Reaction time 85 minutes, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained is 28000, pungent by terephthalic acid (TPA) segment, ethylene glycol segment and 2- The Mole percent ratio of base -1,5 pentanediol segment composition, 2- octyl -1,5 pentanediol segment and ethylene glycol segment is 4.3%.
Embodiment 22
A kind of preparation method of modified poly ester, specifically includes the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
Terephthalic acid (TPA) and 2- heptyl -1,5 pentanediol that molar ratio is 1:1.43 are made into slurry to be added in reactor, Concentration is 55wt%, and additional amount is 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 to be added in reactor after 1:1.87 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, 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 Entering 0.047% catalyst glycol antimony that amount is terephthalic acid (TPA) weight and additional amount is the 0.04% of terephthalic acid (TPA) weight 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 controls the reaction at 279 DEG C Time 83 minutes, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- heptan The Mole percent ratio of base -1,5 pentanediol segment composition, 2- heptyl -1,5 pentanediol segment and ethylene glycol segment is 4.6%.
Embodiment 23
A kind of preparation method of modified poly ester, specifically includes the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
Terephthalic acid (TPA) and 2- hexyl -1,5 pentanediol that molar ratio is 1:1.457 are made into slurry to be added in reactor, It is 55% in concentration, additional amount 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 to be added in reactor after 1:1.81 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, 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, Additional amount is 0.042% the catalytic antimony trioxide of terephthalic acid (TPA) weight and additional amount 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, the reaction time 85 minutes, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained be 28000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- oneself The Mole percent ratio of base -1,5 pentanediol segment composition, 2- hexyl -1,5 pentanediol segment and ethylene glycol segment is 4.41%.
Embodiment 24
A kind of preparation method of modified poly ester, specifically includes the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
Terephthalic acid (TPA) and 2- amyl -1,5 pentanediol that molar ratio is 1:1.47 are made into slurry to be added in reactor, Concentration is 55wt%, and additional amount is 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 to be added in reactor after 1:1.81 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, 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, Additional amount is 0.041% the catalytic antimony trioxide of terephthalic acid (TPA) weight and additional amount 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, Reaction time 89 minutes, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- penta The Mole percent ratio of base -1,5 pentanediol segment composition, 2- amyl -1,5 pentanediol segment and ethylene glycol segment is 4.67%.
Embodiment 25
A kind of preparation method of modified poly ester, specifically includes the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
It is the terephthalic acid (TPA) of 1:1.45 and mixing for -1,4 butanediol of -1,5 pentanediol of 2- hexyl and 2- amyl by molar ratio Object is closed to be made into slurry addition reactor, wherein 2- hexyl -1,5 pentanediol and 2- amyl-Isosorbide-5-Nitrae butanediol molar ratio are 3:1, It is 55% in concentration, additional amount 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 to be added in reactor after 1:1.8 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, carries 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 Entering 0.042% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and additional amount is terephthalic acid (TPA) weight 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, the reaction time 88 minutes, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment, 2- hexyl- 1,5 pentanediol segment and 2- amyl-Isosorbide-5-Nitrae butanediol segment composition, 2- hexyl -1,5 pentanediol segment and 2- amyl-Isosorbide-5-Nitrae fourth two The summation of alcohol segment and the Mole percent ratio of ethylene glycol segment are 4.4%.
Embodiment 26
A kind of preparation method of modified poly ester, specifically includes the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
By terephthalic acid (TPA) that molar ratio is 1:1.45 and -1,6 hexylene glycol of 2- octyl and 2- amyl -1,5 pentanediol Mixture is made into slurry and is added in reactor, and wherein the molar ratio of 2- octyl -1,6 hexylene glycol and 2- amyl -1,5 pentanediol is 3: 2, it is 60% in concentration, additional amount 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 to be added in reactor after 1:1.84 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, 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 Entering 0.0423% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and additional amount is terephthalic acid (TPA) weight 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, the reaction time 85 minutes, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained is 28000, by terephthalic acid (TPA) segment, ethylene glycol segment, 2- octyl- 1,6 hexylene glycol segment and 2- amyl -1,5 pentanediol segment composition, 2- octyl -1,6 hexylene glycol segment and 2- amyl -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 the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
It is the terephthalic acid (TPA) of 1:1.45 and mixing for -1,4 butanediol of -1,5 pentanediol of 2- hexyl and 2- amyl by molar ratio Object is closed to be made into slurry addition reactor, wherein 2- hexyl -1,5 pentanediol and 2- amyl-Isosorbide-5-Nitrae butanediol molar ratio are 3:1, It is 55% in concentration, additional amount 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 to be added in reactor after 1:1.8 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, carries 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 Entering 0.042% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and additional amount is terephthalic acid (TPA) weight 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, the reaction time 88 minutes, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment, 2- hexyl- 1,5 pentanediol segment and 2- amyl-Isosorbide-5-Nitrae butanediol segment composition, 2- hexyl -1,5 pentanediol segment and 2- amyl-Isosorbide-5-Nitrae fourth two The summation of alcohol segment and the Mole percent ratio of ethylene glycol segment are 4.4%.
Embodiment 28
A kind of preparation method of modified poly ester, specifically includes the following steps:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
By molar ratio be 1:1.45 terephthalic acid (TPA) and -1,3 propylene glycol of 2- octyl, -1,4 butanediol of 2- amyl and 2- oneself The mixture of base -1,6 hexylene glycol is made into slurry and is added in reactor, wherein 2- octyl -1,3 propylene glycol, 2- amyl-Isosorbide-5-Nitrae fourth two The molar ratio of pure and mild 2- hexyl -1,6 hexylene glycol is 3:2:1, is 60% in concentration, additional amount 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, it is esterification terminal when the water quantity of distillate in esterification reaches the 92% of theoretical value that temperature, which is 235 DEG C, Obtain terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
It is to be added in reactor after 1:1.8 terephthalic acid (TPA) and ethylene glycol are made into slurry by molar ratio, carries 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, Additional amount is 0.04% the catalytic antimony trioxide of terephthalic acid (TPA) weight and additional amount 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, the reaction time 84 minutes, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment, band branch Glycol segment composition, wherein branched glycol segment be 2- octyl -1,3 propylene glycol segment, 2- amyl-Isosorbide-5-Nitrae butanediol chain Section and 2- hexyl -1,6 hexylene glycol segment composition, the Mole percent ratio of branched glycol segment and ethylene glycol segment are 4.71%.
Embodiment 29
A kind of preparation method of the high-strength middle miniature polyester industrial fiber of high uniformity, the high-strength middle miniature polyester industrial of high uniformity Silk is made using porous spinneret, and the arrangement mode of spinneret orifice is oval shaped arrangements on spinneret, and oval shaped arrangements refer to spinneret The hole center in hole is located on concentration ellipse, and concentration ellipse is that series is oval, and all elliptical long axis are conllinear, and short axle is conllinear.
As shown in Figure 1, elliptical long axis and the ratio of minor axis length are 1.3, the spacing of adjacent spinneret orifice is equal to spinneret orifice Guide hole diameter add 1.5mm, spinneret is round spinneret, the oval maximum long axial length of diameter and series of round spinneret The difference of degree is 11mm, and the guide hole diameter of spinneret orifice is 2.0mm, and the spinneret hole count of spinneret is 374, the spinneret orifice of spinneret Cross-sectional shape be circle.
Modified poly ester made from embodiment 1 is viscosified through solid phase polycondensation, is measured, porous spinneret squeezes out, is cooled down, is oiled, drawing It stretches, thermal finalization and winding, the obtained high-strength middle miniature polyester industrial fiber of high uniformity cool down wherein the temperature squeezed out is 280 DEG C Wind-warm syndrome is 20 DEG C, GR-1 speed 480m/min；Temperature is room temperature；GR-2 speed 500m/min；80 DEG C of temperature；GR-3 speed 1800m/min；100 DEG C of temperature；GR-4 speed 2800m/min；200 DEG C of temperature；GR-5 speed 2800m/min；200 DEG C of temperature； GR-6 speed 2600m/min；150 DEG C of temperature；The speed of winding is 2600m/min.
The breaking strength of the high-strength middle miniature polyester industrial fiber of high uniformity obtained is 8.4cN/dtex；Line density deviation ratio It is 0.6%, breaking strength CV value is 1.8%, and extension at break CV value is 4.5%, extension at break 12.0, network 5,260 At DEG C, melt viscosity decline 11%, in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, xeothermic contraction Rate is 6%.
Embodiment 30
A kind of preparation method of the high-strength middle miniature polyester industrial fiber of high uniformity, the high-strength middle miniature polyester industrial of high uniformity Silk is made using porous spinneret, and the arrangement mode of spinneret orifice is oval shaped arrangements on spinneret, and oval shaped arrangements refer to spinneret The hole center in hole is located on concentration ellipse, and concentration ellipse is that series is oval, and all elliptical long axis are conllinear, and short axle is conllinear.
As shown in figure 3, elliptical long axis and the ratio of minor axis length are 1.6, the spacing of adjacent spinneret orifice is equal to spinneret orifice Guide hole diameter add 1.5mm, spinneret is round spinneret, the oval maximum long axial length of diameter and series of round spinneret The difference of degree is 11mm, and the guide hole diameter of spinneret orifice is 2.0mm, and the spinneret hole count of spinneret is 382, the spinneret orifice of spinneret Cross-sectional shape be circle.
Modified poly ester made from embodiment 1 is viscosified through solid phase polycondensation, is measured, porous spinneret squeezes out, is cooled down, is oiled, drawing It stretches, thermal finalization and winding, the obtained high-strength middle miniature polyester industrial fiber of high uniformity cool down wherein the temperature squeezed out is 280 DEG C Wind-warm syndrome is 20 DEG C, GR-1 speed 480m/min；Temperature is room temperature；GR-2 speed 500m/min；80 DEG C of temperature；GR-3 speed 1800m/min；100 DEG C of temperature；GR-4 speed 2800m/min；200 DEG C of temperature；GR-5 speed 2800m/min；200 DEG C of temperature； GR-6 speed 2600m/min；150 DEG C of temperature；The speed of winding is 2600m/min.
The breaking strength of the high-strength middle miniature polyester industrial fiber of high uniformity obtained is 8.4cN/dtex；Line density deviation ratio It is 0.7%, breaking strength CV value is 1.7%, and extension at break CV value is 4.8%, extension at break 13.0, network 5,260 At DEG C, melt viscosity decline 11%, in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, xeothermic contraction Rate is 5.9%.
Comparative example 1
A kind of preparation method of the high-strength middle miniature polyester industrial fiber of high uniformity, the high-strength middle miniature polyester industrial of high uniformity Silk is made using porous spinneret, and the arrangement mode of spinneret orifice is circular arrangement on spinneret, and circular arrangement refers to spinneret orifice Hole center is located on concentric circles, and concentric circles is that series is round.As shown in Fig. 2, the spacing of adjacent spinneret orifice is equal to leading for spinneret orifice Bore dia adds 1.5mm, and spinneret is round spinneret, the difference of the round maximum diameter of diameter and series of round spinneret For 11mm, the guide hole diameter of spinneret orifice is 2.0mm, and the spinneret hole count of spinneret is 370, the cross section of the spinneret orifice of spinneret Shape is circle.
Modified poly ester made from embodiment 1 is viscosified through solid phase polycondensation, is measured, porous spinneret squeezes out, is cooled down, is oiled, drawing It stretches, thermal finalization and winding, the obtained high-strength middle miniature polyester industrial fiber of high uniformity cool down wherein the temperature squeezed out is 280 DEG C Wind-warm syndrome is 20 DEG C, GR-1 speed 480m/min；Temperature is room temperature；GR-2 speed 500m/min；80 DEG C of temperature；GR-3 speed 1800m/min；100 DEG C of temperature；GR-4 speed 2800m/min；200 DEG C of temperature；GR-5 speed 2800m/min；200 DEG C of temperature； GR-6 speed 2600m/min；150 DEG C of temperature；The speed of winding is 2600m/min.
The breaking strength of the high-strength middle miniature polyester industrial fiber of high uniformity obtained is 8.6cN/dtex；Line density deviation ratio It is 1%, breaking strength CV value is 1.9%, and extension at break CV value is 5.3%, extension at break 13.1, network 5, at 260 DEG C Under, melt viscosity decline 11%, in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, dry-hot shrinkage It is 6.35%.
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, and less than the spinneret orifice number of plies 8 of circular arrangement, cooling effect is more preferable, the spinneret of oval shaped arrangements The hole count 382 in hole is greater than the hole count 370 of the spinneret orifice of circular arrangement, and cooling efficiency is higher.The comparing result of fibre property shows Fiber linear density deviation ratio made from embodiment 29 and embodiment 30, breaking strength CV value, extension at break CV value are less than comparative example 1, under the conditions of illustrating same process, fibre property made from the spinneret using spinneret orifice oval shaped arrangements is better than using spinneret The spinneret of circular arrangement.
Embodiment 31~33
A kind of preparation method of the high-strength middle miniature polyester industrial fiber of high uniformity is made, spinneret using porous spinneret The arrangement mode of upper spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole center of spinneret orifice is located on concentration ellipse, together Heart 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 for being 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, and the guide hole diameter of spinneret orifice is 1.5mm, the spinneret orifice numerical digit 244 of spinneret, spinneret The cross-sectional shape of the spinneret orifice of plate is square.
The high-strength middle miniature polyester industrial fiber of high uniformity is squeezed out through metering, porous spinneret, is cooled down, oiling, stretching, heat is fixed The high-strength middle miniature polyester industrial fiber of high uniformity is made in type and winding, wherein the temperature squeezed out is 300 DEG C, cooling wind-warm syndrome is 25℃；It stretches, heat setting process parameter are as follows: GR-1 speed 600m/min；Temperature is room temperature；GR-2 speed 1000m/min；Temperature 100℃；GR-3 speed 2500m/min；150 DEG C of temperature；GR-4 speed 3500m/min；250 DEG C of temperature；GR-5 speed 3500m/ min；250 DEG C of temperature；GR-6 speed 3400m/min；220 DEG C of temperature；The speed of winding is 3400m/min.
The high-strength middle miniature polyester industrial fiber of high uniformity obtained is at 280 DEG C, melt viscosity decline percentage, under room temperature The mechanical performance data of industrial yarn, and in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, industrial yarn Dry-hot shrinkage such as following table.
Embodiment 34~36
A kind of preparation method of the high-strength middle miniature polyester industrial fiber of high uniformity is made, spinneret using porous spinneret The arrangement mode of upper spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole center of spinneret orifice is located on concentration ellipse, together Heart 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 for being 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, and the guide hole diameter of spinneret orifice is 1.5mm, the spinneret orifice numerical digit 288 of spinneret, spinneret The cross-sectional shape of the spinneret orifice of plate is square.
The high-strength middle miniature polyester industrial fiber of high uniformity is squeezed out through metering, porous spinneret, is cooled down, oiling, stretching, heat is fixed The high-strength middle miniature polyester industrial fiber of high uniformity is made in type and winding, wherein the temperature squeezed out is 310 DEG C, cooling wind-warm syndrome is 30℃；It stretches, heat setting process parameter are as follows: GR-1 speed 500m/min；Temperature is room temperature；GR-2 speed 600m/min；Temperature 90℃；GR-3 speed 2200m/min；130 DEG C of temperature；GR-4 speed 2900m/min；230 DEG C of temperature；GR-5 speed 3200m/ min；230 DEG C of temperature；GR-6 speed 3000m/min；200 DEG C of temperature；The speed of winding is 2800m/min.
The high-strength middle miniature polyester industrial fiber of high uniformity obtained melt viscosity at 290 DEG C declines percentage, under room temperature The mechanical performance data of industrial yarn, and in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, industrial yarn Dry-hot shrinkage such as following table.
Embodiment 37~39
A kind of preparation method of the high-strength middle miniature polyester industrial fiber of high uniformity is made, spinneret using porous spinneret The arrangement mode of upper spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole center of spinneret orifice is located on concentration ellipse, together Heart 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 for being 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, and the guide hole diameter of spinneret orifice is 1.5mm, the spinneret orifice numerical digit 192 of spinneret, spinneret The cross-sectional shape of the spinneret orifice of plate is square.
The high-strength middle miniature polyester industrial fiber of high uniformity is squeezed out through metering, porous spinneret, is cooled down, oiling, stretching, heat is fixed The high-strength middle miniature polyester industrial fiber of high uniformity is made in type and winding, wherein the temperature squeezed out is 290 DEG C, cooling wind-warm syndrome is 20℃；It stretches, heat setting process parameter are as follows: GR-1 speed 500m/min；Temperature is room temperature；GR-2 speed 800m/min；Temperature 85℃；GR-3 speed 2300m/min；120 DEG C of temperature；GR-4 speed 3200m/min；210 DEG C of temperature；GR-5 speed 3200m/ min；230 DEG C of temperature；GR-6 speed 3200m/min；200 DEG C of temperature；The speed of winding is 3200m/min.
The high-strength middle miniature polyester industrial fiber of high uniformity obtained melt viscosity at 270 DEG C declines percentage, under room temperature The mechanical performance data of industrial yarn, and in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, industrial yarn Dry-hot shrinkage such as following table.
Embodiment 40~42
A kind of preparation method of the high-strength middle miniature polyester industrial fiber of high uniformity is made, spinneret using porous spinneret The arrangement mode of upper spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole center of spinneret orifice is located on concentration ellipse, together Heart 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 for being 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, and the guide hole diameter of spinneret orifice is 1.5mm, the spinneret orifice numerical digit 384 of spinneret, spinneret The cross-sectional shape of the spinneret orifice of plate is square.
The high-strength middle miniature polyester industrial fiber of high uniformity is squeezed out through metering, porous spinneret, is cooled down, oiling, stretching, heat is fixed The high-strength middle miniature polyester industrial fiber of high uniformity is made in type and winding, wherein the temperature squeezed out is 300 DEG C, cooling wind-warm syndrome is 25℃；It stretches, heat setting process parameter are as follows: GR-1 speed 600m/min；Temperature is room temperature；GR-2 speed 900m/min；Temperature 100℃；GR-3 speed 2100m/min；120 DEG C of temperature；GR-4 speed 3200m/min；240 DEG C of temperature；GR-5 speed 3100m/ min；230 DEG C of temperature；GR-6 speed 3200m/min；200 DEG C of temperature；The speed of winding is 3200m/min.
The high-strength middle miniature polyester industrial fiber of high uniformity obtained melt viscosity at 260 DEG C declines percentage, under room temperature The mechanical performance data of industrial yarn, and in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, industrial yarn Dry-hot shrinkage such as following table.
Embodiment 43~45
A kind of preparation method of the high-strength middle miniature polyester industrial fiber of high uniformity is made, spinneret using porous spinneret The arrangement mode of upper spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole center of spinneret orifice is located on concentration ellipse, together Heart 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 for being 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, and the guide hole diameter of spinneret orifice is 1.5mm, the spinneret orifice numerical digit 192 of spinneret, spinneret The cross-sectional shape of the spinneret orifice of plate is square.
The high-strength middle miniature polyester industrial fiber of high uniformity is squeezed out through metering, porous spinneret, is cooled down, oiling, stretching, heat is fixed The high-strength middle miniature polyester industrial fiber of high uniformity is made in type and winding, wherein the temperature squeezed out is 290 DEG C, cooling wind-warm syndrome is 30℃；It stretches, heat setting process parameter are as follows: GR-1 speed 480m/min；Temperature is room temperature；GR-2 speed 500m/min；Temperature 100℃；GR-3 speed 1800m/min；150 DEG C of temperature；GR-4 speed 3100m/min；250 DEG C of temperature；GR-5 speed 3300m/ min；240 DEG C of temperature；GR-6 speed 3200m/min；200 DEG C of temperature；The speed of winding is 3000m/min.
The high-strength middle miniature polyester industrial fiber of high uniformity obtained is at 280 DEG C, melt viscosity, the power of industrial yarn under room temperature Performance data is learned, and in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, the xeothermic contraction of industrial yarn Rate such as following table.
Embodiment 46~48
A kind of preparation method of the high-strength middle miniature polyester industrial fiber of high uniformity is made, spinneret using porous spinneret The arrangement mode of upper spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole center of spinneret orifice is located on concentration ellipse, together Heart 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 for being 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, and the guide hole diameter of spinneret orifice is 1.5mm, the spinneret orifice numerical digit 192 of spinneret, spinneret The cross-sectional shape of the spinneret orifice of plate is square.
The high-strength middle miniature polyester industrial fiber of high uniformity is squeezed out through metering, porous spinneret, is cooled down, oiling, stretching, heat is fixed The high-strength middle miniature polyester industrial fiber of high uniformity is made in type and winding, wherein the temperature squeezed out is 310 DEG C, cooling wind-warm syndrome is 25℃；It stretches, heat setting process parameter are as follows: GR-1 speed 580m/min；Temperature is room temperature；GR-2 speed 800m/min；Temperature 100℃；GR-3 speed 2400m/min；140 DEG C of temperature；GR-4 speed 3300m/min；240 DEG C of temperature；GR-5 speed 3200m/ min；230 DEG C of temperature；GR-6 speed 2900m/min；190 DEG C of temperature；The speed of winding is 3100m/min.
The high-strength middle miniature polyester industrial fiber of high uniformity obtained melt viscosity at 280 DEG C declines percentage, under room temperature The mechanical performance data of industrial yarn, and in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, industrial yarn Dry-hot shrinkage such as following table.
Embodiment 49~51
A kind of preparation method of the high-strength middle miniature polyester industrial fiber of high uniformity is made, spinneret using porous spinneret The arrangement mode of upper spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole center of spinneret orifice is located on concentration ellipse, together Heart 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 for being 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, and the guide hole diameter of spinneret orifice is 1.5mm, the spinneret orifice numerical digit 192 of spinneret, spinneret The cross-sectional shape of the spinneret orifice of plate is square.
The high-strength middle miniature polyester industrial fiber of high uniformity is squeezed out through metering, porous spinneret, is cooled down, oiling, stretching, heat is fixed The high-strength middle miniature polyester industrial fiber of high uniformity is made in type and winding, wherein the temperature squeezed out is 310 DEG C, cooling wind-warm syndrome is 30℃；It stretches, heat setting process parameter are as follows: GR-1 speed 480m/min；Temperature is room temperature；GR-2 speed 700m/min；Temperature 90℃；GR-3 speed 2500m/min；140 DEG C of temperature；GR-4 speed 3200m/min；250 DEG C of temperature；GR-5 speed 2900m/ min；240 DEG C of temperature；GR-6 speed 2900m/min；180 DEG C of temperature；The speed of winding is 2900m/min.
The high-strength middle miniature polyester industrial fiber melt viscosity at 280 DEG C of high uniformity obtained, the power of industrial yarn under room temperature Performance data is learned, and in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, the xeothermic contraction of industrial yarn Rate such as following table.
Embodiment 52~57
A kind of preparation method of the high-strength middle miniature polyester industrial fiber of high uniformity is made, spinneret using porous spinneret The arrangement mode of upper spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole center of spinneret orifice is located on concentration ellipse, together Heart 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 for being 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, and the guide hole diameter of spinneret orifice is 1.5mm, the spinneret orifice numerical digit 192 of spinneret, spinneret The cross-sectional shape of the spinneret orifice of plate is square.
The high-strength middle miniature polyester industrial fiber of high uniformity is squeezed out through metering, porous spinneret, is cooled down, oiling, stretching, heat is fixed The high-strength middle miniature polyester industrial fiber of high uniformity is made in type and winding, wherein the temperature squeezed out is 310 DEG C, cooling wind-warm syndrome is 20℃；It stretches, heat setting process parameter are as follows: GR-1 speed 600m/min；Temperature is room temperature；GR-2 speed 1000m/min；Temperature 80℃；1800~2500m/min of GR-3 speed；100 DEG C of temperature；GR-4 speed 2800m/min；200 DEG C of temperature；GR-5 speed 3500m/min；200 DEG C of temperature；GR-6 speed 3400m/min；220 DEG C of temperature；The speed of winding is 3400m/min.
The high-strength middle miniature polyester industrial fiber of high uniformity obtained melt viscosity at 280 DEG C declines percentage, under room temperature The mechanical performance data of industrial yarn, and in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, industrial yarn Dry-hot shrinkage such as following table.

Claims (8)

1. a kind of high-strength middle shrinkage type polyester industrial fiber of high uniformity, it is characterized in that: the high-strength middle shrinkage type of the high uniformity is poly- By modified poly ester, the spinning after solid-phase tack producing obtains ester industrial yarn；The material of the high-strength middle shrinkage type polyester industrial fiber of high uniformity For modified poly ester, the modified poly ester is made of terephthalic acid (TPA) segment, ethylene glycol segment and dihydric alcohol segment containing branch；Institute The high-strength middle shrinkage type polyester industrial fiber of high uniformity is stated at 260~290 DEG C, melt viscosity declines 10-20%, is in temperature Under the test condition of 177 DEG C × 10min × 0.05cN/dtex, dry-hot shrinkage is 6.0 ± 0.5%, and the high uniformity is high-strength Breaking strength >=8.1cN/dtex of middle shrinkage type polyester industrial fiber, line density deviation ratio≤1.0%, breaking strength CV value≤ 2.0%, extension at break CV value≤5.5%, the melt viscosity decline refers to modified poly ester with normal polyester mutually synthermal The comparison of melt viscosity；
The dihydric alcohol segment containing branch is -1,3 propylene glycol segment of 2- amyl, -1,3 propylene glycol segment of 2- hexyl, 2- heptyl - 1,3 propylene glycol segments, -1,3 propylene glycol segment of 2- octyl, -1,3 propylene glycol segment of 2- nonyl, -1,3 propylene glycol segment of 2- decyl, - 1,4 butanediol segment of 2- amyl, -1,4 butanediol segment of 2- hexyl, -1,4 butanediol segment of 2- heptyl, -1,4 fourth two of 2- octyl Alcohol segment, -1,4 butanediol segment of 2- nonyl, -1,4 butanediol segment of 2- decyl, -1,5 pentanediol segment of 2- amyl, 2- hexyl - 1,5 pentanediol segments, -1,5 pentanediol segment of 2- heptyl, -1,5 pentanediol segment of 2- octyl, -1,5 pentanediol segment of 2- nonyl, - 1,5 pentanediol segment of 2- decyl, -1,6 hexylene glycol segment of 2- amyl, -1,6 hexylene glycol segment of 2- hexyl, 2- heptyl -1,6 oneself two One in alcohol segment, -1,6 hexylene glycol segment of -1,6 hexylene glycol segment of 2- octyl, -1,6 hexylene glycol segment of 2- nonyl or 2- decyl Kind or more；The Mole percent ratio of the dihydric alcohol segment containing branch and ethylene glycol segment is 2~5%.
2. the high-strength middle shrinkage type polyester industrial fiber of a kind of high uniformity according to claim 1, which is characterized in that the height The extension at break of the high-strength middle shrinkage type polyester industrial fiber of uniformity is 13.0 ± 1.5%, network 6 ± 2；The number of the modified poly ester Average molecular weight is 15000-30000.
3. such as a kind of preparation side of the high-strength middle shrinkage type polyester industrial fiber of high uniformity of any of claims 1-2 Method, it is characterized in that: modified poly ester is squeezed out through solid phase polycondensation thickening, metering, porous spinneret, is cooled down, is oiled, is stretched, heat is determined The high-strength middle shrinkage type polyester industrial fiber of high uniformity is made in type and winding；
The arrangement mode of spinneret orifice is oval shaped arrangements on the porous spinneret, and the oval shaped arrangements refer to the hole of spinneret orifice Center is located on concentration ellipse, and the concentration ellipse is that series is oval, and all elliptical long axis are conllinear, and short axle is conllinear；
The preparation process of modified poly ester the following steps are included:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
After terephthalic acid (TPA) and the dihydric alcohol containing branch are made into slurry, under the catalytic action of the concentrated sulfuric acid, esterification is carried out, Obtain terephthalic acid (TPA) binary alcohol esters；The dihydric alcohol containing branch be -1,3 propylene glycol of 2- amyl, -1,3 propylene glycol of 2- hexyl, - 1,3 propylene glycol of 2- heptyl, -1,3 propylene glycol of 2- octyl, -1,3 propylene glycol of 2- nonyl, -1,3 propylene glycol of 2- decyl, amyl -1 2-, 4 butanediols, -1,4 butanediol of 2- hexyl, -1,4 butanediol of 2- heptyl, -1,4 butanediol of 2- octyl, -1,4 butanediol of 2- nonyl, - 1,4 butanediol of 2- decyl, -1,5 pentanediol of 2- amyl, -1,5 pentanediol of 2- hexyl, -1,5 pentanediol of 2- heptyl, octyl -1 2-, 5 pentanediols, 2- nonyl -1,5 pentanediol, 2- decyl -1,5 pentanediol, 2- amyl -1,6 hexylene glycol, 2- hexyl -1,6 hexylene glycol, One of -1,6 hexylene glycol of 2- heptyl, -1,6 hexylene glycol of -1,6 hexylene glycol of 2- octyl, -1,6 hexylene glycol of 2- nonyl or 2- decyl More than；
(2) preparation of ethylene glycol terephthalate:
After terephthalic acid (TPA) and ethylene glycol are made into slurry, esterification is carried out, ethylene glycol terephthalate is obtained；
(3) preparation of modified poly ester:
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, stirring is mixed It closes, under the action of catalyst and stabilizer, under conditions of negative pressure, successively carries out polycondensation reaction and the Gao Zhen of low vacuum stage Modified poly ester is made in the polycondensation reaction in empty stage.
4. the preparation method of the high-strength middle shrinkage type polyester industrial fiber of high uniformity according to claim 3, which is characterized in that The specific steps of the modified poly ester preparation are as follows:
(1) preparation of terephthalic acid (TPA) binary alcohol esters:
Terephthalic acid (TPA) and the dihydric alcohol containing branch are made into slurry to be added in reactor, under the catalytic action of the concentrated sulfuric acid, into Row esterification, esterification compressive reaction in nitrogen atmosphere, moulding pressure are normal pressure~0.3MPa, and temperature is 180~240 DEG C, it is esterification terminal when the water quantity of distillate in esterification reaches 90% or more of theoretical value；Obtain terephthalic acid (TPA) Binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
It is added in reactor after terephthalic acid (TPA) and ethylene glycol are made into slurry, carries out esterification, esterification is in nitrogen atmosphere Middle compressive reaction is enclosed, moulding pressure is normal pressure~0.3MPa, and temperature is 250~260 DEG C, when the water quantity of distillate in esterification reaches To 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, 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 100Pa, reaction temperature are controlled at 275~280 DEG C, the reaction time 50~90 minutes, and modified poly ester is made；
Modified poly ester is obtained into Modified polyester chips through pelletizing again, acquired polyester slice is viscosified by solid phase polycondensation, makes polyester The inherent viscosity of slice is increased to 1.0~1.2dL/g, as high-viscosity slicing；Squeezed out again through metering, porous spinneret, be cooling, on Oil, stretching, thermal finalization and winding, are made the high-strength middle shrinkage type polyester industrial fiber of high uniformity；
Spinning main technologic parameters are as follows:
The temperature of the extrusion is 290~320 DEG C；
The wind-warm syndrome of the cooling is 20~30 DEG C；
The stretching, heat setting process:
480~600m/min of GR-1 speed；Temperature is room temperature；
500~1000m/min of GR-2 speed；80~100 DEG C of temperature；
1800~2500m/min of GR-3 speed；100~150 DEG C of temperature；
2800~3500m/min of GR-4 speed；200~250 DEG C of temperature；
2800~3500m/min of GR-5 speed；200~250 DEG C of temperature；
2600~3400m/min of GR-6 speed；150~220 DEG C of temperature；
The speed of the winding is 2600~3400m/min.
5. a kind of preparation method of the high-strength middle shrinkage type polyester industrial fiber of high uniformity according to claim 4, feature It is, in the step (1), the molar ratio of terephthalic acid (TPA) and the dihydric alcohol containing branch is 1:1.3-1.5；Concentrated sulfuric acid additional amount For the 0.3-0.5% of terephthalic acid (TPA) weight；The concentration of the concentrated sulfuric acid is 50-60wt%；In the step (2), to benzene two The molar ratio of formic acid and ethylene glycol is 1:1.2~2.0；In the step (3), the terephthalic acid (TPA) binary alcohol esters with to benzene two The Mole percent ratio of formic acid glycol ester is 2~5%；The catalyst is antimony oxide, antimony glycol or antimony acetate, is urged Agent additional amount is the 0.01%~0.05% of terephthalic acid (TPA) total weight；The stabilizer is triphenyl phosphate, tripotassium phosphate Ester or Trimethyl phosphite, stabilizer additional amount are the 0.01%~0.05% of the terephthalic acid (TPA) total weight.
6. a kind of preparation method of the high-strength middle shrinkage type polyester industrial fiber of high uniformity according to claim 3, feature It is, the porous spinneret is round spinneret or elliptical spinneret plate；The diameter and series of the circle spinneret are oval The difference of maximum long axis length is greater than 10mm, and the elliptical spinneret plate and the difference of serial oval maximum long axis length are big In 10mm.
7. a kind of preparation method of the high-strength middle shrinkage type polyester industrial fiber of high uniformity according to claim 3, feature Be, on the porous spinneret spinneret orifice be arranged as long axis and/or short axle is symmetrical, the spacing of adjacent spinneret orifice is more than or equal to The guide hole diameter of spinneret orifice adds 1.5mm；Elliptical long axis and the ratio of minor axis length are 1.3~1.8.
8. a kind of preparation method of the high-strength middle shrinkage type polyester industrial fiber of high uniformity according to claim 3, feature It is, the guide hole diameter of the spinneret orifice is 1.5~2.5mm；The spinneret hole count of the spinneret is more than or equal to 192, the spray The cross-sectional shape of the spinneret orifice of filament plate is circle, square, diamond shape, "-" type, triangular form, trilobal cross, hollow type or flat Flat pattern.
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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
CN102797054A (en) * 2012-09-03 2012-11-28 江苏恒力化纤股份有限公司 Manufacturing method of high-strength, high-modulus and low-shrinkage polyester industrial yarn
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