CN106400162B - A kind of high uniformity high intensity low shrinkage type polyester industrial fiber and preparation method thereof - Google Patents

A kind of high uniformity high intensity low shrinkage type polyester industrial fiber and preparation method thereof Download PDF

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Publication number
CN106400162B
CN106400162B CN201610776461.7A CN201610776461A CN106400162B CN 106400162 B CN106400162 B CN 106400162B CN 201610776461 A CN201610776461 A CN 201610776461A CN 106400162 B CN106400162 B CN 106400162B
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tpa
segment
terephthalic acid
spinneret
temperature
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CN106400162A (en
Inventor
范红卫
王丽丽
范晓兵
张元华
杨大矛
赵慧荣
宋光坤
刘千涵
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D4/00—Spinnerette packs; Cleaning thereof
    • D01D4/02—Spinnerettes
    • D01D4/025—Melt-blowing or solution-blowing dies
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor

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

Abstract

The present invention relates to a kind of high uniformity high intensity low shrinkage type polyester industrial fiber and preparation method thereof, the raw material of polyester fiber 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 polyester fiber is to carry out esterification and obtain terephthalic acid (TPA) binary alcohol esters terephthalic acid (TPA) in the catalysis of the concentrated sulfuric acid with containing the dihydric alcohol of branch；Then terephthalic acid (TPA) 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, obtained high uniformity high intensity low shrinkage type polyester industrial fiber.

Description

A kind of high uniformity high intensity low shrinkage type polyester industrial fiber and preparation method thereof
Technical field
The invention belongs to polyester fiber technical field, it is related to a kind of high uniformity high intensity low shrinkage type polyester industrial fiber and its preparation Method.
Background technology
Polyethylene terephthalate (PET fiber or polyester fiber) fiber since the advent of the world, have fracture strength and Elasticity modulus is high, and resilience is moderate, and thermal finalization is excellent, and heat-resisting light resistance is good and acid-fast alkali-proof corrosion resistance etc. is a series of excellent Performance, and fabric 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 work( Energy.The PVC shelter cloths produced using high-strength low-shrinkage polyester industrial filament yarn as raw material have higher peel strength and tearing 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 having many advantages, such as light, soft, high-strength, wear-resisting, anticorrosive, non-conductive, damping.Make It is used time safe ready, 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 repair 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 carrying in the expansion of application field and industrial chain whole competitiveness It goes up and obtains substantive effect.
The Main way that high intensity, lower shrinkage, dimensional stability develop Pet Industrial Fiber, and influence fiber quality Be polyester macromolecule collection state structure, the active force being mainly concerned between polyester molecule, form and structure, the alignment state of crystallization Structure etc., and the form and structure that crystallize are emphasis therein.Low-shrinkage high-strength PET industrial yarn is the major class in polyester, Due to its intensity height, percent thermal shrinkage is low, and impact resistance is excellent, and fabric or manufactured rubber product have good size steady Qualitative and heat-resistant stability can absorb impact load, and have the characteristics that polyamide fibre softness, therefore the neck that is widely used Domain.Low-shrinkage high-strength PET industrial yarn is mainly used for coated fabric (lamp house cloth, tent, shelter cloth, billboard, puggaree, waterproof Cloth, Puffer-type swimming pool, roof drape, for building, agriculture use, aircushion vehicle, pneumatic boat etc.), canvas, soft water pipe, fire-fighting Rotary hose, pitch tube, sewing thread, Industry thread, geotextile, filter cloth etc..
There are many parameter during melt spinning, these parameters determine the course of fiberizing and spin fiber structure and Performance, be exactly in production be made by controlling these parameters needed for performance fiber.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 ring blowing device.Ring blowing device not only has the uniform advantage of every synnema wind-engaging, Er Qieneng Consumption compared to relatively low, effective solution cross air blasting due to blowing area is big and caused by wind energy lose problem.
In spinning process, although ring blowing has apparent advantage, the cooling of porous yarn can not be well solved Uneven problem：Since spun silk is after round spinneret extrusion, by ring wind quenching, due to the round spinneret number of turns compared with It is more so that ring blowing hardly enters innermost layer, leads to that the silk of innermost layer may be also uncolled after cooling in outermost silk, There is the problems such as fiber number is irregular, and intensity is irregular to the silk of gained, the further processing subsequently to silk is caused difficulty occur.
Invention content
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 uniformity high intensity low shrinkage type The raw material of polyester industrial fiber and preparation method thereof, high uniformity high intensity low shrinkage type polyester industrial fiber of the present invention is modified poly ester, is changed Property polyester strand in introduce the dihydric alcohol segment containing branch, modification high uniformity high intensity low shrinkage type prepared by modified polyester Polyester industrial fiber, under the conditions of certain temperature, the spatial joint clearance of high uniformity high intensity low shrinkage type polyester industrial fiber interior molecules interchain Increasing degree be far longer than high uniformity high intensity low shrinkage type polyester industrial fiber unbranched at same temperature, high uniformity is high-strength The melt viscosity of low-shrinkage type polyester industrial fiber reduces, and reduces processing temperature, reduces degradation rate, is conducive to process.In addition this hair The arrangement mode of spinneret orifice is oval shaped arrangements on the porous spinneret of bright high uniformity high intensity low shrinkage type polyester industrial fiber, ellipse Circular arrangement refers to that the hole center of spinneret orifice is located on concentration ellipse, and concentration ellipse is that series is oval, and all elliptical long axis are total Line, and short axle is conllinear；Higher cooling efficiency and preferable cooling effect can be reached.
A kind of high uniformity high intensity low shrinkage type polyester industrial fiber, the high uniformity high intensity low shrinkage type polyester industrial fiber is by changing Property polyester spinning after solid-phase tack producing obtains；The material of the high uniformity high intensity low shrinkage type polyester industrial fiber is modified poly ester, institute Modified poly ester is stated to be made of terephthalic acid (TPA) segment, ethylene glycol segment and dihydric alcohol segment containing branch, it is described containing branch two First alcohol segment refers on a non-end group carbon that branch is located in dihydric alcohol segment and branch is straight containing 5-10 carbon atom The dihydric alcohol segment of chain carbochain；Fracture strength >=7.5cN/dtex of the high uniformity high intensity low shrinkage type polyester industrial fiber breaks Resistance to spalling >=7.5cN/dtex, line density deviation ratio≤1.0%, fracture strength CV value≤2.0%, extension at break CV values≤ 5.5%；The high uniformity high intensity low shrinkage type polyester industrial fiber is at 260~290 DEG C, and melt viscosity declines 10-20%, in temperature Degree is under the test condition of 177 DEG C × 10min × 0.05cN/dtex, and dry-hot shrinkage is 8.5 ± 1.5%；
The melt viscosity declines refer to modified poly ester with normal polyester mutually synthermal melt viscosity comparison.
A kind of high uniformity high intensity low shrinkage type polyester industrial fiber is modified poly ester, is introduced on modified poly ester macromolecular long-chain Dihydric alcohol segment containing branch, and the influence of the length of branch and quantity 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 prepare a kind of high uniformity high intensity low shrinkage type polyester industrial fiber, under the conditions of certain temperature, industrial yarn interior molecules The increasing degree of the spatial joint clearance of interchain is far longer than industrial yarn unbranched at same temperature, is conducive to industrial yarn melt viscosity It reduces, convenient for further processing.
As preferred technical solution：
A kind of high uniformity high intensity low shrinkage type polyester industrial fiber as described above, the high uniformity high intensity low shrinkage type polyester The extension at break of industrial yarn is 12.0 ± 1.5%, and the number-average molecular weight of the modified poly ester is 15000-30000.
A kind of high uniformity high intensity low shrinkage type polyester industrial fiber as described above, the dihydric alcohol segment containing branch are 2- - 1,3 propylene glycol segment of amyl, -1,3 propylene glycol segment of 2- hexyls, -1,3 propylene glycol segment of 2- heptyl, -1,3 propylene glycol of 2- octyls Segment, -1,3 propylene glycol segment of 2- nonyls, -1,3 propylene glycol segment of 2- decyls, -1,4 butanediol segment of 2- amyls, hexyl -1 2-, 4 butanediol segments, -1,4 butanediol segment of 2- heptyl, -1,4 butanediol segment of 2- octyls, -1,4 butanediol segment of 2- nonyls, 2- - 1,4 butanediol segment of decyl, -1,5 pentanediol segment of 2- amyls, -1,5 pentanediol segment of 2- hexyls, -1,5 pentanediol of 2- heptyl Segment, -1,5 pentanediol segment of 2- octyls, -1,5 pentanediol segment of 2- nonyls, -1,5 pentanediol segment of 2- decyls, amyl -1 2-, 6 hexylene glycol segments, -1,6 hexylene glycol segment of 2- hexyls, -1,6 hexylene glycol segment of 2- heptyl, -1,6 hexylene glycol segment of 2- octyls, 2- One or more of -1,6 hexylene glycol segment of -1,6 hexylene glycol segment of nonyl or 2- decyls；The dihydric alcohol segment containing branch with The Mole percent ratio of ethylene glycol segment is 2~5%.
A kind of preparation method of high uniformity high intensity low shrinkage type polyester industrial fiber of the present invention, modified poly ester is contracted through solid phase Poly- thickening, metering, porous spinneret squeeze out, cool down, oil, stretching, thermal finalization and winding, obtained high uniformity high intensity low shrinkage type 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 includes the following steps：
(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 be the linear carbon chain containing 5-10 carbon atom dihydric alcohol；
For the dihydric alcohol containing branch, branch is alkyl, is electron-withdrawing group, in the presence of branch, makes strand Spatial volume increases, and solvation becomes smaller, and proton is not easy to dissociate in dihydric alcohol so that the dihydric alcohol containing branch and terephthaldehyde The reactivity of acid is less than ethylene glycol, mixes according to same ethylene glycol and is reacted with terephthalic acid (TPA), can cause the binary containing branch Alcohol reaction is imperfect, to influence ratio of the dihydric alcohol containing branch in polyester macromolecule, and then influences the performance of polyester.This Using the dihydric alcohol containing branch is first carried out esterification under the catalytic action of sulfuric acid with terephthalic acid (TPA), product exists for invention It is added after ethylene glycol and p phthalic acid esterification, ensure that the stability of the dihydric alcohol proportioning containing branch.
(2) preparation of ethylene glycol terephthalate：
After terephthalic acid (TPA) and ethylene glycol are made into slurry, esterification is carried out, ethylene glycol terephthalate is obtained；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, stir Mix mixing, under the action of catalyst and stabilizer, under conditions of negative pressure, successively carry out low vacuum stage polycondensation reaction and Modified poly ester is made in the polycondensation reaction of high vacuum stage of Fig.
It is prepared by a kind of preparation method of high uniformity high intensity low shrinkage type polyester industrial fiber as described above, the modified poly ester The specific steps are：
(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 Modified poly ester is made in 275~280 DEG C, 50~90 minutes reaction time in 100Pa, reaction temperature control；
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 viscous slice；It is squeezed out again through metering, porous spinneret, is cold But it, oils, stretch, thermal finalization and winding, high uniformity high intensity low shrinkage type polyester industrial fiber is made；
Spinning main technologic parameters are：
The temperature of the extrusion is 290~310 DEG C；
The wind-warm syndrome of the cooling is 20~30 DEG C；
The stretching, heat setting process parameter are：
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 high uniformity high intensity low shrinkage type polyester industrial fiber as described above is right in the step (1) The molar ratio of phthalic acid and the dihydric alcohol containing branch is 1:1.3-1.5；Concentrated sulfuric acid addition is terephthalic acid (TPA) weight 0.3-0.5%；A concentration of 50-60wt% of the concentrated sulfuric acid；In the step (2), mole of terephthalic acid (TPA) and ethylene glycol Than being 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 addition is the terephthalic acid (TPA) total weight.
A kind of preparation method of high uniformity high intensity low shrinkage type polyester industrial fiber as described above, the binary containing branch Alcohol is -1,3 propylene glycol of 2- amyls, -1,3 propylene glycol of 2- hexyls, -1,3 propylene glycol of 2- heptyl, -1,3 propylene glycol of 2- octyls, 2- nonyls - 1,3 propylene glycol of base, -1,3 propylene glycol of 2- decyls, -1,4 butanediol of 2- amyls, -1,4 butanediol of 2- hexyls, -1,4 fourth of 2- heptyl Glycol, -1,4 butanediol of 2- octyls, -1,4 butanediol of 2- nonyls, -1,4 butanediol of 2- decyls, -1,5 pentanediol of 2- amyls, 2- oneself - 1,5 pentanediol of base, -1,5 pentanediol of 2- heptyl, -1,5 pentanediol of 2- octyls, -1,5 pentanediol of 2- nonyls, 2- decyls -1,5 penta Glycol, 2- amyls -1,6 hexylene glycol, 2- hexyl -1,6 hexylene glycols, 2- heptyl -1,6 hexylene glycol, 2- octyls -1,6 hexylene glycol, 2- nonyls One or more of -1,6 hexylene glycol of -1,6 hexylene glycol of base or 2- decyls.
A kind of preparation method of high uniformity high intensity low shrinkage type polyester industrial fiber as described above, the porous spinneret are Round spinneret or elliptical spinneret plate；The diameter of the circle spinneret and the difference of serial oval maximum long axis length are big In 10mm, the elliptical spinneret plate and the difference of the oval maximum long axis length of series are more than 10mm.
A kind of preparation method of high uniformity high intensity low shrinkage type polyester industrial fiber as described above, on the porous spinneret 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 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 more than circular perimeter, spinneret orifice ellipse The number of plies of arrangement is less than the number of plies of circular arrangement, and the hole count of spinneret orifice oval shaped arrangements is more than the hole count of circular arrangement, therefore, spray Wire hole oval shaped arrangements are conducive to the cooling of ring blowing, improve the cooling efficiency of ring blowing, 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 significantly improves, and individual pen hole count accordingly increases by 16%；Long axis and short axle When the ratio of length is 1.8, cooling effect raising is larger, the accordingly increase by 33% of individual pen hole count, in the case of identical hole count, the present invention Oval shaped arrangements than conventional concentric circle best-fit the number of turns reduce, be easy to cooling wind and blow through, make the fiber cooling condition of Internal and external cycle Evenly；When long axis and the ratio of minor axis length are more 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 high uniformity high intensity low shrinkage type polyester industrial fiber as described above, the guide hole of the spinneret orifice A diameter of 1.5~2.5mm；The spinneret hole count of the spinneret is more than or equal to 192, the cross section of the spinneret orifice of the spinneret Shape is circle, square, diamond shape, "-" type, triangular form, trilobal cross, hollow type or platypelloid type
The principle of the present invention is：
The raw material of the high uniformity high intensity low shrinkage type polyester industrial fiber of the present invention is modified poly ester, in modified poly ester macromolecular The dihydric alcohol segment containing branch contained, when temperature is higher than glass transition temperature, branch is prior to backbone motion, modified polyester system The free volume of standby industrial yarn 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 the spinneret of the present 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 ring blowing 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 more than the hole count of circular arrangement, and oval shaped arrangements can realize a greater degree of cooling, significantly improve cooling efficiency.
Advantageous effect：
The raw material of the high uniformity high intensity low shrinkage type polyester industrial fiber of gained of the invention is modified poly ester, and modified poly ester divides greatly The dihydric alcohol segment containing branch contained in son, when temperature is higher than glass transition temperature, branch makes free body prior to backbone motion Long-pending increasing degree is far longer than the characteristic of unbranched polyester macromolecule chain, and the increase of free volume advantageously reduces melt and glues Degree, improves its processing performance.
The raw material of the high uniformity high intensity low shrinkage type polyester industrial fiber of gained of the invention is modified poly ester, the binary containing branch The not big destruction of structural regularity for the modified poly ester of alcohol segment introduced pair, maintains the excellent performance of polyester fiber.
The arrangement mode of spinneret orifice is ellipse on the high uniformity high intensity low shrinkage type polyester industrial fiber spinneret of the present invention 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, and ring is dried more It is easy 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 uniformity high intensity low shrinkage type polyester industrial fiber spinneret of the present invention Arrangement, when the effective area of spinneret is identical, the hole count of spinneret orifice oval shaped arrangements is more than the hole count of circular arrangement, ellipse row Row can realize a greater degree of cooling, significantly improve cooling efficiency.
Description of the drawings
Fig. 1 is the oval shaped arrangements figure of 374 spinneret orifices, and the aperture of spinneret orifice is 2.0mm, the length of transverse and short axle It is 1.3 to spend ratio；
Fig. 2 is the circular arrangement figure of 370 spinneret orifices, and the aperture of spinneret orifice is 2.0mm；
Fig. 3 is the oval shaped arrangements figure of 382 spinneret orifices, and the aperture of spinneret orifice is 2.0mm, the length of transverse and short axle It is 1.6 to spend ratio.
Specific implementation mode
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Fixed range.
Embodiment 1
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.3 terephthalic acid (TPA) is made into slurry with 2- amyl -1,3 propylene glycol and is added in reactor, A concentration of 50wt%, addition are to carry out esterification under the catalytic action of 0.3% concentrated sulfuric acid of terephthalic acid (TPA) weight, Esterification compressive reaction in nitrogen atmosphere, moulding pressure are normal pressure, and temperature is 180 DEG C, when the water in esterification distillates Amount is esterification terminal when reaching the 90% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.2 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure are normal pressure, and temperature is 250 DEG C, when the water in esterification distillates Amount is esterification terminal when reaching the 90% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 2%, is stirred 15 minutes, is being added Amount is 0.01% the catalytic antimony trioxide of terephthalic acid (TPA) total weight and addition is terephthalic acid (TPA) total weight Under the action of 0.01% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure It is 500Pa that section pressure, which is steadily evacuated to absolute pressure by normal pressure, and at 260 DEG C, the reaction time is 30 minutes for temperature control；It then proceedes to It vacuumizes, carries out the polycondensation reaction of high vacuum stage of Fig, it is 100Pa so that reaction pressure is down to absolute pressure, and reaction temperature control exists 275 DEG C, modified poly ester was made in 50 minutes reaction time.
The number-average molecular weight of modified poly ester is 15000, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- penta Base -1,3 propylene glycol segment forms, and the Mole percent ratio of the dihydric alcohol segment containing branch and ethylene glycol segment is 2%.
Table 1：Embodiment 2-12 important technological parameters
Embodiment 2
The preparation method of the modified poly ester of embodiment 2, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 16 minutes, is in addition 0.011% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are the 0.02% of terephthalic acid (TPA) total weight Stabilizer triphenyl phosphate under the action of, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure Absolute pressure 490Pa is steadily evacuated to by normal pressure, at 262 DEG C, the reaction time is 31 minutes for temperature control；It then proceedes to vacuumize, The polycondensation reaction for carrying out high vacuum stage of Fig makes reaction pressure be down to absolute pressure 90Pa, and reaction temperature is controlled at 276 DEG C, reaction Modified poly ester was made in 51 minutes time.
The number-average molecular weight of modified poly ester be 16000, modified poly ester by terephthalic acid (TPA) segment, ethylene glycol segment and 2- oneself Base -1,3 propylene glycol segment forms, and the Mole percent ratio of 2- hexyl -1,3 propylene glycol segments and ethylene glycol segment is 2.1%.
Embodiment 3
The preparation method of the modified poly ester of embodiment 3, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 16 minutes, is in addition 0.03% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are the 0.02% of terephthalic acid (TPA) total weight Stabilizer triphenyl phosphate under the action of, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure Absolute pressure 498Pa is steadily evacuated to by normal pressure, at 263 DEG C, the reaction time is 32 minutes for temperature control；It then proceedes to vacuumize, The polycondensation reaction for carrying out high vacuum stage of Fig makes reaction pressure be down to absolute pressure 90Pa, and reaction temperature is controlled at 277 DEG C, reaction Modified poly ester was made in 57 minutes time.
The number-average molecular weight of modified poly ester is 15900, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- heptan Base -1,3 propylene glycol segment forms, and the Mole percent ratio of 2- heptyl -1,3 propylene glycol segments and ethylene glycol segment is 2.2%.
Embodiment 4
The preparation method of the modified poly ester of embodiment 4, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 17 minutes, is in addition 0.033% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are terephthalic acid (TPA) total weight Under the action of 0.023% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure It is 497Pa that section pressure, which is steadily evacuated to absolute pressure by normal pressure, and at 264 DEG C, the reaction time is 33 minutes for temperature control；It then proceedes to It vacuumizes, carries out the polycondensation reaction of high vacuum stage of Fig, it is 80Pa so that reaction pressure is down to absolute pressure, and reaction temperature control exists 278 DEG C, modified poly ester was made in 58 minutes reaction time.
The number-average molecular weight of modified poly ester is 15800, and modified poly ester is pungent by terephthalic acid (TPA) segment, ethylene glycol segment and 2- Base -1,3 propylene glycol segment forms, and the Mole percent ratio of 2- octyl -1,3 propylene glycol segments and ethylene glycol segment is 2.3%.
Embodiment 5
The preparation method of the modified poly ester of embodiment 5, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 17 minutes, is in addition 0.034% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are terephthalic acid (TPA) total weight Under the action of 0.024% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and at 265 DEG C, the reaction time is 34 minutes for temperature control；It then proceedes to take out Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and it is 80Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled 277 DEG C, modified poly ester was made in 59 minutes reaction time.
The number-average molecular weight of modified poly ester is 15900, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- nonyls Base -1,3 propylene glycol segment forms, and the Mole percent ratio of 2- nonyl -1,3 propylene glycol segments and ethylene glycol segment is 2.4%.
Embodiment 6
The preparation method of the modified poly ester of embodiment 6, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 18 minutes, is in addition 0.035% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are terephthalic acid (TPA) total weight Under the action of 0.025% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure Section pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 266 DEG C, the reaction time is 35 minutes for temperature control；It then proceedes to take out Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and it is 70Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled 278 DEG C, modified poly ester was made in 60 minutes reaction time.
The number-average molecular weight of modified poly ester is 16000, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and the 2- last of the ten Heavenly stems Base -1,3 propylene glycol segment forms, and the Mole percent ratio of 2- decyl -1,3 propylene glycol segments and ethylene glycol segment is 2.5%.
Embodiment 7
The preparation method of the modified poly ester of embodiment 7, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 19 minutes, is in addition 0.036% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are terephthalic acid (TPA) total weight Under the action of 0.025% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and at 267 DEG C, the reaction time is 36 minutes for temperature control；It then proceedes to take out Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and it is 70Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled 278 DEG C, modified poly ester was made in 61 minutes reaction time.
The number-average molecular weight of modified poly ester is 16000, and the number-average molecular weight of modified poly ester is 16000, and modified poly ester is by right Phthalic acid segment, ethylene glycol segment and 2- amyls-Isosorbide-5-Nitrae butanediol segment composition, 2- amyls-Isosorbide-5-Nitrae butanediol segment and second two The Mole percent ratio of alcohol segment is 2.6%.
Embodiment 8
The preparation method of the modified poly ester of embodiment 8, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 19 minutes, is in addition 0.036% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are terephthalic acid (TPA) total weight Under the action of 0.025% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and at 267 DEG C, the reaction time is 36 minutes for temperature control；It then proceedes to take out Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and it is 70Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled 278 DEG C, modified poly ester was made in 61 minutes reaction time.
The number-average molecular weight of modified poly ester be 17000, modified poly ester by terephthalic acid (TPA) segment, ethylene glycol segment and 2- oneself The Mole percent ratio of base-Isosorbide-5-Nitrae butanediol segment composition, 2- hexyls-Isosorbide-5-Nitrae butanediol segment and ethylene glycol segment is 2.7%.
Embodiment 9
The preparation method of the modified poly ester of embodiment 9, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 16 minutes, is in addition 0.04% catalyst glycol antimony and addition of terephthalic acid (TPA) total weight are the 0.026% of terephthalic acid (TPA) total weight Under the action of stabilizer trimethyl phosphate, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure by Normal pressure is steadily evacuated to absolute pressure 497Pa, and at 268 DEG C, the reaction time is 38 minutes for temperature control；It then proceedes to vacuumize, into The polycondensation reaction of row high vacuum stage of Fig, it is 60Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled at 279 DEG C, reaction Modified poly ester was made in 62 minutes time.
The number-average molecular weight of modified poly ester is 17000, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- heptan The Mole percent ratio of base-Isosorbide-5-Nitrae butanediol segment composition, 2- heptyl-Isosorbide-5-Nitrae butanediol segment and ethylene glycol segment is 2.8%.
Embodiment 10
The preparation method of the modified poly ester of embodiment 10, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 17 minutes, is in addition 0.03% catalyst glycol antimony and addition of terephthalic acid (TPA) total weight are the 0.027% of terephthalic acid (TPA) total weight Under the action of stabilizer trimethyl phosphate, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure by Normal pressure is steadily evacuated to absolute pressure 498Pa, and at 269 DEG C, the reaction time is 39 minutes for temperature control；It then proceedes to vacuumize, into The polycondensation reaction of row high vacuum stage of Fig, it is 60Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled at 278 DEG C, reaction Modified poly ester was made in 64 minutes time.
The number-average molecular weight of modified poly ester is 17000, and modified poly ester is pungent by terephthalic acid (TPA) segment, ethylene glycol segment and 2- The Mole percent ratio of base-Isosorbide-5-Nitrae butanediol segment composition, 2- octyls-Isosorbide-5-Nitrae butanediol segment and ethylene glycol segment is 3%.
Embodiment 11
The preparation method of the modified poly ester of embodiment 11, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 18 minutes, is in addition 0.04% catalyst glycol antimony and addition of terephthalic acid (TPA) total weight are the 0.03% of terephthalic acid (TPA) total weight Under the action of stabilizer trimethyl phosphate, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure by Normal pressure is steadily evacuated to absolute pressure 497Pa, and at 260 DEG C, the reaction time is 40 minutes for temperature control；It then proceedes to vacuumize, into The polycondensation reaction of row high vacuum stage of Fig, it is 60Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled at 277 DEG C, reaction Modified poly ester was made in 63 minutes time.
The number-average molecular weight of modified poly ester is 18000, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- nonyls The Mole percent ratio of base-Isosorbide-5-Nitrae butanediol segment composition, 2- nonyls-Isosorbide-5-Nitrae butanediol segment and ethylene glycol segment is 4%.
Embodiment 12
The preparation method of the modified poly ester of embodiment 12, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 18 minutes, is in addition The catalyst acetic acid antimony and addition of the 0.038% of terephthalic acid (TPA) weight are 0.03% stabilizer of terephthalic acid (TPA) weight Under the action of Trimethyl phosphite, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, the staged pressure is by normal pressure Steady to be evacuated to absolute pressure 497Pa, at 265 DEG C, the reaction time is 42 minutes for temperature control；It then proceedes to vacuumize, carry out high The polycondensation reaction of vacuum stages, it is 40Pa so that reaction pressure is down to absolute pressure, and reaction temperature control is at 277 DEG C, the reaction time 70 minutes, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained is 26000, by terephthalic acid (TPA) segment, ethylene glycol segment and the 2- last of the ten Heavenly stems The Mole percent ratio of base-Isosorbide-5-Nitrae butanediol segment composition, 2- decyls-Isosorbide-5-Nitrae butanediol segment and ethylene glycol segment is 4%.
Embodiment 13
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.5 terephthalic acid (TPA) is made into slurry with 2- decyl -1,6 hexylene glycols and is added in reactor, A concentration of 60wt%, addition are to carry out esterification under the catalytic action of 0.5% concentrated sulfuric acid of terephthalic acid (TPA) weight, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.3MPa, temperature is 240 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:2.0 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.3MPa, temperature is 260 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 5%, is stirred 20 minutes, is being added Amount be 0.05% catalyst acetic acid antimony of terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight 0.05% it is steady Under the action of determining agent Trimethyl phosphite, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure by It is 450Pa that normal pressure, which is steadily evacuated to absolute pressure, and at 270 DEG C, the reaction time is 50 minutes for temperature control；It then proceedes to vacuumize, The polycondensation reaction for carrying out high vacuum stage of Fig, it is 30Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled at 280 DEG C, instead 90 minutes between seasonable, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained is 30000, by terephthalic acid (TPA) segment, ethylene glycol segment and the 2- last of the ten Heavenly stems Base -1,6 hexylene glycol segment forms, and the Mole percent ratio of 2- decyl -1,6 hexylene glycol segments and ethylene glycol segment is 5%.
Embodiment 14
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.47 terephthalic acid (TPA) is made into slurry with 2- nonyl -1,6 hexylene glycols and is added in reactor, A concentration of 60wt%, addition are to carry out esterification under the catalytic action of 0.47% concentrated sulfuric acid of terephthalic acid (TPA) weight, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 220 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.8 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.27MPa, temperature is 258 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4%, is stirred 18 minutes, is being added Amount is 0.04% catalyst glycol antimony of terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight 0.04% Under the action of stabilizer trimethyl phosphate, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure by Normal pressure is steadily evacuated to absolute pressure 460Pa, and at 263 DEG C, the reaction time is 47 minutes for temperature control；It then proceedes to vacuumize, into The polycondensation reaction of row high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature is controlled at 278 DEG C, reaction Between 85 minutes, be made modified poly ester.
The number-average molecular weight of modified poly ester obtained is 28000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- nonyls Base -1,6 hexylene glycol segment forms, and the Mole percent ratio of 2- nonyl -1,6 hexylene glycol segments and ethylene glycol segment is 4%.
Embodiment 15
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.46 terephthalic acid (TPA) is made into slurry with 2- octyl -1,6 hexylene glycols and is added in reactor, A concentration of 60wt%, addition are to carry out esterification under the catalytic action of 0.49% concentrated sulfuric acid of terephthalic acid (TPA) weight, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 233 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.8 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 259 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.5%, is stirred 19 minutes, is adding It is terephthalic acid (TPA) weight to enter 0.044% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition Under the action of 0.046% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure Section pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 269 DEG C, the reaction time is 48 minutes for temperature control；It then proceedes to take out Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be down to absolute pressure 40Pa, and reaction temperature is controlled at 279 DEG C, Modified poly ester was made in 87 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 29000, pungent by terephthalic acid (TPA) segment, ethylene glycol segment and 2- Base -1,6 hexylene glycol segment forms, and the Mole percent ratio of 2- octyl -1,6 hexylene glycol segments and ethylene glycol segment is 4.5%.
Embodiment 16
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.49 terephthalic acid (TPA) is made into slurry with 2- heptyl -1,6 hexylene glycols and is added in reactor, A concentration of 60wt%, addition are to carry out esterification under the catalytic action of 0.48% concentrated sulfuric acid of terephthalic acid (TPA) weight, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 230 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.8 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 258 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.7%, is stirred 19 minutes, is adding It is terephthalic acid (TPA) weight to enter 0.048% catalyst glycol antimony that amount is terephthalic acid (TPA) weight and addition Under the action of 0.047% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure Section pressure is steadily evacuated to absolute pressure 460Pa by normal pressure, and at 267 DEG C, the reaction time is 48 minutes for temperature control；It then proceedes to take out Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be down to absolute pressure 40Pa, and reaction temperature is controlled at 279 DEG C, Modified poly ester was made in 83 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 27000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- heptan Base -1,6 hexylene glycol segment forms, and the Mole percent ratio of 2- heptyl -1,6 hexylene glycol segments and ethylene glycol segment is 4.7%.
Embodiment 17
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.467 terephthalic acid (TPA) is made into slurry with 2- hexyl -1,6 hexylene glycols and is added in reactor, In a concentration of 60wt%, addition is be esterified anti-under the catalytic action of 0.47% concentrated sulfuric acid of terephthalic acid (TPA) weight It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.27MPa, temperature is 236 DEG C, when in esterification Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.89 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, be esterified anti- It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 258 DEG C, when in esterification Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.3%, is stirred 18 minutes, is adding It is terephthalic acid (TPA) weight to enter 0.04% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition Under the action of 0.041% stabilizer Trimethyl phosphite, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, it should Staged pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 268 DEG C, the reaction time is 48 minutes for temperature control；It then proceedes to It vacuumizes, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be down to absolute pressure 40Pa, reaction temperature is controlled 278 DEG C, modified poly ester was made in 85 minutes reaction time.
The number-average molecular weight of modified poly ester obtained be 29000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- oneself Base -1,6 hexylene glycol segment forms, and the Mole percent ratio of 2- hexyl -1,6 hexylene glycol segments and ethylene glycol segment is 4.3%.
Embodiment 18
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.48 terephthalic acid (TPA) is made into slurry with 2- amyl -1,6 hexylene glycols and is added in reactor, A concentration of 55wt%, addition are to carry out esterification under the catalytic action of 0.46% concentrated sulfuric acid of terephthalic acid (TPA) weight, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 230 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.88 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, be esterified anti- It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 256 DEG C, when in esterification Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.7%, is stirred 18 minutes, is adding It is terephthalic acid (TPA) weight to enter 0.047% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition Under the action of 0.047% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure Section pressure is steadily evacuated to absolute pressure 480Pa by normal pressure, and at 265 DEG C, the reaction time is 47 minutes for temperature control；It then proceedes to take out Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be down to absolute pressure 40Pa, and reaction temperature is controlled at 279 DEG C, Modified poly ester was made in 85 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 28000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- penta Base -1,6 hexylene glycol segment forms, and the Mole percent ratio of 2- amyl -1,6 hexylene glycol segments and ethylene glycol segment is 4.7%.
Embodiment 19
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.46 terephthalic acid (TPA) is made into slurry with 2- decyl -1,5 pentanediols and is added in reactor, A concentration of 55wt%, addition are to carry out esterification under the catalytic action of 0.47% concentrated sulfuric acid of terephthalic acid (TPA) weight, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 238 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.9 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 259 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching 92% of theoretical value or more, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.7%, is stirred 19 minutes, is adding Enter the 0.046% catalyst acetic acid antimony that amount is terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight 0.048% Stabilizer Trimethyl phosphite under the action of, under conditions of negative pressure start low vacuum stage polycondensation reaction, the stage pressure It is 446Pa that power, which is steadily evacuated to absolute pressure by normal pressure, and at 267 DEG C, the reaction time is 49 minutes for temperature control；It then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and it is 40Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled at 278 DEG C, Modified poly ester was made in 87 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment and the 2- last of the ten Heavenly stems Base -1,5 pentanediol segment forms, and the Mole percent ratio of 2- decyl -1,5 pentanediol segments and ethylene glycol segment is 4.7%.
Embodiment 20
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.46 terephthalic acid (TPA) is made into slurry with 2- nonyl -1,5 pentanediols and is added in reactor, A concentration of 60wt%, addition are to carry out esterification under the catalytic action of 0.46% concentrated sulfuric acid of terephthalic acid (TPA) weight, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.26MPa, temperature is 221 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.89 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, be esterified anti- It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.25MPa, temperature is 259 DEG C, when in esterification Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.1%, is stirred 18 minutes, is adding It is terephthalic acid (TPA) weight to enter 0.041% catalyst glycol antimony that amount is terephthalic acid (TPA) weight and addition Under the action of 0.042% stabilizer trimethyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure Section pressure is steadily evacuated to absolute pressure 460Pa by normal pressure, and at 265 DEG C, the reaction time is 47 minutes for temperature control；It then proceedes to take out Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be down to absolute pressure 40Pa, and reaction temperature is controlled at 278 DEG C, Modified poly ester was made in 85 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 28000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- nonyls Base -1,5 pentanediol segment forms, and the Mole percent ratio of 2- nonyl -1,5 pentanediol segments and ethylene glycol segment is 4.1%.
Embodiment 21
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.43 terephthalic acid (TPA) is made into slurry with 2- octyl -1,5 pentanediols and is added in reactor, A concentration of 60wt%, addition are to carry out esterification under the catalytic action of 0.47% concentrated sulfuric acid of terephthalic acid (TPA) weight, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.27MPa, temperature is 235 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.78 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, be esterified anti- It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.26MPa, temperature is 255 DEG C, when in esterification Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.3%, is stirred 17 minutes, is adding It is terephthalic acid (TPA) weight to enter 0.043% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition Under the action of 0.049% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure Section pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 268 DEG C, the reaction time is 46 minutes for temperature control；It then proceedes to take out Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be down to absolute pressure 40Pa, and reaction temperature is controlled at 275 DEG C, Modified poly ester was made in 85 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 28000, pungent by terephthalic acid (TPA) segment, ethylene glycol segment and 2- Base -1,5 pentanediol segment forms, and the Mole percent ratio of 2- octyl -1,5 pentanediol segments and ethylene glycol segment is 4.3%.
Embodiment 22
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.43 terephthalic acid (TPA) is made into slurry with 2- heptyl -1,5 pentanediols and is added in reactor, A concentration of 55wt%, addition are to carry out esterification under the catalytic action of 0.45% concentrated sulfuric acid of terephthalic acid (TPA) weight, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.29MPa, temperature is 235 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.87 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, be esterified anti- It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.27MPa, temperature is 255 DEG C, when in esterification Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.6%, is stirred 18 minutes, is adding Enter 0.047% catalyst glycol antimony that amount is terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight 0.04% Stabilizer triphenyl phosphate under the action of, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure Absolute pressure 470Pa is steadily evacuated to by normal pressure, at 268 DEG C, the reaction time is 45 minutes for temperature control；It then proceedes to vacuumize, The polycondensation reaction for carrying out high vacuum stage of Fig makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature is controlled at 279 DEG C, reaction Modified poly ester was made in 83 minutes time.
The number-average molecular weight of modified poly ester obtained is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- heptan Base -1,5 pentanediol segment forms, and the Mole percent ratio of 2- heptyl -1,5 pentanediol segments and ethylene glycol segment is 4.6%.
Embodiment 23
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.457 terephthalic acid (TPA) is made into slurry with 2- hexyl -1,5 pentanediols and is added in reactor, A concentration of 55%, addition is to carry out esterification under the catalytic action of 0.46% concentrated sulfuric acid of terephthalic acid (TPA) weight, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 239 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.81 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, be esterified anti- It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.27MPa, temperature is 255 DEG C, when in esterification Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.41%, is stirred 19 minutes, Addition is 0.042% the catalytic antimony trioxide of terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight Under the action of 0.048% stabilizer Trimethyl phosphite, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, it should Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the reaction time is 45 minutes for temperature control；It then proceedes to It vacuumizes, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be down to absolute pressure 50Pa, reaction temperature is controlled 275 DEG C, modified poly ester was made in 85 minutes reaction time.
The number-average molecular weight of modified poly ester obtained be 28000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- oneself Base -1,5 pentanediol segment forms, and the Mole percent ratio of 2- hexyl -1,5 pentanediol segments and ethylene glycol segment is 4.41%.
Embodiment 24
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.47 terephthalic acid (TPA) is made into slurry with 2- amyl -1,5 pentanediols and is added in reactor, A concentration of 55wt%, addition are to carry out esterification under the catalytic action of 0.48% concentrated sulfuric acid of terephthalic acid (TPA) weight, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.27MPa, temperature is 245 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.81 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, be esterified anti- It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.27MPa, temperature is 259 DEG C, when in esterification Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.67%, is stirred 19 minutes, Addition is 0.041% the catalytic antimony trioxide of terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight Under the action of 0.042% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure Section pressure is steadily evacuated to absolute pressure 485Pa by normal pressure, and at 268 DEG C, the reaction time is 46 minutes for temperature control；It then proceedes to take out Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be down to absolute pressure 50Pa, and reaction temperature is controlled at 275 DEG C, Modified poly ester was made in 89 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- penta Base -1,5 pentanediol segment forms, and the Mole percent ratio of 2- amyl -1,5 pentanediol segments and ethylene glycol segment is 4.67%.
Embodiment 25
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.45 terephthalic acid (TPA) is mixed with -1,4 butanediol of -1,5 pentanediol of 2- hexyls and 2- amyls It closes object to be made into slurry addition reactor, wherein the molar ratio of 2- hexyls -1,5 pentanediol and 2- amyls-Isosorbide-5-Nitrae butanediol is 3:1, A concentration of 55%, addition is to carry out esterification under the catalytic action of 0.49% concentrated sulfuric acid of terephthalic acid (TPA) weight, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.26MPa, temperature is 236 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.8 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 258 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.4%, is stirred 18 minutes, is adding It is terephthalic acid (TPA) weight to enter 0.042% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition Under the action of 0.047% stabilizer Trimethyl phosphite, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, it should Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the reaction time is 49 minutes for temperature control；It then proceedes to It vacuumizes, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be down to absolute pressure 50Pa, reaction temperature is controlled 278 DEG C, modified poly ester was made in 88 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment, 2- hexyls- 1,5 pentanediol segment and 2- amyls-Isosorbide-5-Nitrae butanediol segment composition, 2- hexyl -1,5 pentanediol segments and 2- amyls-Isosorbide-5-Nitrae fourth two The summation of alcohol segment is 4.4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 26
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.45 terephthalic acid (TPA) and -1,6 hexylene glycol of 2- octyls and -1,5 pentanediol of 2- amyls Mixture is made into slurry and is added in reactor, and the molar ratio of wherein 2- octyls -1,6 hexylene glycol and 2- amyl -1,5 pentanediols is 3: 2, a concentration of 60%, addition is be esterified anti-under the catalytic action of 0.45% concentrated sulfuric acid of terephthalic acid (TPA) weight It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 239 DEG C, when in esterification Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.84 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, be esterified anti- It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.29MPa, temperature is 255 DEG C, when in esterification Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.6%, is stirred 18 minutes, is adding It is terephthalic acid (TPA) weight to enter 0.0423% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition Under the action of 0.045% stabilizer Trimethyl phosphite, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, it should Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the reaction time is 45 minutes for temperature control；It then proceedes to It vacuumizes, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be down to absolute pressure 50Pa, reaction temperature is controlled 278 DEG C, modified poly ester was made in 85 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 28000, by terephthalic acid (TPA) segment, ethylene glycol segment, 2- octyls- 1,6 hexylene glycol segment and 2- amyl -1,5 pentanediol segments composition, 2- octyl -1,6 hexylene glycol segments and 2- amyls -1,5 penta 2 The Mole percent ratio of alcohol segment and ethylene glycol segment is 4.6%.
Embodiment 27
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.45 terephthalic acid (TPA) is mixed with -1,4 butanediol of -1,5 pentanediol of 2- hexyls and 2- amyls It closes object to be made into slurry addition reactor, wherein the molar ratio of 2- hexyls -1,5 pentanediol and 2- amyls-Isosorbide-5-Nitrae butanediol is 3:1, A concentration of 55%, addition is to carry out esterification under the catalytic action of 0.49% concentrated sulfuric acid of terephthalic acid (TPA) weight, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.26MPa, temperature is 236 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 96% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.8 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 258 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.4%, is stirred 18 minutes, is adding It is terephthalic acid (TPA) weight to enter 0.042% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition Under the action of 0.047% stabilizer Trimethyl phosphite, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, it should Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the reaction time is 49 minutes for temperature control；It then proceedes to It vacuumizes, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be down to absolute pressure 50Pa, reaction temperature is controlled 278 DEG C, modified poly ester was made in 88 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment, 2- hexyls- 1,5 pentanediol segment and 2- amyls-Isosorbide-5-Nitrae butanediol segment composition, 2- hexyl -1,5 pentanediol segments and 2- amyls-Isosorbide-5-Nitrae fourth two The summation of alcohol segment is 4.4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 28
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.45 terephthalic acid (TPA) and -1,3 propylene glycol of 2- octyls, -1,4 butanediol of 2- amyls and 2- oneself The mixture of base -1,6 hexylene glycol is made into slurry and is added in reactor, wherein 2- octyls -1,3 propylene glycol, 2- amyls-Isosorbide-5-Nitrae fourth two The molar ratio of -1,6 hexylene glycol of alcohol and 2- hexyls is 3:2:1, a concentration of 60%, addition is terephthalic acid (TPA) weight Under the catalytic action of 0.47% concentrated sulfuric acid, esterification, esterification compressive reaction in nitrogen atmosphere, moulding pressure are carried out For 0.29MPa, temperature is 235 DEG C, is esterification terminal when the water quantity of distillate in esterification reaches the 92% of theoretical value, Obtain terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.8 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.27MPa, temperature is 258 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.71%, is stirred 18 minutes, Addition is 0.04% the catalytic antimony trioxide of terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight Under the action of 0.041% stabilizer Trimethyl phosphite, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, it should Staged pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 268 DEG C, the reaction time is 49 minutes for temperature control；It then proceedes to It vacuumizes, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be down to absolute pressure 50Pa, reaction temperature is controlled 277 DEG C, modified poly ester was made in 84 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment, band branch Glycol segment composition, wherein branched glycol segment be 2- octyl -1,3 propylene glycol segment, 2- amyls-Isosorbide-5-Nitrae butanediol chain Section and 2- hexyl -1,6 hexylene glycol segments composition, the Mole percent ratio of branched glycol segment and ethylene glycol segment are 4.71%.
Embodiment 29
A kind of preparation method of high uniformity high intensity low shrinkage type polyester industrial fiber, high uniformity high intensity low shrinkage type polyester industrial 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, diameter and the oval maximum long axial length of series of round spinneret The difference of degree is 11mm, and the spinneret hole count of a diameter of 2.0mm of guide hole of spinneret orifice, spinneret are 374, the spinneret orifice of spinneret Cross-sectional shape be circle.
Modified poly ester made from embodiment 1 is viscosified through solid phase polycondensation, is measured, porous spinneret squeezes out, is cooled down, is oiled, drawing It stretches, thermal finalization and winding, obtained high uniformity high intensity low shrinkage type polyester industrial fiber 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 fracture strength of high uniformity high intensity low shrinkage type polyester industrial fiber obtained is 7.9cN/dtex；Line density deviation ratio It is 0.6%, fracture strength CV values are 1.8%, and extension at break CV values are 4.5%, extension at break 11.0, at 260 DEG C, melt Viscosity declines 11%, in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, dry-hot shrinkage 8.8%.
Embodiment 30
A kind of preparation method of high uniformity high intensity low shrinkage type polyester industrial fiber, high uniformity high intensity low shrinkage type polyester industrial 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, diameter and the oval maximum long axial length of series of round spinneret The difference of degree is 11mm, and the spinneret hole count of a diameter of 2.0mm of guide hole of spinneret orifice, spinneret are 382, the spinneret orifice of spinneret Cross-sectional shape be circle.
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, obtained high uniformity high intensity low shrinkage type polyester industrial fiber 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 fracture strength of high uniformity high intensity low shrinkage type polyester industrial fiber obtained is 7.8cN/dtex；Line density deviation ratio It is 0.7%, fracture strength CV values are 1.7%, and extension at break CV values are 4.8%, extension at break 11.0, at 260 DEG C, melt Viscosity declines 11%, in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, dry-hot shrinkage 9.2%.
Comparative example 1
A kind of preparation method of high uniformity high intensity low shrinkage type polyester industrial fiber, high uniformity high intensity low shrinkage type polyester industrial 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 diameter and the round maximum diameter of series of round spinneret Spinneret hole count for 11mm, a diameter of 2.0mm of guide hole of spinneret orifice, 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, obtained high uniformity high intensity low shrinkage type polyester industrial fiber 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 fracture strength of high uniformity high intensity low shrinkage type polyester industrial fiber obtained is 7.6cN/dtex；Line density deviation ratio It is 1%, fracture strength CV values are 1.9%, and extension at break CV values are 5.3%, extension at break 11.1, and at 260 DEG C, melt is viscous Degree declines 11%, in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, dry-hot shrinkage 8.5%.
With embodiment 29 comparison as can be seen that the effective area of spinneret it is identical when, (circular arrangement when spinneret hole count is close Spinneret hole count is 370, and oval shaped arrangements spinneret hole count is that 374), the spinneret orifice number of plies of oval shaped arrangements is 6, is less than circular arrangement The spinneret orifice number of plies 8, cooling effect is more preferable；It is oval with the comparison of embodiment 30 as can be seen that when the identical effective area of spinneret The spinneret orifice number of plies of shape arrangement is 5, is less than the spinneret orifice number of plies 8 of circular arrangement, cooling effect is more preferable, the spinneret of oval shaped arrangements The hole count 382 in hole is more than the hole count 370 of the spinneret orifice of circular arrangement, cooling efficiency higher.The comparing result of fibre property shows Fiber linear density deviation ratio made from embodiment 29 and embodiment 30, fracture strength CV values, extension at break CV values 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 high uniformity high intensity low shrinkage type polyester industrial fiber 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 equal to spinneret orifice, spinneret is round spinneret, and the diameter and series of round spinneret are oval The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 192 of spinneret, spinneret The cross-sectional shape of the spinneret orifice of plate is square.
High uniformity high intensity low shrinkage type polyester industrial fiber is squeezed out through metering, porous spinneret, is cooled down, oiling, stretching, heat is fixed High uniformity high intensity low shrinkage type polyester industrial fiber 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 is：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.
High uniformity high intensity low shrinkage type polyester industrial fiber 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 high uniformity high intensity low shrinkage type polyester industrial fiber 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 equal to spinneret orifice, spinneret is round spinneret, and the diameter and series of round spinneret are oval The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 384 of spinneret, spinneret The cross-sectional shape of the spinneret orifice of plate is square.
High uniformity high intensity low shrinkage type polyester industrial fiber is squeezed out through metering, porous spinneret, is cooled down, oiling, stretching, heat is fixed High uniformity high intensity low shrinkage type polyester industrial fiber 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 is：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.
High uniformity high intensity low shrinkage type polyester industrial fiber 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 high uniformity high intensity low shrinkage type polyester industrial fiber is made using porous spinneret.
Spinneret orifice is arranged as long axial symmetry, and the ratio of elliptical long axis and minor axis length is 1.4, between adjacent spinneret orifice 1.6mm is added away from the guide hole diameter equal to spinneret orifice, spinneret is round spinneret, and the diameter and series of round spinneret are oval The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 192 of spinneret, spinneret The cross-sectional shape of the spinneret orifice of plate is square.
High uniformity high intensity low shrinkage type polyester industrial fiber is squeezed out through metering, porous spinneret, is cooled down, oiling, stretching, heat is fixed High uniformity high intensity low shrinkage type polyester industrial fiber 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 is：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.
High uniformity high intensity low shrinkage type polyester industrial fiber 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 high uniformity high intensity low shrinkage type polyester industrial fiber is made using porous spinneret.
Spinneret orifice is arranged as long axial symmetry, and the ratio of elliptical long axis and minor axis length is 1.4, between adjacent spinneret orifice 1.6mm is added away from the guide hole diameter equal to spinneret orifice, spinneret is round spinneret, and the diameter and series of round spinneret are oval The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 288 of spinneret, spinneret The cross-sectional shape of the spinneret orifice of plate is square.
High uniformity high intensity low shrinkage type polyester industrial fiber is squeezed out through metering, porous spinneret, is cooled down, oiling, stretching, heat is fixed High uniformity high intensity low shrinkage type polyester industrial fiber 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 is：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.
High uniformity high intensity low shrinkage type polyester industrial fiber 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 high uniformity high intensity low shrinkage type polyester industrial fiber is made using porous spinneret.
Spinneret orifice is arranged as long axial symmetry, and the ratio of elliptical long axis and minor axis length is 1.4, between adjacent spinneret orifice 1.6mm is added away from the guide hole diameter equal to spinneret orifice, spinneret is round spinneret, and the diameter and series of round spinneret are oval The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 192 of spinneret, spinneret The cross-sectional shape of the spinneret orifice of plate is square.
High uniformity high intensity low shrinkage type polyester industrial fiber is squeezed out through metering, porous spinneret, is cooled down, oiling, stretching, heat is fixed High uniformity high intensity low shrinkage type polyester industrial fiber 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 is：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.
High uniformity high intensity low shrinkage type polyester industrial fiber 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 high uniformity high intensity low shrinkage type polyester industrial fiber is made using porous spinneret.
Spinneret orifice is arranged as long axial symmetry, and the ratio of elliptical long axis and minor axis length is 1.4, between adjacent spinneret orifice 1.6mm is added away from the guide hole diameter equal to spinneret orifice, spinneret is round spinneret, and the diameter and series of round spinneret are oval The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 288 of spinneret, spinneret The cross-sectional shape of the spinneret orifice of plate is square.
High uniformity high intensity low shrinkage type polyester industrial fiber is squeezed out through metering, porous spinneret, is cooled down, oiling, stretching, heat is fixed High uniformity high intensity low shrinkage type polyester industrial fiber 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 is：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.
High uniformity high intensity low shrinkage type polyester industrial fiber 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 high uniformity high intensity low shrinkage type polyester industrial fiber is made using porous spinneret.
Spinneret orifice is arranged as long axial symmetry, and the ratio of elliptical long axis and minor axis length is 1.4, between adjacent spinneret orifice 1.6mm is added away from the guide hole diameter equal to spinneret orifice, spinneret is round spinneret, and the diameter and series of round spinneret are oval The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 192 of spinneret, spinneret The cross-sectional shape of the spinneret orifice of plate is square.
High uniformity high intensity low shrinkage type polyester industrial fiber is squeezed out through metering, porous spinneret, is cooled down, oiling, stretching, heat is fixed High uniformity high intensity low shrinkage type polyester industrial fiber 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 is：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.
High uniformity high intensity low shrinkage type polyester industrial fiber obtained melt viscosity at 280 DEG C, 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 high uniformity high intensity low shrinkage type polyester industrial fiber is made using porous spinneret.
Spinneret orifice is arranged as long axial symmetry, and the ratio of elliptical long axis and minor axis length is 1.4, between adjacent spinneret orifice 1.6mm is added away from the guide hole diameter equal to spinneret orifice, spinneret is round spinneret, and the diameter and series of round spinneret are oval The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 244 of spinneret, spinneret The cross-sectional shape of the spinneret orifice of plate is square.
High uniformity high intensity low shrinkage type polyester industrial fiber is squeezed out through metering, porous spinneret, is cooled down, oiling, stretching, heat is fixed High uniformity high intensity low shrinkage type polyester industrial fiber 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 is：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.
High uniformity high intensity low shrinkage type polyester industrial fiber 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 uniformity high intensity low shrinkage type polyester industrial fiber, it is characterized in that：The high uniformity high intensity low shrinkage type polyester work By modified poly ester, the spinning after solid-phase tack producing obtains industry silk；The material of the high uniformity high intensity low shrinkage type polyester industrial fiber is to be modified Polyester, the modified poly ester are made of terephthalic acid (TPA) segment, ethylene glycol segment and dihydric alcohol segment containing branch；The Gao Jun Fracture strength >=7.5cN/dtex of even property high intensity low shrinkage type polyester industrial fiber, line density deviation ratio≤1.0%, fracture strength CV Value≤2.0%, extension at break CV value≤5.5%；The high uniformity high intensity low shrinkage type polyester industrial fiber 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 It is 8.5 ± 1.5%；
The dihydric alcohol segment containing branch is -1,3 propylene glycol segment of 2- amyls, -1,3 propylene glycol segment of 2- hexyls, 2- heptyl - 1,3 propylene glycol segments, -1,3 propylene glycol segment of 2- octyls, -1,3 propylene glycol segment of 2- nonyls, -1,3 propylene glycol segment of 2- decyls, - 1,4 butanediol segment of 2- amyls, -1,4 butanediol segment of 2- hexyls, -1,4 butanediol segment of 2- heptyl, -1,4 fourth two of 2- octyls Alcohol segment, -1,4 butanediol segment of 2- nonyls, -1,4 butanediol segment of 2- decyls, -1,5 pentanediol segment of 2- amyls, 2- hexyls - 1,5 pentanediol segments, -1,5 pentanediol segment of 2- heptyl, -1,5 pentanediol segment of 2- octyls, -1,5 pentanediol segment of 2- nonyls, - 1,5 pentanediol segment of 2- decyls, -1,6 hexylene glycol segment of 2- amyls, -1,6 hexylene glycol segment of 2- hexyls, 2- heptyl -1,6 oneself two One in alcohol segment, -1,6 hexylene glycol segment of -1,6 hexylene glycol segment of 2- octyls, -1,6 hexylene glycol segment of 2- nonyls or 2- decyls Kind or more；The Mole percent ratio of the dihydric alcohol segment containing branch and ethylene glycol segment is 2~5%.
2. a kind of high uniformity high intensity low shrinkage type polyester industrial fiber according to claim 1, which is characterized in that the Gao Jun The extension at break of even property high intensity low shrinkage type polyester industrial fiber is 12.0 ± 1.5%, and the number-average molecular weight of the modified poly ester is 15000-30000。
3. a kind of preparation method of high uniformity high intensity low shrinkage type polyester industrial fiber as described in any one of claim 1-2, It is characterized in that：Modified poly ester is squeezed out, cooled down, oiled, stretched through solid phase polycondensation thickening, metering, porous spinneret, thermal finalization and High uniformity high intensity low shrinkage type polyester industrial fiber is made in 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 includes the following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
After terephthalic acid (TPA) and the dihydric alcohol containing branch are made into slurry, under the catalytic action of the concentrated sulfuric acid, esterification is carried out, Obtain terephthalic acid (TPA) binary alcohol esters；The dihydric alcohol containing branch be -1,3 propylene glycol of 2- amyls, -1,3 propylene glycol of 2- hexyls, - 1,3 propylene glycol of 2- heptyl, -1,3 propylene glycol of 2- octyls, -1,3 propylene glycol of 2- nonyls, -1,3 propylene glycol of 2- decyls, amyl -1 2-, 4 butanediols, -1,4 butanediol of 2- hexyls, -1,4 butanediol of 2- heptyl, -1,4 butanediol of 2- octyls, -1,4 butanediol of 2- nonyls, - 1,4 butanediol of 2- decyls, -1,5 pentanediol of 2- amyls, -1,5 pentanediol of 2- hexyls, -1,5 pentanediol of 2- heptyl, octyl -1 2-, 5 pentanediols, 2- nonyls -1,5 pentanediol, 2- decyls -1,5 pentanediol, 2- amyls -1,6 hexylene glycol, 2- hexyl -1,6 hexylene glycols, One kind in -1,6 hexylene glycol of 2- heptyl, -1,6 hexylene glycol of -1,6 hexylene glycol of 2- octyls, -1,6 hexylene glycol of 2- nonyls or 2- decyls More than；
(2) preparation of ethylene glycol terephthalate：
After terephthalic acid (TPA) and ethylene glycol are made into slurry, esterification is carried out, ethylene glycol terephthalate is obtained；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, stirring is mixed It closes, under the action of catalyst and stabilizer, under conditions of negative pressure, carries out polycondensation reaction and the Gao Zhen of low vacuum stage successively Modified poly ester is made in the polycondensation reaction in empty stage.
4. the preparation method of high uniformity high intensity low shrinkage type polyester industrial fiber according to claim 3, which is characterized in that institute State modified poly ester preparation the specific steps are：
(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 Modified poly ester is made in 275~280 DEG C, 50~90 minutes reaction time in 100Pa, reaction temperature control；
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 viscous slice；Squeezed out again through metering, porous spinneret, be cooling, on Oil, stretching, thermal finalization and winding, are made high uniformity high intensity low shrinkage type polyester industrial fiber；
Spinning main technologic parameters are：
The temperature of the extrusion is 290~310 DEG C；
The wind-warm syndrome of the cooling is 20~30 DEG C；
The stretching, heat setting process parameter are：
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 high uniformity high intensity low shrinkage type polyester industrial fiber according to claim 4, feature exist In 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 addition is The 0.3-0.5% of terephthalic acid (TPA) weight；A concentration of 50-60wt% of the concentrated sulfuric acid；In the step (2), terephthaldehyde The molar ratio of acid and ethylene glycol is 1:1.2~2.0；In the step (3), the terephthalic acid (TPA) binary alcohol esters and terephthaldehyde The Mole percent ratio of sour glycol ester is 2~5%；The catalyst is antimony oxide, antimony glycol or antimony acetate, catalysis Agent addition is the 0.01%~0.05% of terephthalic acid (TPA) total weight；The stabilizer is triphenyl phosphate, trimethyl phosphate Or Trimethyl phosphite, stabilizer addition are the 0.01%~0.05% of the terephthalic acid (TPA) total weight.
6. a kind of preparation method of high uniformity high intensity low shrinkage type polyester industrial fiber according to claim 3, feature exist In the porous spinneret is round spinneret or elliptical spinneret plate；The diameter of the circle spinneret and series are oval most The difference of big long axis length is more than 10mm, and the elliptical spinneret plate and the difference of serial oval maximum long axis length are more than 10mm。
7. a kind of preparation method of high uniformity high intensity low shrinkage type polyester industrial fiber according to claim 3, feature exist In, 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 spray The guide hole diameter of wire hole 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 high uniformity high intensity low shrinkage type polyester industrial fiber according to claim 3, feature exist In a diameter of 1.5~2.5mm of guide hole of the spinneret orifice；The spinneret hole count of the spinneret is more than or equal to 192, the spinneret The cross-sectional shape of the spinneret orifice of plate is circle, square, diamond shape, "-" type, triangular form, trilobal cross, hollow type or flat Type.
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