CN106400162A - High-uniformity, high-strength and low-shrinkage polyester industrial filament and production method thereof - Google Patents

High-uniformity, high-strength and low-shrinkage polyester industrial filament and production method thereof Download PDF

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Publication number
CN106400162A
CN106400162A CN201610776461.7A CN201610776461A CN106400162A CN 106400162 A CN106400162 A CN 106400162A CN 201610776461 A CN201610776461 A CN 201610776461A CN 106400162 A CN106400162 A CN 106400162A
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segment
tpa
terephthalic acid
spinneret
preparation
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CN201610776461.7A
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CN106400162B (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 invention relates to a high-uniformity, high-strength and low-shrinkage polyester industrial filament and a production method thereof. The above polyester fiber comprises modified polyester, and the modified polyester comprises a terephthalic acid chain segment, an ethylene glycol chain segment and a branched chain-containing diol chain segment. The production method of the polyester fibers comprises the following steps: carrying out an esterification reaction on terephthalic acid and branched chain-containing diol under the catalysis of concentrated sulfuric acid in order to obtain diol terephthalate; carrying out an esterification reaction on terephthalic acid and ethylene glycol to obtain ethylene terephthalate; and mixing the diol terephthalate with the ethylene terephthalate, carrying out low-vacuum stage and high-vacuum stage condensation polymerization reaction under the action of a catalyst and a stabilizer in order to prepare the modified polyester, metering the modified polyester, extruding the modified polyester through a porous spinneret, and carrying out cooling, oiling, stretching, heat setting and reeling in order to produce the high-uniformity, high-strength and low-shrinkage polyester industrial filament.

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 or polyester fiber) fiber since the advent of the world, have fracture strength and Elastic modelling quantity 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 crease-resistant exempt to provide, the advantages of stiffness is good, be 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 to have relatively special physicalchemical structure, performance and purposes, or has the chemical fibre of specific function, major embodiment Being 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 cloth being produced as raw material using high-strength low-shrinkage polyester industrial filament yarn, has higher peel strength and tear is strong Degree, makes shelter cloth be applied to various uses, flexible body advertising lamp box material, inflatable structure material, fluffy lid architectural fabrics sunshade account Paulin etc..Based on high-strength low-shrinkage industrial yarn, textile material obtains in terms of the military supplies such as special protective garment, camouflage, covering, knapsack To application.One kind as earth working material has the advantages that light, soft, high-strength, wear-resisting, anticorrosive, non-conductive, damping.Make Used time safe ready, efficiency high, and lifting object will not be damaged.The application of Pet Industrial Fiber is expanded and is driven application The whole competitiveness lifting in field, no matter in the weight mitigating composite, the durability of use and minimizing are keeped in repair, are raised cost Etc. all many-sides, polyesters high-performance fiber has increasingly given play to its synthetic competitive advantages.Following many decades, high-performance polyester The development of fiber not only has considerable progress in quantity, more in the expansion of application and carrying of industrial chain whole competitiveness Go up the substantial effect of acquirement.
The Main way that Pet Industrial Fiber is developed by high intensity, lower shrinkage, dimensional stability, and affect fiber quality Be polyester macromolecule collection state structure, be mainly concerned with the active force between polyester molecule, the form of crystallization and structure, alignment state Structure etc., and the form crystallizing and structure are emphasis therein.Low-shrinkage high-strength PET industrial yarn, is the big class in polyester, Because its intensity is high, percent thermal shrinkage is low, and impact resistance is excellent, and it is steady that its fabric or the rubber made have good size Qualitative and heat-resistant stability, can absorb impact load, and has the characteristics that polyamide fibre is soft, and be therefore widely used neck Domain.Low-shrinkage high-strength PET industrial yarn is mainly used in 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..
Have many parameters during melt spinning, these parameters determine fiberizing course and spin fiber structure and Performance, production is exactly the fiber of desired properties is obtained by controlling these parameters.Experimental branch line all adopts side for a long time As the type of cooling, energy resource consumption accounts for the significant portion of long filament production cost, with people to chemical fibre performance and quality for blowing Require increasingly to improve, the exploitation of chemical-fibres filaments new product develops it is desirable to higher is cold to the fibre in differentiation direction of high added value But blowing condition, then proposes ring blowing device.Ring blowing device not only possesses the uniform advantage of every synnema wind-engaging, Er Qieneng Consumption is compared relatively low, effectively solves the wind energy loss problem that cross air blasting causes because blowing area is big.
In spinning process, although ring blowing has obvious advantage, but still the cooling of porous yarn cannot be solved well Uneven problem：Because spun silk is after circular spinneret is extruded, by ring wind quenching, due to the circular spinneret number of turns relatively Many lead to that the silk of innermost layer may be also uncolled after cooling in outermost silk so that ring blowing hardly enters innermost layer, Thus the problems such as fiber number is irregular, and intensity is irregular in the silk of gained, cause follow-up to silk be processed further difficulty occurs.
Content of the invention
The technical problem to be solved in the present invention is for the deficiencies in the prior art, provides a kind of high uniformity high intensity low shrinkage type Polyester industrial fiber and preparation method thereof, the raw material of high uniformity high intensity low shrinkage type polyester industrial fiber of the present invention is modified poly ester, changes Property polyester strand in introduce dihydroxylic alcohols segment containing side chain, the modified high uniformity high intensity low shrinkage type of modified polyester preparation Polyester industrial fiber, under the conditions of uniform 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 unbranched high uniformity high intensity low shrinkage type polyester industrial fiber at equal 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 processing.In addition this On the bright porous spinneret of high uniformity high intensity low shrinkage type polyester industrial fiber, the arrangement mode of spinneret orifice is oval shaped arrangements, ellipse Circular arrangement refers to that the hole of spinneret orifice is centrally located on concentration ellipse, and concentration ellipse is that series is oval, and all oval major axis are altogether Line, and short axle is conllinear；Higher cooling effectiveness and preferable cooling effect can be reached.
A kind of high uniformity high intensity low shrinkage type polyester industrial fiber, described 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 described high uniformity high intensity low shrinkage type polyester industrial fiber is modified poly ester, institute State modified poly ester form by terephthalic acid (TPA) segment, ethylene glycol segment and containing the dihydroxylic alcohols segment of side chain, described containing side chain two First alcohol segment refers to that side chain is located on one of dihydroxylic alcohols segment non-end group carbon and side chain is straight containing 5-10 carbon atom The dihydroxylic alcohols segment of chain carbochain；Fracture strength >=the 7.5cN/dtex of described 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 value≤ 5.5%；At 260～290 DEG C, melt viscosity declines 10-20% to described high uniformity high intensity low shrinkage type polyester industrial fiber, in temperature Spend under the test condition for 177 DEG C × 10min × 0.05cN/dtex, dry-hot shrinkage is 8.5 ± 1.5%；
Described melt viscosity declines the contrast referring to modified poly ester and normal polyester in mutually synthermal melt viscosity.
A kind of high uniformity high intensity low shrinkage type polyester industrial fiber is modified poly ester, introduces on modified poly ester macromolecular long-chain Dihydroxylic alcohols segment containing side chain, and the impact to the crystal property of modified poly ester and flow behavior of the length of side chain and quantity is relatively Greatly, the too short purpose not reaching polyester modification of branch lengths, length is oversize to cause new entanglement, affect its flow behavior, when When side chain is located on one of dihydroxylic alcohols segment non-end group carbon and side chain is the linear carbon chain containing 5-10 carbon atom, through changing Property polyester preparation a kind of high uniformity high intensity low shrinkage type polyester industrial fiber, under the conditions of uniform temperature, industrial yarn interior molecules The increasing degree of the spatial joint clearance of interchain is far longer than unbranched industrial yarn at equal temperature, is conducive to industrial yarn melt viscosity Reduce, be easy to further process.
As preferred technical scheme：
A kind of high uniformity high intensity low shrinkage type polyester industrial fiber as above, described 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 described modified poly ester is 15000-30000.
A kind of high uniformity high intensity low shrinkage type polyester industrial fiber as above, the described dihydroxylic alcohols segment containing side chain is 2- Amyl group -1,3 propane diols segment, 2- hexyl -1,3 propane diols segment, 2- heptyl -1,3 propane diols segment, 2- octyl group -1,3 propane diols Segment, 2- nonyl -1,3 propane diols segment, 2- decyl -1,3 propane diols segment, 2- amyl group -1,4 butanediol segment, 2- hexyl -1, 4 butanediol segments, 2- heptyl -1,4 butanediol segment, 2- octyl group -1,4 butanediol segment, 2- nonyl -1,4 butanediol segment, 2- Decyl -1,4 butanediol segment, 2- amyl group -1,5 pentanediol segment, 2- hexyl -1,5 pentanediol segment, 2- heptyl -1,5 pentanediol Segment, 2- octyl group -1,5 pentanediol segment, 2- nonyl -1,5 pentanediol segment, 2- decyl -1,5 pentanediol segment, 2- amyl group -1, 6 hexylene glycol segments, 2- hexyl -1,6 hexylene glycol segment, 2- heptyl -1,6 hexylene glycol segment, 2- octyl group -1,6 hexylene glycol segment, 2- One or more of nonyl -1,6 hexylene glycol segment or 2- decyl -1,6 hexylene glycol segment；The described dihydroxylic alcohols segment containing side chain 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 are extruded, cool down, oiling, stretching, thermal finalization and winding, prepared high uniformity high intensity low shrinkage type Polyester industrial fiber；
On described porous spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and described oval shaped arrangements refer to spinneret orifice Hole be centrally located on concentration ellipse, described concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear；
The preparation process of modified poly ester comprises the following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Terephthalic acid (TPA) is made into after slurry with the dihydroxylic alcohols containing side chain, under the catalytic action of the concentrated sulfuric acid, is esterified Reaction, obtains terephthalic acid (TPA) binary alcohol esters；It is non-that the described dihydroxylic alcohols containing side chain is that side chain is located at one of dihydroxylic alcohols segment On end group carbon and side chain is the dihydroxylic alcohols of the linear carbon chain containing 5-10 carbon atom；
For the dihydroxylic alcohols containing side chain, its side chain is alkyl, is electron withdraw group, in the presence of side chain, makes strand Spatial volume increases, and solvation diminishes, and in dihydroxylic alcohols, proton is difficult to dissociate so that containing dihydroxylic alcohols and the terephthaldehyde of side chain The reactivity of acid is less than ethylene glycol, according to the mixing of same ethylene glycol and terephthaldehyde's acid reaction, can cause the binary containing side chain Alcohol reaction is imperfect, thus ratio in polyester macromolecule for the dihydroxylic alcohols containing side chain for the impact, and then affect the performance of polyester.This Using first the dihydroxylic alcohols containing side chain being carried out esterification with terephthalic acid (TPA) under the catalytic action of sulfuric acid, its product exists for invention Ethylene glycol and p phthalic acid esterification add it is ensured that containing the stability of the dihydroxylic alcohols proportioning of side chain after terminating.
(2) preparation of ethylene glycol terephthalate：
Terephthalic acid (TPA) and ethylene glycol are made into after slurry, carry out esterification, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), stir Mix mixing, in the presence of catalyst and stabilizer, under conditions of negative pressure, carry out successively the low vacuum stage polycondensation reaction and The polycondensation reaction of high vacuum stage of Fig, prepared modified poly ester.
A kind of preparation method of high uniformity high intensity low shrinkage type polyester industrial fiber as above, described modified poly ester preparation Concretely comprise the following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Terephthalic acid (TPA) and the dihydroxylic alcohols containing side chain are made into slurry and add in reactor, in the catalytic action of the concentrated sulfuric acid Under, carry out esterification, esterification compressive reaction in nitrogen atmosphere, moulding pressure is normal pressure～0.3MPa, temperature is 180 ～240 DEG C, be esterification terminal when the water quantity of distillate in esterification reaches more than the 90% of theoretical value；Obtain to benzene two Formic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Terephthalic acid (TPA) and ethylene glycol are made into after slurry and add in reactor, carry 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 It is esterification terminal that amount reaches during more than the 90% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), stir Mix mixing 15-20 minute, in the presence of catalyst and stabilizer, the polycondensation starting the low vacuum stage under conditions of negative pressure is anti- Should, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, and at 260～270 DEG C, the reaction time is temperature control 30～50 minutes；Then proceed to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure and be less than 100Pa, reaction temperature controls at 275～280 DEG C, 50～90 minutes reaction time, prepared modified poly ester；
Again modified poly ester is obtained Modified polyester chips through pelletizing, obtained polyester slice is viscosified by solid phase polycondensation, makes The inherent viscosity of polyester slice brings up to 1.0～1.2dL/g, as high viscous section；Again through metering, porous spinneret extrusion, cold But, oil, stretch, thermal finalization and winding, prepared high uniformity high intensity low shrinkage type polyester industrial fiber；
Spinning main technologic parameters are：
The temperature of described extrusion is 290～310 DEG C；
The wind-warm syndrome of described cooling is 20～30 DEG C；
Described stretching, heat setting process parameter are：
GR-1 speed 480～600m/min；Temperature is normal temperature；
GR-2 speed 500～1000m/min；80～100 DEG C of temperature；
GR-3 speed 1800～2500m/min；100～150 DEG C of temperature；
GR-4 speed 2800～3500m/min；200～250 DEG C of temperature；
GR-5 speed 2800～3500m/min；200～250 DEG C of temperature；
GR-6 speed 2600～3400m/min；150～220 DEG C of temperature；
The speed of described winding is 2600～3400m/min.
A kind of preparation method of high uniformity high intensity low shrinkage type polyester industrial fiber, in described step (1), right as above Phthalic acid is 1 with the mol ratio of the dihydroxylic alcohols containing side chain:1.3-1.5；Concentrated sulfuric acid addition is terephthalic acid (TPA) weight 0.3-0.5%；The concentration of the described concentrated sulfuric acid is 50-60wt%；In described step (2), terephthalic acid (TPA) and ethylene glycol mole Than for 1:1.2～2.0；In described step (3), described terephthalic acid (TPA) binary alcohol esters and ethylene glycol terephthalate mole Percent value is 2～5%；Described catalyst is antimony oxide, antimony glycol or antimony acetate, and catalyst charge is to benzene two The 0.01%～0.05% of formic acid gross weight；Described stabilizer is triphenyl phosphate, trimethyl phosphate or Trimethyl phosphite, surely Determine that agent addition is described terephthalic acid (TPA) gross weight 0.01%～0.05%.
A kind of preparation method of high uniformity high intensity low shrinkage type polyester industrial fiber as above, the described binary containing side chain Alcohol is 2- amyl group -1,3 propane diols, 2- hexyl -1,3 propane diols, 2- heptyl -1,3 propane diols, 2- octyl group -1,3 propane diols, 2- nonyl Base -1,3 propane diols, 2- decyl -1,3 propane diols, 2- amyl group -1,4 butanediol, 2- hexyl -1,4 butanediol, 2- heptyl -1,4 fourth Glycol, 2- octyl group -1,4 butanediol, 2- nonyl -1,4 butanediol, 2- decyl -1,4 butanediol, 2- amyl group -1,5 pentanediol, 2- are own Base -1,5 pentanediol, 2- heptyl -1,5 pentanediol, 2- octyl group -1,5 pentanediol, 2- nonyl -1,5 pentanediol, 2- decyl -1,5 penta Glycol, 2- amyl group -1,6 hexylene glycols, 2- hexyl -1,6 hexylene glycols, 2- heptyl -1,6 hexylene glycols, 2- octyl group -1,6 hexylene glycols, 2- nonyl One or more of base -1,6 hexylene glycol or 2- decyl -1,6 hexylene glycol.
A kind of preparation method of high uniformity high intensity low shrinkage type polyester industrial fiber as above, described porous spinneret is Circular spinneret or elliptical spinneret plate；The diameter of described circle spinneret is big with the difference of the oval maximum long axis length of series In 10mm, described elliptical spinneret plate is more than 10mm with the difference of the oval maximum long axis length of series.
A kind of preparation method of high uniformity high intensity low shrinkage type polyester industrial fiber as above, on described porous spinneret Spinneret orifice be arranged as that major axis and/or short axle are symmetrical, the guide hole diameter that the spacing of adjacent spinneret orifice is more than or equal to spinneret orifice adds 1.5mm；Oval major axis is 1.3～1.8 with the ratio of minor axis length.
When the effective area phase of spinneret is simultaneously as the girth of ellipse is more than circular girth, spinneret orifice is oval 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 Silk hole oval shaped arrangements are conducive to the cooling of ring blowing, improve the cooling effectiveness of ring blowing, the fibre property of preparation is also more excellent Good.Major axis is closer to 1 with the ratio of minor axis length, and ellipse is more similar to justify, and the difference of cooling effectiveness and cooling effect is little； When the ratio of major axis and minor axis length is 1.3, cooling effect significantly improves, and individual pen hole count is corresponding to increase by 16%；Major axis and short axle When the ratio of length is 1.8, cooling effect improves larger, the corresponding increase by 33% of individual pen hole count, in the case of identical hole count, the present invention Oval shaped arrangements reduce than the number of turns of conventional concentric circle best-fit it is easy to cooling wind thoroughly, makes the fiber cooling condition of Internal and external cycle Evenly；When the ratio of major axis and minor axis length is more than 1.8, ellipse is partial to form flat shape, is difficult to punch, simultaneously cold But effect no longer raises.Therefore, the oval major 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 above, the guide hole of described spinneret orifice A diameter of 1.5～2.5mm；The spinneret hole count of described spinneret is more than or equal to 192, the cross section of the spinneret orifice of described spinneret Generally circular in shape, square, rhombus, yi word pattern, 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 dihydroxylic alcohols segment containing side chain containing, when temperature be higher than vitrification point when, side chain prior to backbone motion, modified polyester system The free volume of standby industrial yarn is far longer than unbranched industrial yarn at equal temperature, advantageously reduces its melt viscosity.
On the spinneret of the present invention, the arrangement mode of spinneret orifice is oval shaped arrangements, 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 More preferably, the industrial yarn of preparation is also more excellent for cooling effect.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 are capable of greatly cooling down, and significantly improve cooling effectiveness.
Beneficial effect：
The raw material of the high uniformity high intensity low shrinkage type polyester industrial fiber of gained of the present invention is modified poly ester, and modified poly ester divides greatly The dihydroxylic alcohols segment containing side chain containing in son, when temperature is higher than vitrification point, side chain, prior to backbone motion, makes free body 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 characteristics.
The raw material of the high uniformity high intensity low shrinkage type polyester industrial fiber of gained of the present invention is modified poly ester, the binary containing side chain The introducing of alcohol segment to the structural regularity of modified poly ester there is no big destruction, maintain the premium properties of polyester fiber.
On the high uniformity high intensity low shrinkage type polyester industrial fiber spinneret of the present invention, the arrangement mode of spinneret orifice is ellipse 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 Easily blow through dynamic analysis of spinning, more preferably, the fibre property of preparation is also more excellent for the cooling effect of dynamic analysis of spinning.
On the high uniformity high intensity low shrinkage type polyester industrial fiber spinneret of the present invention, the arrangement mode of spinneret orifice is ellipse 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, oval row Row are capable of greatly cooling down, and significantly improve cooling effectiveness.
Brief description
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 Degree ratio is 1.3；
Fig. 2 is the circular arrangement figure of 370 spinneret orifices, and the aperture of spinneret orifice is 2.0mm；
Fig. 3 is the oval shaped arrangements figure of 382 spinneret orifices, and the aperture of spinneret orifice is 2.0mm, the length of transverse and short axle Degree ratio is 1.6.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate this Bright rather than limit the scope of the present invention.In addition, it is to be understood that after having read the content of present invention instruction, art technology Personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited Fixed scope.
Embodiment 1
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.3 terephthalic acid (TPA) and 2- amyl group -1,3 propane diols are made into slurry and add in reactor, Concentration is 50wt%, and addition is under the catalytic action of 0.3% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is normal pressure, and temperature is 180 DEG C, when the water in esterification distillates It is esterification terminal that amount reaches during the 90% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.2 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is normal pressure, and temperature is 250 DEG C, when the water in esterification distillates It is esterification terminal that amount reaches during the 90% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 2% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 15 minutes is adding Measure for terephthalic acid (TPA) gross weight 0.01% the catalytic antimony trioxide and addition be terephthalic acid (TPA) gross weight Under conditions of negative pressure, in the presence of 0.01% stabilizer triphenyl phosphate, start the polycondensation reaction in low vacuum stage, this rank It is 500Pa that section pressure is steadily evacuated to absolute pressure by normal pressure, and at 260 DEG C, the reaction time is 30 minutes to temperature control；Then proceed to Vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 100Pa, and reaction temperature controls 275 DEG C, 50 minutes reaction time, prepared modified poly ester.
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 propane diols segment compositions, the dihydroxylic alcohols segment containing side chain is 2% with the Mole percent ratio of ethylene glycol segment.
Table 1：Embodiment 2-12 important technological parameters
Embodiment 2
The preparation process of the preparation method of the modified poly ester of embodiment 2, wherein modified poly ester with embodiment 1, wherein mainly Technical parameter referring to table 1；After step (3) adds terephthalic acid (TPA) binary alcohol esters, stirring mixing 16 minutes, in addition be The catalytic antimony trioxide of the 0.011% of terephthalic acid (TPA) gross weight and addition are the 0.02% of terephthalic acid (TPA) gross weight Stabilizer triphenyl phosphate in the presence of, under conditions of negative pressure start the low vacuum stage polycondensation reaction, this staged pressure Absolute pressure 490Pa is steadily evacuated to by normal pressure, at 262 DEG C, the reaction time is 31 minutes to temperature control；Then proceed to vacuumize, Carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 90Pa, reaction temperature controls at 276 DEG C, reaction 51 minutes time, prepared modified poly ester.
The number-average molecular weight of modified poly ester is 16000, and modified poly ester is own by terephthalic acid (TPA) segment, ethylene glycol segment and 2- Base -1,3 propane diols segment compositions, 2- hexyl -1,3 propane diols segments are 2.1% with the Mole percent ratio of ethylene glycol segment.
Embodiment 3
The preparation process of the preparation method of the modified poly ester of embodiment 3, wherein modified poly ester with embodiment 1, wherein mainly Technical parameter referring to table 1；After step (3) adds terephthalic acid (TPA) binary alcohol esters, stirring mixing 16 minutes, in addition be The catalytic antimony trioxide of the 0.03% of terephthalic acid (TPA) gross weight and addition are the 0.02% of terephthalic acid (TPA) gross weight Stabilizer triphenyl phosphate in the presence of, under conditions of negative pressure start the low vacuum stage polycondensation reaction, this staged pressure Absolute pressure 498Pa is steadily evacuated to by normal pressure, at 263 DEG C, the reaction time is 32 minutes to temperature control；Then proceed to vacuumize, Carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 90Pa, reaction temperature controls at 277 DEG C, reaction 57 minutes time, prepared modified poly ester.
The number-average molecular weight of modified poly ester is 15900, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- heptan Base -1,3 propane diols segment compositions, 2- heptyl -1,3 propane diols segments are 2.2% with the Mole percent ratio of ethylene glycol segment.
Embodiment 4
The preparation process of the preparation method of the modified poly ester of embodiment 4, wherein modified poly ester with embodiment 1, wherein mainly Technical parameter referring to table 1；After step (3) adds terephthalic acid (TPA) binary alcohol esters, stirring mixing 17 minutes, in addition be The catalytic antimony trioxide of the 0.033% of terephthalic acid (TPA) gross weight and addition are terephthalic acid (TPA) gross weight Under conditions of negative pressure, in the presence of 0.023% stabilizer triphenyl phosphate, start the polycondensation reaction in low vacuum stage, this rank It is 497Pa that section pressure is steadily evacuated to absolute pressure by normal pressure, and at 264 DEG C, the reaction time is 33 minutes to temperature control；Then proceed to Vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 80Pa, and reaction temperature controls 278 DEG C, 58 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of modified poly ester is 15800, and modified poly ester is pungent by terephthalic acid (TPA) segment, ethylene glycol segment and 2- Base -1,3 propane diols segment compositions, 2- octyl group -1,3 propane diols segments are 2.3% with the Mole percent ratio of ethylene glycol segment.
Embodiment 5
The preparation process of the preparation method of the modified poly ester of embodiment 5, wherein modified poly ester with embodiment 1, wherein mainly Technical parameter referring to table 1；After step (3) adds terephthalic acid (TPA) binary alcohol esters, stirring mixing 17 minutes, in addition be The catalytic antimony trioxide of the 0.034% of terephthalic acid (TPA) gross weight and addition are terephthalic acid (TPA) gross weight Under conditions of negative pressure, in the presence of 0.024% stabilizer triphenyl phosphate, start the polycondensation reaction in low vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and at 265 DEG C, the reaction time is 34 minutes to temperature control；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 80Pa, and reaction temperature controls 277 DEG C, 59 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of modified poly ester is 15900, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- nonyl Base -1,3 propane diols segment compositions, 2- nonyl -1,3 propane diols segments are 2.4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 6
The preparation process of the preparation method of the modified poly ester of embodiment 6, wherein modified poly ester with embodiment 1, wherein mainly Technical parameter referring to table 1；After step (3) adds terephthalic acid (TPA) binary alcohol esters, stirring mixing 18 minutes, in addition be The catalytic antimony trioxide of the 0.035% of terephthalic acid (TPA) gross weight and addition are terephthalic acid (TPA) gross weight Under conditions of negative pressure, in the presence of 0.025% stabilizer triphenyl phosphate, start the polycondensation reaction in low vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 266 DEG C, the reaction time is 35 minutes to temperature control；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 70Pa, and reaction temperature controls 278 DEG C, 60 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of modified poly ester is 16000, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and the 2- last of the ten Heavenly stems Base -1,3 propane diols segment compositions, 2- decyl -1,3 propane diols segments are 2.5% with the Mole percent ratio of ethylene glycol segment.
Embodiment 7
The preparation process of the preparation method of the modified poly ester of embodiment 7, wherein modified poly ester with embodiment 1, wherein mainly Technical parameter referring to table 1；After step (3) adds terephthalic acid (TPA) binary alcohol esters, stirring mixing 19 minutes, in addition be The catalytic antimony trioxide of the 0.036% of terephthalic acid (TPA) gross weight and addition are terephthalic acid (TPA) gross weight Under conditions of negative pressure, in the presence of 0.025% stabilizer triphenyl phosphate, start the polycondensation reaction in low vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and at 267 DEG C, the reaction time is 36 minutes to temperature control；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 70Pa, and reaction temperature controls 278 DEG C, 61 minutes reaction time, prepared modified poly ester.
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- amyl group-Isosorbide-5-Nitrae butanediol segment composition, 2- amyl group-Isosorbide-5-Nitrae butanediol segment and second two The Mole percent ratio of alcohol segment is 2.6%.
Embodiment 8
The preparation process of the preparation method of the modified poly ester of embodiment 8, wherein modified poly ester with embodiment 1, wherein mainly Technical parameter referring to table 1；After step (3) adds terephthalic acid (TPA) binary alcohol esters, stirring mixing 19 minutes, in addition be The catalytic antimony trioxide of the 0.036% of terephthalic acid (TPA) gross weight and addition are terephthalic acid (TPA) gross weight Under conditions of negative pressure, in the presence of 0.025% stabilizer triphenyl phosphate, start the polycondensation reaction in low vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and at 267 DEG C, the reaction time is 36 minutes to temperature control；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 70Pa, and reaction temperature controls 278 DEG C, 61 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of modified poly ester is 17000, and modified poly ester is own by terephthalic acid (TPA) segment, ethylene glycol segment and 2- Base-Isosorbide-5-Nitrae butanediol segment composition, 2- hexyl-Isosorbide-5-Nitrae butanediol segment is 2.7% with the Mole percent ratio of ethylene glycol segment.
Embodiment 9
The preparation process of the preparation method of the modified poly ester of embodiment 9, wherein modified poly ester with embodiment 1, wherein mainly Technical parameter referring to table 1；After step (3) adds terephthalic acid (TPA) binary alcohol esters, stirring mixing 16 minutes, in addition be The catalyst glycol antimony of the 0.04% of terephthalic acid (TPA) gross weight and addition are the 0.026% of terephthalic acid (TPA) gross weight In the presence of stabilizer trimethyl phosphate, under conditions of negative pressure start the low vacuum stage polycondensation reaction, this staged pressure by Normal pressure is steadily evacuated to absolute pressure 497Pa, and at 268 DEG C, the reaction time is 38 minutes to temperature control；Then proceed to vacuumize, enter The polycondensation reaction of row high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 60Pa, and reaction temperature controls at 279 DEG C, reaction 62 minutes time, prepared modified poly ester.
The number-average molecular weight of modified poly ester is 17000, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- heptan Base-Isosorbide-5-Nitrae butanediol segment composition, 2- heptyl-Isosorbide-5-Nitrae butanediol segment is 2.8% with the Mole percent ratio of ethylene glycol segment.
Embodiment 10
The preparation process of the preparation method of the modified poly ester of embodiment 10, wherein modified poly ester with embodiment 1, wherein mainly Technical parameter referring to table 1；After step (3) adds terephthalic acid (TPA) binary alcohol esters, stirring mixing 17 minutes, in addition be The catalyst glycol antimony of the 0.03% of terephthalic acid (TPA) gross weight and addition are the 0.027% of terephthalic acid (TPA) gross weight In the presence of stabilizer trimethyl phosphate, under conditions of negative pressure start the low vacuum stage polycondensation reaction, this staged pressure by Normal pressure is steadily evacuated to absolute pressure 498Pa, and at 269 DEG C, the reaction time is 39 minutes to temperature control；Then proceed to vacuumize, enter The polycondensation reaction of row high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 60Pa, and reaction temperature controls at 278 DEG C, reaction 64 minutes time, prepared modified poly ester.
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- Base-Isosorbide-5-Nitrae butanediol segment composition, 2- octyl group-Isosorbide-5-Nitrae butanediol segment is 3% with the Mole percent ratio of ethylene glycol segment.
Embodiment 11
The preparation process of the preparation method of the modified poly ester of embodiment 11, wherein modified poly ester with embodiment 1, wherein mainly Technical parameter referring to table 1；After step (3) adds terephthalic acid (TPA) binary alcohol esters, stirring mixing 18 minutes, in addition be The catalyst glycol antimony of the 0.04% of terephthalic acid (TPA) gross weight and addition are the 0.03% of terephthalic acid (TPA) gross weight In the presence of stabilizer trimethyl phosphate, under conditions of negative pressure start the low vacuum stage polycondensation reaction, this staged pressure by Normal pressure is steadily evacuated to absolute pressure 497Pa, and at 260 DEG C, the reaction time is 40 minutes to temperature control；Then proceed to vacuumize, enter The polycondensation reaction of row high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 60Pa, and reaction temperature controls at 277 DEG C, reaction 63 minutes time, prepared modified poly ester.
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- nonyl Base-Isosorbide-5-Nitrae butanediol segment composition, 2- nonyl-Isosorbide-5-Nitrae butanediol segment is 4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 12
The preparation process of the preparation method of the modified poly ester of embodiment 12, wherein modified poly ester with embodiment 1, wherein mainly Technical parameter referring to table 1；After step (3) adds terephthalic acid (TPA) binary alcohol esters, stirring mixing 18 minutes, in addition be The catalyst acetic acid antimony of the 0.038% of terephthalic acid (TPA) weight and addition are the stabilizer of the 0.03% of terephthalic acid (TPA) weight Under conditions of negative pressure, in the presence of Trimethyl phosphite, start the polycondensation reaction in low vacuum stage, this staged pressure is by normal pressure Steadily it is evacuated to absolute pressure 497Pa, at 265 DEG C, the reaction time is 42 minutes to temperature control；Then proceed to vacuumize, carry out height The polycondensation reaction of vacuum stages, making reaction pressure be down to absolute pressure is 40Pa, and reaction temperature controls at 277 DEG C, the reaction time 70 minutes, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 26000, by terephthalic acid (TPA) segment, ethylene glycol segment and the 2- last of the ten Heavenly stems Base-Isosorbide-5-Nitrae butanediol segment composition, 2- decyl-Isosorbide-5-Nitrae butanediol segment is 4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 13
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.5 terephthalic acid (TPA) and 2- decyl -1,6 hexylene glycols are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of 0.5% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.3MPa, and temperature is 240 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:2.0 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.3MPa, and temperature is 260 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 5% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 20 minutes is adding Measure for terephthalic acid (TPA) weight 0.05% catalyst acetic acid antimony and addition be terephthalic acid (TPA) weight 0.05% steady In the presence of determining agent Trimethyl phosphite, under conditions of negative pressure start the low vacuum stage polycondensation reaction, this staged pressure by It is 450Pa that normal pressure is steadily evacuated to absolute pressure, and at 270 DEG C, the reaction time is 50 minutes to temperature control；Then proceed to vacuumize, Carry out the polycondensation reaction of high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 30Pa, and reaction temperature controls at 280 DEG C, instead 90 minutes between seasonable, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester 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 compositions, 2- decyl -1,6 hexylene glycol segments are 5% with the Mole percent ratio of ethylene glycol segment.
Embodiment 14
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.47 terephthalic acid (TPA) and 2- nonyl -1,6 hexylene glycols are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of 0.47% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 220 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.8 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27MPa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Measure for terephthalic acid (TPA) weight 0.04% catalyst glycol antimony and addition be the 0.04% of terephthalic acid (TPA) weight In the presence of stabilizer trimethyl phosphate, under conditions of negative pressure start the low vacuum stage polycondensation reaction, this staged pressure by Normal pressure is steadily evacuated to absolute pressure 460Pa, and at 263 DEG C, the reaction time is 47 minutes to temperature control；Then proceed to vacuumize, enter The polycondensation reaction of row high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 278 DEG C, during reaction Between 85 minutes, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 28000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- nonyl Base -1,6 hexylene glycol segment compositions, 2- nonyl -1,6 hexylene glycol segments are 4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 15
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.46 terephthalic acid (TPA) and 2- octyl group -1,6 hexylene glycols are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of 0.49% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 233 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.8 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 259 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.5% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 19 minutes is adding Entering 0.044% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight Under conditions of negative pressure, in the presence of 0.046% stabilizer triphenyl phosphate, start the polycondensation reaction in low vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 269 DEG C, the reaction time is 48 minutes to temperature control；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 279 DEG C, 87 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 29000, pungent by terephthalic acid (TPA) segment, ethylene glycol segment and 2- Base -1,6 hexylene glycol segment compositions, 2- octyl group -1,6 hexylene glycol segments are 4.5% with the Mole percent ratio of ethylene glycol segment.
Embodiment 16
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.49 terephthalic acid (TPA) and 2- heptyl -1,6 hexylene glycols are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of 0.48% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 230 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.8 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.7% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 19 minutes is adding Entering 0.048% catalyst glycol antimony that amount is terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight Under conditions of negative pressure, in the presence of 0.047% stabilizer triphenyl phosphate, start the polycondensation reaction in low vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 460Pa by normal pressure, and at 267 DEG C, the reaction time is 48 minutes to temperature control；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 279 DEG C, 83 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 27000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- heptan Base -1,6 hexylene glycol segment compositions, 2- heptyl -1,6 hexylene glycol segments are 4.7% with the Mole percent ratio of ethylene glycol segment.
Embodiment 17
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.467 terephthalic acid (TPA) and 2- hexyl -1,6 hexylene glycols are made into slurry and add in reactor, It is 60wt% in concentration, addition is under the catalytic action of 0.47% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27MPa, and temperature is 236 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.89 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 258 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.3% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Entering 0.04% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight Under conditions of negative pressure, in the presence of 0.041% stabilizer Trimethyl phosphite, start the polycondensation reaction in low vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 268 DEG C, the reaction time is 48 minutes to temperature control；Then proceed to Vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 40Pa, reaction temperature controls 278 DEG C, 85 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 29000, own by terephthalic acid (TPA) segment, ethylene glycol segment and 2- Base -1,6 hexylene glycol segment compositions, 2- hexyl -1,6 hexylene glycol segments are 4.3% with the Mole percent ratio of ethylene glycol segment.
Embodiment 18
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.48 terephthalic acid (TPA) and 2- amyl group -1,6 hexylene glycols are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of 0.46% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 230 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.88 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 256 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.7% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Entering 0.047% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight Under conditions of negative pressure, in the presence of 0.047% stabilizer triphenyl phosphate, start the polycondensation reaction in low vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 480Pa by normal pressure, and at 265 DEG C, the reaction time is 47 minutes to temperature control；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 279 DEG C, 85 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 28000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- penta Base -1,6 hexylene glycol segment compositions, 2- amyl group -1,6 hexylene glycol segments are 4.7% with the Mole percent ratio of ethylene glycol segment.
Embodiment 19
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.46 terephthalic acid (TPA) and 2- decyl -1,5 pentanediols are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of 0.47% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 238 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.9 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 259 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during more than the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.7% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 19 minutes is adding Entering the 0.046% catalyst acetic acid antimony that amount is terephthalic acid (TPA) weight and addition is the 0.048% of terephthalic acid (TPA) weight Stabilizer Trimethyl phosphite in the presence of, under conditions of negative pressure start the low vacuum stage polycondensation reaction, this stage press It is 446Pa that power is steadily evacuated to absolute pressure by normal pressure, and at 267 DEG C, the reaction time is 49 minutes to temperature control；Then proceed to take out very Sky, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 40Pa, and reaction temperature controls at 278 DEG C, 87 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment and the 2- last of the ten Heavenly stems Base -1,5 pentanediol segment compositions, 2- decyl -1,5 pentanediol segments are 4.7% with the Mole percent ratio of ethylene glycol segment.
Embodiment 20
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.46 terephthalic acid (TPA) and 2- nonyl -1,5 pentanediols are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of 0.46% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.26MPa, and temperature is 221 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.89 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.25MPa, and temperature is 259 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.1% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Entering 0.041% catalyst glycol antimony that amount is terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight Under conditions of negative pressure, in the presence of 0.042% stabilizer trimethyl phosphate, start the polycondensation reaction in low vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 460Pa by normal pressure, and at 265 DEG C, the reaction time is 47 minutes to temperature control；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 278 DEG C, 85 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 28000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- nonyl Base -1,5 pentanediol segment compositions, 2- nonyl -1,5 pentanediol segments are 4.1% with the Mole percent ratio of ethylene glycol segment.
Embodiment 21
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.43 terephthalic acid (TPA) and 2- octyl group -1,5 pentanediols are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of 0.47% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27MPa, and temperature is 235 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.78 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.26MPa, and temperature is 255 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.3% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 17 minutes is adding Entering 0.043% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight Under conditions of negative pressure, in the presence of 0.049% stabilizer triphenyl phosphate, start the polycondensation reaction in low vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 268 DEG C, the reaction time is 46 minutes to temperature control；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 275 DEG C, 85 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 28000, pungent by terephthalic acid (TPA) segment, ethylene glycol segment and 2- Base -1,5 pentanediol segment compositions, 2- octyl group -1,5 pentanediol segments are 4.3% with the Mole percent ratio of ethylene glycol segment.
Embodiment 22
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.43 terephthalic acid (TPA) and 2- heptyl -1,5 pentanediols are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of 0.45% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.29MPa, and temperature is 235 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.87 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27MPa, and temperature is 255 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.6% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Entering 0.047% catalyst glycol antimony that amount is terephthalic acid (TPA) weight and addition is the 0.04% of terephthalic acid (TPA) weight Stabilizer triphenyl phosphate in the presence of, under conditions of negative pressure start the low vacuum stage polycondensation reaction, this staged pressure Absolute pressure 470Pa is steadily evacuated to by normal pressure, at 268 DEG C, the reaction time is 45 minutes to temperature control；Then proceed to vacuumize, Carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 40Pa, reaction temperature controls at 279 DEG C, reaction 83 minutes time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- heptan Base -1,5 pentanediol segment compositions, 2- heptyl -1,5 pentanediol segments are 4.6% with the Mole percent ratio of ethylene glycol segment.
Embodiment 23
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.457 terephthalic acid (TPA) and 2- hexyl -1,5 pentanediols are made into slurry and add in reactor, It is 55% in concentration, addition is under the catalytic action of 0.46% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 239 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.81 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27MPa, and temperature is 255 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.41% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 19 minutes, Addition is 0.042% the catalytic antimony trioxide of terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight Under conditions of negative pressure, in the presence of 0.048% stabilizer Trimethyl phosphite, start the polycondensation reaction in low vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the reaction time is 45 minutes to temperature control；Then proceed to Vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 50Pa, reaction temperature controls 275 DEG C, 85 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 28000, own by terephthalic acid (TPA) segment, ethylene glycol segment and 2- Base -1,5 pentanediol segment compositions, 2- hexyl -1,5 pentanediol segments are 4.41% with the Mole percent ratio of ethylene glycol segment.
Embodiment 24
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.47 terephthalic acid (TPA) and 2- amyl group -1,5 pentanediols are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of 0.48% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27MPa, and temperature is 245 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.81 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27MPa, and temperature is 259 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.67% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 19 minutes, Addition is 0.041% the catalytic antimony trioxide of terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight Under conditions of negative pressure, in the presence of 0.042% stabilizer triphenyl phosphate, start the polycondensation reaction in low vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 485Pa by normal pressure, and at 268 DEG C, the reaction time is 46 minutes to temperature control；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50Pa, and reaction temperature controls at 275 DEG C, 89 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- penta Base -1,5 pentanediol segment compositions, 2- amyl group -1,5 pentanediol segments are 4.67% with the Mole percent ratio of ethylene glycol segment.
Embodiment 25
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.45 terephthalic acid (TPA) and 2- hexyl -1,5 pentanediol and 2- amyl group -1,4 butanediol mixed Compound is made into slurry and adds in reactor, wherein 2- hexyl -1, and the mol ratio of 5 pentanediols and 2- amyl group-Isosorbide-5-Nitrae butanediol is 3:1, It is 55% in concentration, addition is under the catalytic action of 0.49% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.26MPa, and temperature is 236 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.8 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.4% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Entering 0.042% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight Under conditions of negative pressure, in the presence of 0.047% stabilizer Trimethyl phosphite, start the polycondensation reaction in low vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the reaction time is 49 minutes to temperature control；Then proceed to Vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 50Pa, reaction temperature controls 278 DEG C, 88 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester be 29000, by terephthalic acid (TPA) segment, ethylene glycol segment, 2- hexyl- 1,5 pentanediol segment and 2- amyl group-Isosorbide-5-Nitrae butanediol segment composition, 2- hexyl -1,5 pentanediol segments and 2- amyl group-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：
Mol ratio is 1:2- octyl group -1,6 hexylene glycol of 1.45 terephthalic acid (TPA) sum and 2- amyl group -1,5 pentanediol Mixture is made into slurry and adds in reactor, wherein 2- octyl group -1,6 hexylene glycols and 2- amyl group -1, and the mol ratio of 5 pentanediols is 3: 2, it is 60% in concentration, addition is under the catalytic action of 0.45% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 239 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.84 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.29MPa, and temperature is 255 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.6% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Entering 0.0423% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight Under conditions of negative pressure, in the presence of 0.045% stabilizer Trimethyl phosphite, start the polycondensation reaction in low vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the reaction time is 45 minutes to temperature control；Then proceed to Vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 50Pa, reaction temperature controls 278 DEG C, 85 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester be 28000, by terephthalic acid (TPA) segment, ethylene glycol segment, 2- octyl group- 1,6 hexylene glycol segment and 2- amyl group -1,5 pentanediol segment compositions, 2- octyl group -1,6 hexylene glycol segments and 2- amyl group -1,5 penta 2 Alcohol segment is 4.6% with the Mole percent ratio of ethylene glycol segment.
Embodiment 27
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.45 terephthalic acid (TPA) and 2- hexyl -1,5 pentanediol and 2- amyl group -1,4 butanediol mixed Compound is made into slurry and adds in reactor, wherein 2- hexyl -1, and the mol ratio of 5 pentanediols and 2- amyl group-Isosorbide-5-Nitrae butanediol is 3:1, It is 55% in concentration, addition is under the catalytic action of 0.49% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.26MPa, and temperature is 236 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 96% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.8 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.4% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Entering 0.042% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight Under conditions of negative pressure, in the presence of 0.047% stabilizer Trimethyl phosphite, start the polycondensation reaction in low vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the reaction time is 49 minutes to temperature control；Then proceed to Vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 50Pa, reaction temperature controls 278 DEG C, 88 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester be 29000, by terephthalic acid (TPA) segment, ethylene glycol segment, 2- hexyl- 1,5 pentanediol segment and 2- amyl group-Isosorbide-5-Nitrae butanediol segment composition, 2- hexyl -1,5 pentanediol segments and 2- amyl group-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：
Mol ratio is 1:1.45 terephthalic acid (TPA) is own with 2- octyl group -1,3 propane diols, 2- amyl group -1,4 butanediol and 2- Base -1, the mixture of 6 hexylene glycols is made into slurry and adds in reactor, wherein 2- octyl group -1,3 propane diols, 2- amyl group-Isosorbide-5-Nitrae fourth two The mol ratio of alcohol and 2- hexyl -1,6 hexylene glycol is 3:2:1, it is 60% in concentration, addition is terephthalic acid (TPA) weight Under the catalytic action of 0.47% concentrated sulfuric acid, carry out esterification, esterification compressive reaction in nitrogen atmosphere, moulding pressure 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：
Mol ratio is 1:1.8 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27MPa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.71% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, Addition is 0.04% the catalytic antimony trioxide of terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight Under conditions of negative pressure, in the presence of 0.041% stabilizer Trimethyl phosphite, start the polycondensation reaction in low vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 268 DEG C, the reaction time is 49 minutes to temperature control；Then proceed to Vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 50Pa, reaction temperature controls 277 DEG C, 84 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment, band side chain Glycol segment composition, wherein branched glycol segment be 2- octyl group -1,3 propane diols segments, 2- amyl group-Isosorbide-5-Nitrae butanediol chain Section and 2- hexyl -1,6 hexylene glycol segments form, and branched glycol segment with the Mole percent ratio of ethylene glycol segment is 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 obtained using porous spinneret, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to spinneret The hole in hole is centrally located on concentration ellipse, and concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear.
As shown in figure 1, the major axis of ellipse is 1.3 with the ratio of minor axis length, the spacing of adjacent spinneret orifice is equal to spinneret orifice Guide hole diameter add 1.5mm, spinneret is circular spinneret, the diameter of circular spinneret oval maximum long axial length with series The difference of degree is 11mm, a diameter of 2.0mm of guide hole of spinneret orifice, and the spinneret hole count of spinneret is 374, the spinneret orifice of spinneret Shape of cross section be circle.
The modified poly ester that embodiment 1 is obtained is extruded, cools down, oils, is drawn through solid phase polycondensation thickening, metering, porous spinneret Stretch, thermal finalization and winding, prepared high uniformity high intensity low shrinkage type polyester industrial fiber, the wherein temperature of extrusion be 280 DEG C, cooling Wind-warm syndrome is 20 DEG C, GR-1 speed 480m/min；Temperature is normal 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 prepared high uniformity high intensity low shrinkage type polyester industrial fiber is 7.9cN/dtex；Line density deviation ratio For 0.6%, fracture strength CV value is 1.8%, and extension at break CV value is 4.5%, and extension at break is 11.0, at 260 DEG C, melt Viscosity declines 11%, and under the test condition for 177 DEG C × 10min × 0.05cN/dtex for the temperature, dry-hot shrinkage is 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 obtained using porous spinneret, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to spinneret The hole in hole is centrally located on concentration ellipse, and concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear.
As shown in figure 3, the major axis of ellipse is 1.6 with the ratio of minor axis length, the spacing of adjacent spinneret orifice is equal to spinneret orifice Guide hole diameter add 1.5mm, spinneret is circular spinneret, the diameter of circular spinneret oval maximum long axial length with series The difference of degree is 11mm, a diameter of 2.0mm of guide hole of spinneret orifice, and the spinneret hole count of spinneret is 382, the spinneret orifice of spinneret Shape of cross section be circle.
The modified poly ester that embodiment 1 is obtained is extruded, cools down, oils, is drawn through solid phase polycondensation thickening, metering, porous spinneret Stretch, thermal finalization and winding, prepared high uniformity high intensity low shrinkage type polyester industrial fiber, the wherein temperature of extrusion be 280 DEG C, cooling Wind-warm syndrome is 20 DEG C, GR-1 speed 480m/min；Temperature is normal 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 prepared high uniformity high intensity low shrinkage type polyester industrial fiber is 7.8cN/dtex；Line density deviation ratio For 0.7%, fracture strength CV value is 1.7%, and extension at break CV value is 4.8%, and extension at break is 11.0, at 260 DEG C, melt Viscosity declines 11%, and under the test condition for 177 DEG C × 10min × 0.05cN/dtex for the temperature, dry-hot shrinkage is 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 obtained using porous spinneret, and on spinneret, the arrangement mode of spinneret orifice is circular arrangement, and circular arrangement refers to spinneret orifice Hole is centrally located on concentric circles, and concentric circles is that series is circular.As shown in Fig. 2 the spacing of adjacent spinneret orifice is equal to leading of spinneret orifice Bore dia adds 1.5mm, and spinneret is circular spinneret, the difference of the diameter of circular spinneret and the circular maximum diameter of series For 11mm, a diameter of 2.0mm of guide hole of spinneret orifice, the spinneret hole count of spinneret is 370, the cross section of the spinneret orifice of spinneret Generally circular in shape.
The modified poly ester that embodiment 1 is obtained is extruded, cools down, oils, is drawn through solid phase polycondensation thickening, metering, porous spinneret Stretch, thermal finalization and winding, prepared high uniformity high intensity low shrinkage type polyester industrial fiber, the wherein temperature of extrusion be 280 DEG C, cooling Wind-warm syndrome is 20 DEG C, GR-1 speed 480m/min；Temperature is normal 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 prepared high uniformity high intensity low shrinkage type polyester industrial fiber is 7.6cN/dtex；Line density deviation ratio For 1%, fracture strength CV value is 1.9%, and extension at break CV value is 5.3%, and extension at break is 11.1, and at 260 DEG C, melt glues Degree decline 11%, under the test condition for 177 DEG C × 10min × 0.05cN/dtex for the temperature, dry-hot shrinkage is 8.5%.
When identical with the effective area that embodiment 29 contrast can be seen that spinneret, (circular arrangement when spinneret hole count is close Spinneret hole count is 370, and oval shaped arrangements spinneret hole count is 374), the spinneret orifice number of plies of oval shaped arrangements is 6, less than circular arrangement The spinneret orifice number of plies 8, cooling effect is more preferable；When identical with the effective area that embodiment 30 contrast can be seen that spinneret, oval The spinneret orifice number of plies of shape arrangement is 5, and less than the spinneret orifice number of plies 8 of circular arrangement, cooling effect is more preferable, the spinneret of oval shaped arrangements The hole count 382 in hole is more than the hole count 370 of the spinneret orifice of circular arrangement, and cooling effectiveness is higher.The comparing result of fibre property shows, Fiber linear density deviation ratio that embodiment 29 and embodiment 30 are obtained, fracture strength CV value, extension at break CV value are less than comparative example 1, under the conditions of same process is described, it is better than adopting spinneret using the fibre property that the spinneret of spinneret orifice oval shaped arrangements is obtained 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 obtained using porous spinneret, spinneret The arrangement mode of upper spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located on concentration ellipse, with The heart is oval oval for series, and all oval major axis are conllinear, and short axle is conllinear.
Spinneret orifice be arranged as long axial symmetry, oval major axis is 1.4 with the ratio of minor axis length, between adjacent spinneret orifice Add 1.6mm away from the guide hole diameter equal to spinneret orifice, spinneret is circular spinneret, the diameter of circular spinneret is oval with series 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 shape of cross section of the spinneret orifice of plate is square.
High uniformity high intensity low shrinkage type polyester industrial fiber is extruded, cools down, oiling, stretching through metering, porous spinneret, heat is fixed Type and winding, prepared high uniformity high intensity low shrinkage type polyester industrial fiber, the wherein temperature of extrusion are 300 DEG C, and the wind-warm syndrome of cooling is 25℃；Stretching, heat setting process parameter are：GR-1 speed 600m/min；Temperature is normal 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.
At 280 DEG C, melt viscosity declines percentage to prepared high uniformity high intensity low shrinkage type polyester industrial fiber, under normal temperature The mechanical performance data of industrial yarn, and under the test condition for 177 DEG C × 10min × 0.05cN/dtex for the temperature, 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 obtained using porous spinneret, spinneret The arrangement mode of upper spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located on concentration ellipse, with The heart is oval oval for series, and all oval major axis are conllinear, and short axle is conllinear.
Spinneret orifice be arranged as long axial symmetry, oval major axis is 1.4 with the ratio of minor axis length, between adjacent spinneret orifice Add 1.6mm away from the guide hole diameter equal to spinneret orifice, spinneret is circular spinneret, the diameter of circular spinneret is oval with series 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 shape of cross section of the spinneret orifice of plate is square.
High uniformity high intensity low shrinkage type polyester industrial fiber is extruded, cools down, oiling, stretching through metering, porous spinneret, heat is fixed Type and winding, prepared high uniformity high intensity low shrinkage type polyester industrial fiber, the wherein temperature of extrusion are 310 DEG C, and the wind-warm syndrome of cooling is 30℃；Stretching, heat setting process parameter are：GR-1 speed 500m/min；Temperature is normal 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.
Prepared high uniformity high intensity low shrinkage type polyester industrial fiber melt viscosity at 290 DEG C declines percentage, under normal temperature The mechanical performance data of industrial yarn, and under the test condition for 177 DEG C × 10min × 0.05cN/dtex for the temperature, 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 obtained using porous spinneret.
Spinneret orifice be arranged as long axial symmetry, oval major axis is 1.4 with the ratio of minor axis length, between adjacent spinneret orifice Add 1.6mm away from the guide hole diameter equal to spinneret orifice, spinneret is circular spinneret, the diameter of circular spinneret is oval with series 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 shape of cross section of the spinneret orifice of plate is square.
High uniformity high intensity low shrinkage type polyester industrial fiber is extruded, cools down, oiling, stretching through metering, porous spinneret, heat is fixed Type and winding, prepared high uniformity high intensity low shrinkage type polyester industrial fiber, the wherein temperature of extrusion are 290 DEG C, and the wind-warm syndrome of cooling is 20℃；Stretching, heat setting process parameter are：GR-1 speed 500m/min；Temperature is normal 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.
Prepared high uniformity high intensity low shrinkage type polyester industrial fiber melt viscosity at 270 DEG C declines percentage, under normal temperature The mechanical performance data of industrial yarn, and under the test condition for 177 DEG C × 10min × 0.05cN/dtex for the temperature, 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 obtained using porous spinneret.
Spinneret orifice be arranged as long axial symmetry, oval major axis is 1.4 with the ratio of minor axis length, between adjacent spinneret orifice Add 1.6mm away from the guide hole diameter equal to spinneret orifice, spinneret is circular spinneret, the diameter of circular spinneret is oval with series 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 shape of cross section of the spinneret orifice of plate is square.
High uniformity high intensity low shrinkage type polyester industrial fiber is extruded, cools down, oiling, stretching through metering, porous spinneret, heat is fixed Type and winding, prepared high uniformity high intensity low shrinkage type polyester industrial fiber, the wherein temperature of extrusion are 300 DEG C, and the wind-warm syndrome of cooling is 25℃；Stretching, heat setting process parameter are：GR-1 speed 600m/min；Temperature is normal 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.
Prepared high uniformity high intensity low shrinkage type polyester industrial fiber melt viscosity at 260 DEG C declines percentage, under normal temperature The mechanical performance data of industrial yarn, and under the test condition for 177 DEG C × 10min × 0.05cN/dtex for the temperature, 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 obtained using porous spinneret.
Spinneret orifice be arranged as long axial symmetry, oval major axis is 1.4 with the ratio of minor axis length, between adjacent spinneret orifice Add 1.6mm away from the guide hole diameter equal to spinneret orifice, spinneret is circular spinneret, the diameter of circular spinneret is oval with series 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 shape of cross section of the spinneret orifice of plate is square.
High uniformity high intensity low shrinkage type polyester industrial fiber is extruded, cools down, oiling, stretching through metering, porous spinneret, heat is fixed Type and winding, prepared high uniformity high intensity low shrinkage type polyester industrial fiber, the wherein temperature of extrusion are 290 DEG C, and the wind-warm syndrome of cooling is 30℃；Stretching, heat setting process parameter are：GR-1 speed 480m/min；Temperature is normal 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.
Prepared high uniformity high intensity low shrinkage type polyester industrial fiber at 280 DEG C, melt viscosity, the power of industrial yarn under normal temperature Learn performance data, and under the test condition for 177 DEG C × 10min × 0.05cN/dtex for the temperature, 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 obtained using porous spinneret.
Spinneret orifice be arranged as long axial symmetry, oval major axis is 1.4 with the ratio of minor axis length, between adjacent spinneret orifice Add 1.6mm away from the guide hole diameter equal to spinneret orifice, spinneret is circular spinneret, the diameter of circular spinneret is oval with series 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 shape of cross section of the spinneret orifice of plate is square.
High uniformity high intensity low shrinkage type polyester industrial fiber is extruded, cools down, oiling, stretching through metering, porous spinneret, heat is fixed Type and winding, prepared high uniformity high intensity low shrinkage type polyester industrial fiber, the wherein temperature of extrusion are 310 DEG C, and the wind-warm syndrome of cooling is 25℃；Stretching, heat setting process parameter are：GR-1 speed 580m/min；Temperature is normal 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.
Prepared high uniformity high intensity low shrinkage type polyester industrial fiber melt viscosity at 280 DEG C declines percentage, under normal temperature The mechanical performance data of industrial yarn, and under the test condition for 177 DEG C × 10min × 0.05cN/dtex for the temperature, 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 obtained using porous spinneret.
Spinneret orifice be arranged as long axial symmetry, oval major axis is 1.4 with the ratio of minor axis length, between adjacent spinneret orifice Add 1.6mm away from the guide hole diameter equal to spinneret orifice, spinneret is circular spinneret, the diameter of circular spinneret is oval with series 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 shape of cross section of the spinneret orifice of plate is square.
High uniformity high intensity low shrinkage type polyester industrial fiber is extruded, cools down, oiling, stretching through metering, porous spinneret, heat is fixed Type and winding, prepared high uniformity high intensity low shrinkage type polyester industrial fiber, the wherein temperature of extrusion are 310 DEG C, and the wind-warm syndrome of cooling is 30℃；Stretching, heat setting process parameter are：GR-1 speed 480m/min；Temperature is normal 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.
Prepared high uniformity high intensity low shrinkage type polyester industrial fiber melt viscosity at 280 DEG C, the power of industrial yarn under normal temperature Learn performance data, and under the test condition for 177 DEG C × 10min × 0.05cN/dtex for the temperature, 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 obtained using porous spinneret.
Spinneret orifice be arranged as long axial symmetry, oval major axis is 1.4 with the ratio of minor axis length, between adjacent spinneret orifice Add 1.6mm away from the guide hole diameter equal to spinneret orifice, spinneret is circular spinneret, the diameter of circular spinneret is oval with series 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 shape of cross section of the spinneret orifice of plate is square.
High uniformity high intensity low shrinkage type polyester industrial fiber is extruded, cools down, oiling, stretching through metering, porous spinneret, heat is fixed Type and winding, prepared high uniformity high intensity low shrinkage type polyester industrial fiber, the wherein temperature of extrusion are 310 DEG C, and the wind-warm syndrome of cooling is 20℃；Stretching, heat setting process parameter are：GR-1 speed 600m/min；Temperature is normal temperature；GR-2 speed 1000m/min；Temperature 80℃；GR-3 speed 1800～2500m/min；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.
Prepared high uniformity high intensity low shrinkage type polyester industrial fiber melt viscosity at 280 DEG C declines percentage, under normal temperature The mechanical performance data of industrial yarn, and under the test condition for 177 DEG C × 10min × 0.05cN/dtex for the temperature, industrial yarn Dry-hot shrinkage such as following table.

Claims (10)

1. a kind of high uniformity high intensity low shrinkage type polyester industrial fiber, is characterized in that：Described high uniformity high intensity low shrinkage type polyester work By modified poly ester, spinning after solid-phase tack producing obtains industry silk；The material of described high uniformity high intensity low shrinkage type polyester industrial fiber is modification Polyester, described modified poly ester form by terephthalic acid (TPA) segment, ethylene glycol segment and containing the dihydroxylic alcohols segment of side chain, described containing The dihydroxylic alcohols segment of chain refers to that side chain is located on one of dihydroxylic alcohols segment non-end group carbon and side chain is former containing 5-10 carbon The dihydroxylic alcohols segment of the linear carbon chain of son；Fracture strength >=the 7.5cN/ of described high uniformity high intensity low shrinkage type polyester industrial fiber Dtex, line density deviation ratio≤1.0%, fracture strength CV value≤2.0%, extension at break CV value≤5.5%；Described high uniformity High intensity low shrinkage type polyester industrial fiber at 260～290 DEG C, melt viscosity decline 10-20%, temperature be 177 DEG C × 10min × Under the test condition of 0.05cN/dtex, dry-hot shrinkage is 8.5 ± 1.5%.
2. a kind of high uniformity high intensity low shrinkage type polyester industrial fiber according to claim 1 is it is characterised in that described 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 described modified poly ester is 15000-30000.
3. a kind of high uniformity high intensity low shrinkage type polyester industrial fiber according to claim 1 it is characterised in that described containing The dihydroxylic alcohols segment of chain is 2- amyl group -1,3 propane diols segment, 2- hexyl -1,3 propane diols segment, 2- heptyl -1,3 propane diols chain Section, 2- octyl group -1,3 propane diols segment, 2- nonyl -1,3 propane diols segment, 2- decyl -1,3 propane diols segment, 2- amyl group -1,4 Butanediol segment, 2- hexyl -1,4 butanediol segment, 2- heptyl -1,4 butanediol segment, 2- octyl group -1,4 butanediol segment, 2- Nonyl -1,4 butanediol segment, 2- decyl -1,4 butanediol segment, 2- amyl group -1,5 pentanediol segment, 2- hexyl -1,5 pentanediol Segment, 2- heptyl -1,5 pentanediol segment, 2- octyl group -1,5 pentanediol segment, 2- nonyl -1,5 pentanediol segment, 2- decyl -1, 5 pentanediol segments, 2- amyl group -1,6 hexylene glycol segment, 2- hexyl -1,6 hexylene glycol segment, 2- heptyl -1,6 hexylene glycol segment, 2- One or more of octyl group -1,6 hexylene glycol segment, 2- nonyl -1,6 hexylene glycol segment or 2- decyl -1,6 hexylene glycol segment；Institute The dihydroxylic alcohols segment stated containing side chain is 2～5% with the Mole percent ratio of ethylene glycol segment.
4. the preparation method of a kind of high uniformity high intensity low shrinkage type polyester industrial fiber as any one of claim 1-3, It is characterized in that：By modified poly ester through solid phase polycondensation thickening, metering, porous spinneret extrude, cool down, oiling, stretching, thermal finalization and Winding, prepared high uniformity high intensity low shrinkage type polyester industrial fiber；
On described porous spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and described oval shaped arrangements refer to the hole of spinneret orifice It is centrally located on concentration ellipse, described concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear；
The preparation process of modified poly ester comprises the following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Terephthalic acid (TPA) is made into after slurry with the dihydroxylic alcohols containing side chain, under the catalytic action of the concentrated sulfuric acid, carries out esterification, Obtain terephthalic acid (TPA) binary alcohol esters；The described dihydroxylic alcohols containing side chain is that side chain is located at one of dihydroxylic alcohols segment non-end group carbon Upper and side chain is the dihydroxylic alcohols of the linear carbon chain containing 5-10 carbon atom；
(2) preparation of ethylene glycol terephthalate：
Terephthalic acid (TPA) and ethylene glycol are made into after slurry, carry out esterification, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), stirring is mixed Close, in the presence of catalyst and stabilizer, under conditions of negative pressure, carry out polycondensation reaction and the Gao Zhen in low vacuum stage successively The polycondensation reaction in empty stage, prepared modified poly ester.
5. the preparation method of high uniformity high intensity low shrinkage type polyester industrial fiber according to claim 4 is it is characterised in that institute State concretely comprising the following steps of modified poly ester preparation：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Terephthalic acid (TPA) and the dihydroxylic alcohols containing side chain are made into slurry add in reactor, under the catalytic action of the concentrated sulfuric acid, enter Row esterification, esterification compressive reaction in nitrogen atmosphere, moulding pressure is normal pressure～0.3MPa, and temperature is 180～240 DEG C, it is esterification terminal when the water quantity of distillate in esterification reaches more than the 90% of theoretical value；Obtain terephthalic acid (TPA) Binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Terephthalic acid (TPA) and ethylene glycol are made into after slurry and add in reactor, carry out esterification, esterification is in blanket of nitrogen Enclose middle compressive reaction, 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 more than 90% when be esterification terminal, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), stirring is mixed Close 15-20 minute, under conditions of negative pressure, in the presence of catalyst and stabilizer, start the polycondensation reaction in low vacuum stage, This staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature control at 260～270 DEG C, the reaction time be 30～ 50 minutes；Then proceed to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure and be less than 100Pa, reaction temperature controls at 275～280 DEG C, 50～90 minutes reaction time, prepared modified poly ester；
Again modified poly ester is obtained Modified polyester chips through pelletizing, obtained polyester slice is viscosified by solid phase polycondensation, makes polyester The inherent viscosity of section brings up to 1.0～1.2dL/g, as high viscous section；Again through metering, porous spinneret extrusion, cooling, on Oil, stretching, thermal finalization and winding, prepared high uniformity high intensity low shrinkage type polyester industrial fiber；
Spinning main technologic parameters are：
The temperature of described extrusion is 290～310 DEG C；
The wind-warm syndrome of described cooling is 20～30 DEG C；
Described stretching, heat setting process parameter are：
GR-1 speed 480～600m/min；Temperature is normal temperature；
GR-2 speed 500～1000m/min；80～100 DEG C of temperature；
GR-3 speed 1800～2500m/min；100～150 DEG C of temperature；
GR-4 speed 2800～3500m/min；200～250 DEG C of temperature；
GR-5 speed 2800～3500m/min；200～250 DEG C of temperature；
GR-6 speed 2600～3400m/min；150～220 DEG C of temperature；
The speed of described winding is 2600～3400m/min.
6. the preparation method of a kind of high uniformity high intensity low shrinkage type polyester industrial fiber according to claim 5, its feature exists In, in described step (1), terephthalic acid (TPA) is 1 with the mol ratio of the dihydroxylic alcohols containing side chain:1.3-1.5；Concentrated sulfuric acid addition is The 0.3-0.5% of terephthalic acid (TPA) weight；The concentration of the described concentrated sulfuric acid is 50-60wt%；In described step (2), terephthaldehyde Acid is 1 with the mol ratio of ethylene glycol:1.2～2.0；In described step (3), described terephthalic acid (TPA) binary alcohol esters and terephthaldehyde The Mole percent ratio of sour glycol ester is 2～5%；Described catalyst is antimony oxide, antimony glycol or antimony acetate, catalysis Agent addition is the 0.01%～0.05% of terephthalic acid (TPA) gross weight；Described stabilizer is triphenyl phosphate, trimethyl phosphate Or Trimethyl phosphite, stabilizer addition is the 0.01%～0.05% of described terephthalic acid (TPA) gross weight.
7. the preparation method of a kind of high uniformity high intensity low shrinkage type polyester industrial fiber according to claim 5, its feature exists In the described dihydroxylic alcohols containing side chain is 2- amyl group -1,3 propane diols, 2- hexyl -1,3 propane diols, 2- heptyl -1,3 propane diols, 2- Octyl group -1,3 propane diols, 2- nonyl -1,3 propane diols, 2- decyl -1,3 propane diols, 2- amyl group -1,4 butanediol, 2- hexyl -1,4 Butanediol, 2- heptyl -1,4 butanediol, 2- octyl group -1,4 butanediol, 2- nonyl -1,4 butanediol, 2- decyl -1,4 butanediol, 2- Amyl group -1,5 pentanediol, 2- hexyl -1,5 pentanediol, 2- heptyl -1,5 pentanediol, 2- octyl group -1,5 pentanediol, 2- nonyl -1,5 Pentanediol, 2- decyl -1,5 pentanediols, 2- amyl group -1,6 hexylene glycols, 2- hexyl -1,6 hexylene glycols, 2- heptyl -1,6 hexylene glycols, 2- One or more of octyl group -1,6 hexylene glycol, 2- nonyl -1,6 hexylene glycol or 2- decyl -1,6 hexylene glycol.
8. the preparation method of a kind of high uniformity high intensity low shrinkage type polyester industrial fiber according to claim 4, its feature exists In described porous spinneret is circular spinneret or elliptical spinneret plate；The diameter of described circle spinneret is with serial ellipse The difference of big long axis length is more than 10mm, and described elliptical spinneret plate is more than with the difference of the oval maximum long axis length of series 10mm.
9. the preparation method of a kind of high uniformity high intensity low shrinkage type polyester industrial fiber according to claim 4, its feature exists In, on described porous spinneret spinneret orifice be arranged as that major axis and/or short axle are symmetrical, the spacing of adjacent spinneret orifice is more than or equal to spray The guide hole diameter in silk hole adds 1.5mm；Oval major axis is 1.3～1.8 with the ratio of minor axis length.
10. the preparation method of a kind of high uniformity high intensity low shrinkage type polyester industrial fiber according to claim 4, its feature exists In a diameter of 1.5～2.5mm of guide hole of described spinneret orifice；The spinneret hole count of described spinneret is more than or equal to 192, described spinneret The shape of cross section of the spinneret orifice of plate is circle, square, rhombus, yi word pattern, triangular form, trilobal cross, hollow type or flat Type.
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