CN106283250A - A kind of high-strength ultralow miniature polyester industrial fiber of high uniformity and preparation method thereof - Google Patents

A kind of high-strength ultralow miniature polyester industrial fiber of high uniformity and preparation method thereof Download PDF

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CN106283250A
CN106283250A CN201610770671.5A CN201610770671A CN106283250A CN 106283250 A CN106283250 A CN 106283250A CN 201610770671 A CN201610770671 A CN 201610770671A CN 106283250 A CN106283250 A CN 106283250A
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segment
phthalic acid
preparation
miniature
modified poly
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CN106283250B (en
Inventor
范红卫
汤方明
宋光坤
赵慧荣
王山水
杨大矛
范晓兵
张元华
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Jiangsu Hengli Chemical Fiber Co Ltd
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Jiangsu Hengli Chemical Fiber Co Ltd
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D4/00—Spinnerette packs; Cleaning thereof
    • D01D4/02—Spinnerettes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods

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

Abstract

The present invention relates to a kind of high-strength ultralow miniature polyester industrial fiber of high uniformity and preparation method thereof, the raw material of the high-strength ultralow miniature polyester industrial fiber of high uniformity is the modified poly ester being made up of p-phthalic acid segment, ethylene glycol segment and the dihydroxylic alcohols segment containing side chain.The preparation method of the high-strength ultralow miniature polyester industrial fiber of high uniformity is by p-phthalic acid and the dihydroxylic alcohols containing side chain, in the catalysis of concentrated sulphuric acid, carries out esterification and obtains p-phthalic acid binary alcohol esters；Then p-phthalic acid and ethylene glycol are made into and carry out esterification, obtain ethylene glycol terephthalate；Finally both are stirred mixing, under the effect of catalyst and stabilizer, carry out the polycondensation reaction of coarse vacuum stage and high vacuum stage of Fig, prepare modified poly ester, modified poly ester extrude through metering, porous spinneret, cool down, oils, is stretched, thermal finalization and winding, the prepared high-strength ultralow miniature polyester industrial fiber of high uniformity.

Description

A kind of high-strength ultralow miniature polyester industrial fiber of high uniformity and preparation method thereof
Technical field
The invention belongs to polyester fiber technical field, relate to a kind of high-strength ultralow miniature polyester industrial fiber of high uniformity and system thereof Preparation Method.
Background technology
Polyethylene terephthalate (PET or polyester fiber) fiber from come out since, 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 from money, the advantages such as stiffness is good, be widely used in the field such as clothing, home textile.
Pet Industrial Fiber is primarily referred to as mostly being applied to industry, national defence, medical treatment, environmental conservation and most advanced branches of science each side Face, is to have the most 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 merit Energy.Using high-strength low-shrinkage polyester industrial filament yarn as the PVC shelter cloth of raw material production, there is higher peel strength and tear is strong Degree, makes shelter cloth be applicable to various uses, flexible body advertising lamp box material, inflatable structure material, fluffy lid architectural fabrics sunshade account Paulin etc..It is that main textile material obtains in terms of the military supplies such as special protective garment, camouflage, covering, knapsack with high-strength low-shrinkage industrial yarn To application.One as earth working material has the advantages such as light, soft, high-strength, wear-resisting, anticorrosive, non-conductive, damping.Make Used time safe ready, efficiency are high, and will not damage lifting object.The application of Pet Industrial Fiber is expanded and is driven application The whole competitiveness in field promotes, and no matter is alleviating the weight of composite, and the durability of use and minimizing are keeped in repair, 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 has considerable progress the most 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 the collection state structure of polyester macromolecule, the active force being mainly concerned with between polyester molecule, the form of crystallization and structure, alignment state Structure etc., and the form crystallized and structure are emphasis therein.Low-shrinkage high-strength PET industrial yarn, is the big class of in polyester, Owing to 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 have the advantages that chinlon is soft, and be therefore widely used neck Territory.It is (lamp house cloth, tent, shelter cloth, billboard, puggaree, waterproof that low-shrinkage high-strength PET industrial yarn is mainly used in coated fabric Cloth, Puffer-type swimming pool, roof drape, use for building, agriculture, 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 through the fiber controlling these parameters to prepare desired properties.Experimental branch line all uses side for a long time Blowing is as the type of cooling, and energy resource consumption accounts for the significant portion of long filament production cost, along with people are to chemical fibre performance and quality Requiring day by day to improve, the exploitation of chemical-fibres filaments new product develops to the fibre in differentiation direction of high added value, it is desirable to higher cold But dry condition, then propose ring blowing device.Ring blowing device not only possesses every uniform advantage of synnema wind-engaging, Er Qieneng Consumption is compared relatively low, effectively solves the wind energy loss problem that cross air blasting causes owing to 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: owing to spun silk is after circular jetting filament plate is extruded, by ring quenching, due to the circular jetting filament plate number of turns relatively It is many so that ring blowing hardly enters innermost layer, causes the silk at outermost silk innermost layer the most after cooling may be the most uncolled, Thus the problem such as the silk of gained occurs that fiber number is irregular, and intensity is irregular, cause and follow-up silk is processed further difficulty occur.
Summary of the invention
The technical problem to be solved in the present invention is for the deficiencies in the prior art, it is provided that a kind of high-strength ultralow contracting of high uniformity Type polyester industrial fiber and preparation method thereof, the raw material of the high-strength ultralow miniature polyester industrial fiber of high uniformity of the present invention is modified poly- Ester, introduces containing the dihydroxylic alcohols segment of side chain in the strand of modified poly ester, be modified modified high uniformity prepared by polyester high-strength Ultralow miniature polyester industrial fiber, under the conditions of uniform temperature, the high-strength ultralow miniature polyester industrial fiber interior molecules interchain of high uniformity The increasing degree of spatial joint clearance be far longer than the high-strength ultralow miniature polyester industrial fiber of unbranched high uniformity at equal temperature, The melt viscosity of the high-strength ultralow miniature polyester industrial fiber of high uniformity reduces, and reduces processing temperature, reduces degradation rate, is conducive to Processing.The additionally arrangement mode of spinneret orifice on the porous spinneret of the high-strength ultralow miniature polyester industrial fiber of the high uniformity of the present invention For oval shaped arrangements, oval shaped arrangements refers to that the hole of spinneret orifice is centrally located on concentration ellipse, and concentration ellipse is that series is oval, institute There are the major axis conllinear of ellipse, and short axle conllinear；Higher cooling effectiveness and preferable cooling effect can be reached.
A kind of high-strength ultralow miniature polyester industrial fiber of high uniformity, the high-strength ultralow miniature polyester industrial fiber of described high uniformity Obtained by modified poly ester spinning after solid-phase tack producing；The material of the high-strength ultralow miniature polyester industrial fiber of described high uniformity is modified poly- Ester, described modified poly ester is made up of p-phthalic acid segment, ethylene glycol segment and the dihydroxylic alcohols segment containing side chain, described containing side chain Dihydroxylic alcohols segment refer on the non-end group carbon that side chain is positioned in dihydroxylic alcohols segment and side chain is for containing 5-10 carbon atom The dihydroxylic alcohols segment of linear carbon chain；Fracture strength >=the 7.5cN/ of the high-strength ultralow miniature polyester industrial fiber of described high uniformity Dtex, line density deviation ratio≤1.0%, fracture strength CV value≤2.0%, extension at break CV value≤5.5%；Described high uniformity High-strength ultralow miniature polyester industrial fiber is at 260～290 DEG C, and melt viscosity declines 10-20%, is 177 DEG C × 10min in temperature Under the test condition of × 0.05cN/dtex, dry-hot shrinkage is 1.8 ± 0.25%；
Described melt viscosity declines the contrast referring to modified poly ester and normal polyester in mutually synthermal melt viscosity.
A kind of high-strength ultralow miniature polyester industrial fiber of high uniformity is modified poly ester, draws on modified poly ester macromole long-chain Enter the dihydroxylic alcohols segment containing side chain, and the length of side chain and quantity are on the impact of the crystal property of modified poly ester and flow behavior relatively Greatly, the shortest purpose not reaching polyester modification of branch lengths, the oversize meeting of length causes new entanglement, affects its flow behavior, when On the non-end group carbon that side chain is positioned in dihydroxylic alcohols segment and when side chain is the linear carbon chain containing 5-10 carbon atom, through changing The high-strength ultralow miniature polyester industrial fiber of a kind of high uniformity prepared by property polyester, under the conditions of uniform temperature, part in industrial yarn It is viscous that the increasing degree of the spatial joint clearance between subchain is far longer than unbranched industrial yarn at equal temperature, beneficially industrial yarn melt Degree reduces, it is simple to further process.
As preferred technical scheme:
A kind of high-strength ultralow miniature polyester industrial fiber of high uniformity as above, the high-strength ultralow miniature of described high uniformity The extension at break of polyester industrial fiber is 20.0 ± 1.5%, and the number-average molecular weight of described modified poly ester is 15000-30000.
A kind of high-strength ultralow miniature polyester industrial fiber of high uniformity as above, the described dihydroxylic alcohols segment containing side chain is 2-amyl group-1,3 propylene glycol segment, 2-hexyl-1,3 propylene glycol segment, 2-heptyl-1,3 propylene glycol segment, 2-octyl group-1,3 the third two Alcohol segment, 2-nonyl-1,3 propylene glycol segment, 2-decyl-1,3 propylene glycol 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 penta 2 Alcohol 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 hexanediol segments, 2-hexyl-1,6 hexanediol segment, 2-heptyl-1,6 hexanediol segment, 2-octyl group-1,6 hexanediol segment, More than one in 2-nonyl-1,6 hexanediol segment or 2-decyl-1,6 hexanediol segment；The described dihydroxylic alcohols segment containing side chain It is 2～5% with the Mole percent ratio of ethylene glycol segment.
The preparation method of the high-strength ultralow miniature polyester industrial fiber of a kind of high uniformity of the present invention, by modified poly ester through solid phase Condensation viscosity enhancing, metering, porous spinneret are extruded, cool down, oil, are stretched, thermal finalization and winding, prepare high uniformity high-strength ultralow Miniature polyester industrial fiber；
On described porous spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and described oval shaped arrangements refers to spinneret orifice Hole be centrally located on concentration ellipse, described concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear；
The preparation process of modified poly ester comprises the following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
After p-phthalic acid is made into slurry with the dihydroxylic alcohols containing side chain, under the catalytic action of concentrated sulphuric acid, it is esterified Reaction, obtains p-phthalic acid binary alcohol esters；The described dihydroxylic alcohols containing side chain is that be positioned in dihydroxylic alcohols segment one of side chain is non- On end group carbon and dihydroxylic alcohols that side chain is 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 existence of side chain, makes strand Spatial volume increases, and solvation diminishes, and in dihydroxylic alcohols, proton is difficult to dissociation so that the dihydroxylic alcohols containing side chain and terephthaldehyde The reactivity of acid, 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 the ratio that the dihydroxylic alcohols that impact is containing side chain is in polyester macromolecule, and then affect the performance of polyester.This Invention uses and first with p-phthalic acid, the dihydroxylic alcohols containing side chain is carried out esterification under the catalytic action of sulphuric acid, and its product exists Ethylene glycol and p phthalic acid esterification add after terminating, it is ensured that the stability of the dihydroxylic alcohols proportioning containing side chain.
(2) preparation of ethylene glycol terephthalate:
After p-phthalic acid and ethylene glycol are made into slurry, carry out esterification, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), stir Mix mixing, under the effect of catalyst and stabilizer, under conditions of negative pressure, carry out successively the coarse vacuum stage polycondensation reaction and The polycondensation reaction of high vacuum stage of Fig, prepares modified poly ester.
The preparation method of the high-strength ultralow miniature polyester industrial fiber of a kind of high uniformity as above, described modified poly ester system Standby concretely comprises the following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
P-phthalic acid and the dihydroxylic alcohols containing side chain are made into slurry and add in reactor, in the catalytic action of concentrated sulphuric acid Under, carrying out esterification, esterification is compressive reaction in nitrogen atmosphere, and 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 benzene two Formic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Adding in reactor after p-phthalic acid and ethylene glycol are made into slurry, carry out esterification, esterification is at nitrogen Atmosphere encloses middle compressive reaction, and moulding pressure is normal pressure～0.3MPa, and temperature is 250～260 DEG C, when the water in esterification distillates Amount reach theoretical value more than 90% time be esterification terminal, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), stir Mixing mixing 15-20 minute, under the effect of catalyst and stabilizer, the polycondensation starting the coarse 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 temperature controls at 260～270 DEG C, and the response time is 30～50 minutes；Then proceed to evacuation, 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, response time 50～90 minutes, prepares modified poly ester；
Again through pelletizing, modified poly ester being obtained Modified polyester chips, obtained polyester slice is viscosified by solid phase polycondensation, makes The intrinsic viscosity of polyester slice brings up to 1.0～1.2dL/g, is high viscous section；Again through metering, porous spinneret extrusion, cold But, oil, stretch, thermal finalization and winding, prepare the high-strength ultralow miniature polyester industrial fiber of high uniformity；
Spinning main technologic parameters is:
The temperature of described extrusion is 290～310 DEG C；
The pathogenic wind-warm of described cooling is 20～30 DEG C；
Described stretching, heat setting process parameter be:
GR-1 speed 480～600m/min；Temperature is room temperature；
GR-2 speed 500～1000m/min；Temperature 80～100 DEG C；
GR-3 speed 1800～2500m/min；Temperature 100～150 DEG C；
GR-4 speed 2800～3500m/min；Temperature 200～250 DEG C；
GR-5 speed 2800～3500m/min；Temperature 200～250 DEG C；
GR-6 speed 2600～3400m/min；Temperature 150～220 DEG C；
The speed of described winding is 2600～3400m/min.
The preparation method of the high-strength ultralow miniature polyester industrial fiber of a kind of high uniformity as above, in described step (1), P-phthalic acid is 1:1.3-1.5 with the mol ratio of the dihydroxylic alcohols containing side chain；Concentrated sulphuric acid addition is p-phthalic acid weight 0.3-0.5%；The concentration of described concentrated sulphuric acid is 50-60wt%；In described step (2), p-phthalic acid and ethylene glycol mole Ratio is 1:1.2～2.0；In described step (3), described p-phthalic acid 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 NSC 6513, surely Determine that agent addition is described p-phthalic acid gross weight 0.01%～0.05%.
The preparation method of the high-strength ultralow miniature polyester industrial fiber of a kind of high uniformity as above, described containing side chain two Unit's alcohol is 2-amyl group-1,3 propylene glycol, 2-hexyl-1,3 propylene glycol, 2-heptyl-1,3 propylene glycol, 2-octyl group-1,3 propylene glycol, 2- Nonyl-1,3 propylene glycol, 2-decyl-1,3 propylene glycol, 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 Pentanediol, 2-amyl group-1,6 hexanediol, 2-hexyl-1,6 hexanediol, 2-heptyl-1,6 hexanediol, 2-octyl group-1,6 hexanediol, 2- More than one in nonyl-1,6 hexanediol or 2-decyl-1,6 hexanediol.
The preparation method of the high-strength ultralow miniature polyester industrial fiber of a kind of high uniformity as above, described porous spinneret For circular jetting filament plate or elliptical spinneret plate；The difference of the long axis length that the diameter of described circular jetting filament plate is maximum with series ellipse More than 10mm, the difference of the long axis length that described elliptical spinneret plate is maximum with series ellipse is more than 10mm.
The preparation method of the high-strength ultralow miniature polyester industrial fiber of a kind of high uniformity as above, described porous spinneret Upper spinneret orifice be arranged as major axis and/or short axial symmetry, the spacing of adjacent spinneret orifice adds more than or equal to the guide hole diameter of spinneret orifice Upper 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, and 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, and spray Silk hole oval shaped arrangements is conducive to the cooling that ring is dried, and improves the cooling effectiveness of ring blowing, and the fibre property of preparation is the most excellent Good.Major axis is closer to 1 with the ratio of minor axis length, and ellipse is more similar to circle, 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 increases by 16% accordingly；Major axis and short axle When the ratio of length is 1.8, cooling effect improves relatively big, and individual pen hole count increases by 33%, in the case of identical hole count, the present invention accordingly Oval shaped arrangements reduce than the number of turns of conventional concentric circle best-fit, it is easy to cooling wind is saturating, 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 punching, the coldest But effect no longer raises.Therefore, the major axis that series is oval is 1.3～1.8 with the ratio of minor axis length, it is possible to reach higher cold But efficiency and preferable cooling effect.
The preparation method of the high-strength ultralow miniature polyester industrial fiber of a kind of high uniformity as above, leading of described spinneret orifice Bore dia is 1.5～2.5mm；The spray webbing hole count of described spinneret is more than or equal to 192, the spinneret orifice of described spinneret transversal Face is 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-strength ultralow miniature polyester industrial fiber of high uniformity of the present invention is modified poly ester, modified poly ester macromole In the dihydroxylic alcohols segment containing side chain that contains, when temperature is higher than vitrification point, side chain, prior to backbone motion, is modified polyester The free volume of the industrial yarn of preparation 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 easier to blow through dynamic analysis of spinning less than the number of plies of circular arrangement, ring blowing, dynamic analysis of spinning Cooling effect is more preferable, and the industrial yarn of preparation is the most more excellent.When the effective area of spinneret is identical, spinneret orifice oval shaped arrangements Hole count is more than the hole count of circular arrangement, and oval shaped arrangements is capable of cooling down greatly, significantly improves cooling effectiveness.
Beneficial effect:
The raw material of the high-strength ultralow miniature polyester industrial fiber of high uniformity of gained of the present invention is modified poly ester, and modified poly ester is big The dihydroxylic alcohols segment containing side chain contained in molecule, when temperature is higher than vitrification point, side chain, prior to backbone motion, makes freedom The increasing degree of volume is far longer than the characteristic of unbranched polyester macromolecule chain, and the increase of free volume advantageously reduces melt Viscosity, improves its processing characteristics.
The raw material of the high-strength ultralow miniature polyester industrial fiber of high uniformity of gained of the present invention is modified poly ester, two containing side chain Unit's alcohol segment introduce to the structural regularity of modified poly ester there is no big destruction, maintain the premium properties of polyester fiber.
On the high-strength ultralow miniature polyester industrial fiber spinneret of high uniformity of the present invention, the arrangement mode of spinneret orifice is oval Shape arranges, and when the effective area of spinneret is identical, the number of plies of spinneret orifice oval shaped arrangements is dried less than the number of plies of circular arrangement, ring Being easier to blow through dynamic analysis of spinning, the cooling effect of dynamic analysis of spinning is more preferable, and the fibre property of preparation is the most more excellent.
On the high-strength ultralow miniature polyester industrial fiber spinneret of high uniformity of the present invention, the arrangement mode of spinneret orifice is oval Shape arranges, and 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 Arrangement is capable of cooling down greatly, significantly improves cooling effectiveness.
Accompanying drawing explanation
Fig. 1 is the oval shaped arrangements figure of 374 spinneret orifices, and the aperture of spinneret orifice is 2.0mm, transverse and the length of 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, transverse and the length of short axle Degree ratio is 1.6.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is expanded on further.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 that the present invention lectures, art technology The present invention can be made various changes or modifications by personnel, and these equivalent form of values fall within the application appended claims equally and limited Fixed scope.
Embodiment 1
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.3 and 2-amyl group-1,3 propylene glycol are made into slurry and add in reactor, Concentration is 50wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.3% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is normal pressure, and temperature is 180 DEG C, when the water in esterification distillates Amount reach theoretical value 90% time be esterification terminal, obtain p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.2 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is normal pressure, and temperature is 250 DEG C, when the water in esterification distillates Amount reach theoretical value 90% time be esterification terminal, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 2% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 15 minutes, is adding The catalytic antimony trioxide and addition that amount is the 0.01% of p-phthalic acid gross weight are p-phthalic acid gross weight Under the effect of the stabilizer triphenyl phosphate of 0.01%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank It is 500Pa that section pressure is steadily evacuated to absolute pressure by normal pressure, and temperature controls at 260 DEG C, and the response time is 30 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 100Pa, and reaction temperature controls 275 DEG C, in 50 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 15000, and modified poly ester is by p-phthalic acid segment, ethylene glycol segment and 2-penta Base-1,3 propylene glycol 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 method of the modified poly ester of embodiment 2, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 16 minutes, in addition be The catalytic antimony trioxide of the 0.011% of p-phthalic acid gross weight and addition is p-phthalic acid gross weight 0.02% Stabilizer triphenyl phosphate effect under, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure Steadily be evacuated to absolute pressure 490Pa by normal pressure, temperature controls at 262 DEG C, and the response time is 31 minutes；Then proceed to evacuation, Carrying 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, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 16000, and modified poly ester is own by p-phthalic acid segment, ethylene glycol segment and 2- Base-1,3 propylene glycol segment compositions, 2-hexyl-1,3 propylene glycol segments are 2.1% with the Mole percent ratio of ethylene glycol segment.
Embodiment 3
The preparation method of the modified poly ester of embodiment 3, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 16 minutes, in addition be The catalytic antimony trioxide of the 0.03% of p-phthalic acid gross weight and addition is p-phthalic acid gross weight 0.02% Stabilizer triphenyl phosphate effect under, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure Steadily be evacuated to absolute pressure 498Pa by normal pressure, temperature controls at 263 DEG C, and the response time is 32 minutes；Then proceed to evacuation, Carrying 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, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 15900, and modified poly ester is by p-phthalic acid segment, ethylene glycol segment and 2-heptan Base-1,3 propylene glycol segment compositions, 2-heptyl-1,3 propylene glycol segments are 2.2% with the Mole percent ratio of ethylene glycol segment.
Embodiment 4
The preparation method of the modified poly ester of embodiment 4, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 17 minutes, in addition be The catalytic antimony trioxide of the 0.033% of p-phthalic acid gross weight and addition are p-phthalic acid gross weight Under the effect of the stabilizer triphenyl phosphate of 0.023%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank It is 497Pa that section pressure is steadily evacuated to absolute pressure by normal pressure, and temperature controls at 264 DEG C, and the response time is 33 minutes；Then proceed to Evacuation, 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 278 DEG C, in 58 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 15800, and modified poly ester is pungent by p-phthalic acid segment, ethylene glycol segment and 2- Base-1,3 propylene glycol segment compositions, 2-octyl group-1,3 propylene glycol segments are 2.3% with the Mole percent ratio of ethylene glycol segment.
Embodiment 5
The preparation method of the modified poly ester of embodiment 5, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 17 minutes, in addition be The catalytic antimony trioxide of the 0.034% of p-phthalic acid gross weight and addition are p-phthalic acid gross weight Under the effect of the stabilizer triphenyl phosphate of 0.024%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 34 minutes；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, in 59 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 15900, and modified poly ester is by p-phthalic acid segment, ethylene glycol segment and 2-nonyl Base-1,3 propylene glycol segment compositions, 2-nonyl-1,3 propylene glycol segments are 2.4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 6
The preparation method of the modified poly ester of embodiment 6, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 18 minutes, in addition be The catalytic antimony trioxide of the 0.035% of p-phthalic acid gross weight and addition are p-phthalic acid gross weight Under the effect of the stabilizer triphenyl phosphate of 0.025%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and temperature controls at 266 DEG C, and the response time is 35 minutes；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, in 60 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 16000, and modified poly ester is by p-phthalic acid segment, ethylene glycol segment and 2-last of the ten Heavenly stems Base-1,3 propylene glycol segment compositions, 2-decyl-1,3 propylene glycol segments are 2.5% with the Mole percent ratio of ethylene glycol segment.
Embodiment 7
The preparation method of the modified poly ester of embodiment 7, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 19 minutes, in addition be The catalytic antimony trioxide of the 0.036% of p-phthalic acid gross weight and addition are p-phthalic acid gross weight Under the effect of the stabilizer triphenyl phosphate of 0.025%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and temperature controls at 267 DEG C, and the response time is 36 minutes；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, in 61 minutes response time, prepare 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 method of the modified poly ester of embodiment 8, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 19 minutes, in addition be The catalytic antimony trioxide of the 0.036% of p-phthalic acid gross weight and addition are p-phthalic acid gross weight Under the effect of the stabilizer triphenyl phosphate of 0.025%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and temperature controls at 267 DEG C, and the response time is 36 minutes；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, in 61 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 17000, and modified poly ester is own by p-phthalic acid 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 method of the modified poly ester of embodiment 9, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 16 minutes, in addition be The catalyst glycol antimony of the 0.04% of p-phthalic acid gross weight and addition is p-phthalic acid gross weight 0.026% Under the effect of stabilizer trimethyl phosphate, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure by Normal pressure is steadily evacuated to absolute pressure 497Pa, and temperature controls at 268 DEG C, and the response time is 38 minutes；Then proceed to evacuation, 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, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 17000, and modified poly ester is by p-phthalic acid 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 method of the modified poly ester of embodiment 10, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 17 minutes, in addition be The catalyst glycol antimony of the 0.03% of p-phthalic acid gross weight and addition is p-phthalic acid gross weight 0.027% Under the effect of stabilizer trimethyl phosphate, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure by Normal pressure is steadily evacuated to absolute pressure 498Pa, and temperature controls at 269 DEG C, and the response time is 39 minutes；Then proceed to evacuation, 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, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 17000, and modified poly ester is pungent by p-phthalic acid 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 method of the modified poly ester of embodiment 11, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 18 minutes, in addition be The catalyst glycol antimony of the 0.04% of p-phthalic acid gross weight and addition is p-phthalic acid gross weight 0.03% Under the effect of stabilizer trimethyl phosphate, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure by Normal pressure is steadily evacuated to absolute pressure 497Pa, and temperature controls at 260 DEG C, and the response time is 40 minutes；Then proceed to evacuation, 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, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 18000, and modified poly ester is by p-phthalic acid 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 method of the modified poly ester of embodiment 12, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 18 minutes, in addition be The catalyst acetic acid antimony of the 0.038% of p-phthalic acid weight and addition is p-phthalic acid weight 0.03% stabilizer Under the effect of NSC 6513, starting the polycondensation reaction in coarse vacuum stage under conditions of negative pressure, this staged pressure is by normal pressure Steadily being evacuated to absolute pressure 497Pa, temperature controls at 265 DEG C, and the response time is 42 minutes；Then proceed to evacuation, 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 response time 70 minutes, prepare modified poly ester.
The number-average molecular weight of modified poly ester prepared is 26000, by p-phthalic acid segment, ethylene glycol segment and 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
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.5 and 2-decyl-1,6 hexanediol are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.5% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.3MPa, and temperature is 240 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:2.0 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.3MPa, and temperature is 260 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 5% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 20 minutes, is adding The catalyst acetic acid antimony of 0.05% that amount is p-phthalic acid weight and addition is p-phthalic acid weight 0.05% steady Determine under the effect of agent NSC 6513, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure by It is 450Pa that normal pressure is steadily evacuated to absolute pressure, and temperature controls at 270 DEG C, and the response time is 50 minutes；Then proceed to evacuation, Carrying 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 Between Ying Shi 90 minutes, prepare modified poly ester.
The number-average molecular weight of modified poly ester prepared is 30000, by p-phthalic acid segment, ethylene glycol segment and 2-last of the ten Heavenly stems Base-1,6 hexanediol segment compositions, 2-decyl-1,6 hexanediol segments are 5% with the Mole percent ratio of ethylene glycol segment.
Embodiment 14
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.47 and 2-nonyl-1,6 hexanediol are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.47% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 220 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.8 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.27MPa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, is adding The catalyst glycol antimony of 0.04% that amount is p-phthalic acid weight and addition is p-phthalic acid weight 0.04% Under the effect of stabilizer trimethyl phosphate, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure by Normal pressure is steadily evacuated to absolute pressure 460Pa, and temperature controls at 263 DEG C, and the response time is 47 minutes；Then proceed to evacuation, 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, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 28000, by p-phthalic acid segment, ethylene glycol segment and 2-nonyl Base-1,6 hexanediol segment compositions, 2-nonyl-1,6 hexanediol segments are 4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 15
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.46 and 2-octyl group-1,6 hexanediol are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.49% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 233 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.8 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 259 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.5% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 19 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.044% are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.046%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and temperature controls at 269 DEG C, and the response time is 48 minutes；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, In 87 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 29000, pungent by p-phthalic acid segment, ethylene glycol segment and 2- Base-1,6 hexanediol segment compositions, 2-octyl group-1,6 hexanediol segments are 4.5% with the Mole percent ratio of ethylene glycol segment.
Embodiment 16
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.49 and 2-heptyl-1,6 hexanediol are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.48% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 230 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.8 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.7% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 19 minutes, is adding The catalyst glycol antimony and the addition that enter amount is p-phthalic acid weight 0.048% are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.047%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 460Pa by normal pressure, and temperature controls at 267 DEG C, and the response time is 48 minutes；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, In 83 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester prepared is 27000, by p-phthalic acid segment, ethylene glycol segment and 2-heptan Base-1,6 hexanediol segment compositions, 2-heptyl-1,6 hexanediol segments are 4.7% with the Mole percent ratio of ethylene glycol segment.
Embodiment 17
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.467 and 2-hexyl-1,6 hexanediol are made into slurry and add in reactor, Being 60wt% in concentration, addition is under the catalytic action of the concentrated sulphuric acid of the 0.47% of p-phthalic acid weight, carries out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.27MPa, and temperature is 236 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.89 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 258 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.3% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.04% are p-phthalic acid weight Under the effect of the stabilizer NSC 6513 of 0.041%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and temperature controls at 268 DEG C, and the response time is 48 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls 278 DEG C, in 85 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 29000, own by p-phthalic acid segment, ethylene glycol segment and 2- Base-1,6 hexanediol segment compositions, 2-hexyl-1,6 hexanediol segments are 4.3% with the Mole percent ratio of ethylene glycol segment.
Embodiment 18
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.48 and 2-amyl group-1,6 hexanediol are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.46% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 230 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.88 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 256 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.7% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.047% are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.047%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 480Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 47 minutes；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, In 85 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 28000, by p-phthalic acid segment, ethylene glycol segment and 2-penta Base-1,6 hexanediol segment compositions, 2-amyl group-1,6 hexanediol segments are 4.7% with the Mole percent ratio of ethylene glycol segment.
Embodiment 19
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.46 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 the concentrated sulphuric acid of the 0.47% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 238 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.9 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 259 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches more than the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.7% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 19 minutes, is adding Enter the catalyst acetic acid antimony of amount is p-phthalic acid weight 0.046% and addition is p-phthalic acid weight 0.048% Stabilizer NSC 6513 effect under, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this stage press It is 446Pa that power is steadily evacuated to absolute pressure by normal pressure, and temperature controls at 267 DEG C, and the response time is 49 minutes；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, In 87 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester prepared is 29000, by p-phthalic acid segment, ethylene glycol segment and 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
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.46 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 the concentrated sulphuric acid of the 0.46% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.26MPa, and temperature is 221 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.89 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.25MPa, and temperature is 259 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.1% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, is adding The catalyst glycol antimony and the addition that enter amount is p-phthalic acid weight 0.041% are p-phthalic acid weight Under the effect of the stabilizer trimethyl phosphate of 0.042%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 460Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 47 minutes；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, In 85 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 28000, by p-phthalic acid 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
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.43 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 the concentrated sulphuric acid of the 0.47% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.27MPa, and temperature is 235 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.78 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.26MPa, and temperature is 255 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.3% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 17 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.043% are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.049%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and temperature controls at 268 DEG C, and the response time is 46 minutes；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, In 85 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 28000, pungent by p-phthalic acid 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
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.43 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 the concentrated sulphuric acid of the 0.45% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.29MPa, and temperature is 235 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.87 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.27MPa, and temperature is 255 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.6% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, is adding Enter the catalyst glycol antimony of amount is p-phthalic acid weight 0.047% and addition is p-phthalic acid weight 0.04% Stabilizer triphenyl phosphate effect under, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure Steadily be evacuated to absolute pressure 470Pa by normal pressure, temperature controls at 268 DEG C, and the response time is 45 minutes；Then proceed to evacuation, Carrying 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, prepare modified poly ester.
The number-average molecular weight of modified poly ester prepared is 29000, by p-phthalic acid 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
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.457 and 2-hexyl-1,5 pentanediols are made into slurry and add in reactor, Being 55% in concentration, addition is under the catalytic action of the concentrated sulphuric acid of the 0.46% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 239 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.81 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.27MPa, and temperature is 255 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.41% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 19 minutes, Addition is the catalytic antimony trioxide of the 0.042% of p-phthalic acid weight and addition is p-phthalic acid weight Under the effect of the stabilizer NSC 6513 of 0.048%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 45 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50Pa, and reaction temperature controls 275 DEG C, in 85 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 28000, own by p-phthalic acid 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
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.47 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 the concentrated sulphuric acid of the 0.48% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.27MPa, and temperature is 245 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.81 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.27MPa, and temperature is 259 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.67% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 19 minutes, Addition is the catalytic antimony trioxide of the 0.041% of p-phthalic acid weight and addition is p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.042%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 485Pa by normal pressure, and temperature controls at 268 DEG C, and the response time is 46 minutes；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, In 89 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 29000, by p-phthalic acid 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
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
Mixed by p-phthalic acid that mol ratio is 1:1.45 and 2-hexyl-1,5 pentanediol and 2-amyl group-1,4 butanediol 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, Being 55% in concentration, addition is under the catalytic action of the concentrated sulphuric acid of the 0.49% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.26MPa, and temperature is 236 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.8 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.4% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.042% are p-phthalic acid weight Under the effect of the stabilizer NSC 6513 of 0.047%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 49 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50Pa, and reaction temperature controls 278 DEG C, in 88 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester prepared is 29000, by p-phthalic acid 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
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By 2-octyl group-1,6 hexanediol of p-phthalic acid sum that mol ratio is 1:1.45 and 2-amyl group-1,5 pentanediol Mixture is made into slurry and adds in reactor, wherein 2-octyl group-1,6 hexanediol 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 the concentrated sulphuric acid of the 0.45% of p-phthalic acid weight, carries out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 239 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.84 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.29MPa, and temperature is 255 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.6% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.0423% are p-phthalic acid weight Under the effect of the stabilizer NSC 6513 of 0.045%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 45 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50Pa, and reaction temperature controls 278 DEG C, in 85 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester prepared is 28000, by p-phthalic acid segment, ethylene glycol segment, 2-octyl group- 1,6 hexanediol segment and 2-amyl group-1,5 pentanediol segment compositions, 2-octyl group-1,6 hexanediol 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
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
Mixed by p-phthalic acid that mol ratio is 1:1.45 and 2-hexyl-1,5 pentanediol and 2-amyl group-1,4 butanediol 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, Being 55% in concentration, addition is under the catalytic action of the concentrated sulphuric acid of the 0.49% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.26MPa, and temperature is 236 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 96% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.8 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.4% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.042% are p-phthalic acid weight Under the effect of the stabilizer NSC 6513 of 0.047%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 49 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50Pa, and reaction temperature controls 278 DEG C, in 88 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester prepared is 29000, by p-phthalic acid 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
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.45 and 2-octyl group-1,3 propylene glycol, 2-amyl group-1,4 butanediol and 2-oneself Base-1, the mixture of 6 hexanediol is made into slurry and adds in reactor, wherein 2-octyl group-1,3 propylene glycol, 2-amyl group-Isosorbide-5-Nitrae fourth two Alcohol and 2-hexyl-1, the mol ratio of 6 hexanediol is 3:2:1, is 60% in concentration, and addition is p-phthalic acid weight Under the catalytic action of the concentrated sulphuric acid of 0.47%, carrying out esterification, esterification is 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 p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.8 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.27MPa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.71% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, Addition is the catalytic antimony trioxide of the 0.04% of p-phthalic acid weight and addition is p-phthalic acid weight Under the effect of the stabilizer NSC 6513 of 0.041%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and temperature controls at 268 DEG C, and the response time is 49 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50Pa, and reaction temperature controls 277 DEG C, in 84 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 29000, by p-phthalic acid segment, ethylene glycol segment, band side chain Glycol segment composition, the most branched glycol segment is 2-octyl group-1,3 propylene glycol segments, 2-amyl group-Isosorbide-5-Nitrae butanediol chain Section and 2-hexyl-1,6 hexanediol segment compositions, branched glycol segment with the Mole percent ratio of ethylene glycol segment is 4.71%.
Embodiment 29
A kind of preparation method of the high-strength ultralow miniature polyester industrial fiber of high uniformity, the high-strength ultralow miniature polyester of high uniformity Industrial yarn uses porous spinneret to prepare, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to The hole of spinneret orifice is centrally located on concentration ellipse, and concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle is altogether Line.
As it is shown in figure 1, the ratio of the major axis of ellipse and minor axis length is 1.3, the spacing of adjacent spinneret orifice is equal to spinneret orifice Guide hole diameter plus 1.5mm, spinneret is circular jetting filament plate, the long axial length that the diameter of circular jetting filament plate is maximum with series ellipse The difference of degree is 11mm, and a diameter of 2.0mm of guide hole of spinneret orifice, the spray webbing hole count of spinneret is 374, the spinneret orifice of spinneret Shape of cross section be circular.
The modified poly ester that embodiment 1 prepares is extruded through solid phase polycondensation thickening, metering, porous spinneret, cool down, oils, is drawn Stretch, thermal finalization and winding, prepare the high-strength ultralow miniature polyester industrial fiber of high uniformity, the temperature wherein extruded is 280 DEG C, cooling Pathogenic wind-warm be 20 DEG C, GR-1 speed 480m/min；Temperature is room temperature；GR-2 speed 500m/min；Temperature 80 DEG C；GR-3 speed 1800m/min；Temperature 100 DEG C；GR-4 speed 2800m/min；Temperature 200 DEG C；GR-5 speed 2800m/min；Temperature 200 DEG C； GR-6 speed 2600m/min；Temperature 150 DEG C；The speed of winding is 2600m/min.
The fracture strength of the high-strength ultralow miniature polyester industrial fiber of high uniformity prepared is 7.9cN/dtex；Line density deviation Rate is 0.6%, and fracture strength CV value is 1.8%, and extension at break CV value is 4.5%, and extension at break is 19.0, at 260 DEG C, molten Body viscosity declines 11%, and under the test condition that temperature is 177 DEG C × 10min × 0.05cN/dtex, dry-hot shrinkage is 1.8%.
Embodiment 30
A kind of preparation method of the high-strength ultralow miniature polyester industrial fiber of high uniformity, the high-strength ultralow miniature polyester of high uniformity Industrial yarn uses porous spinneret to prepare.
As it is shown on figure 3, the ratio of the major axis of ellipse and minor axis length is 1.6, the spacing of adjacent spinneret orifice is equal to spinneret orifice Guide hole diameter plus 1.5mm, spinneret is circular jetting filament plate, the long axial length that the diameter of circular jetting filament plate is maximum with series ellipse The difference of degree is 11mm, and a diameter of 2.0mm of guide hole of spinneret orifice, the spray webbing hole count of spinneret is 382, the spinneret orifice of spinneret Shape of cross section be circular.
The modified poly ester that embodiment 1 prepares is extruded through solid phase polycondensation thickening, metering, porous spinneret, cool down, oils, is drawn Stretch, thermal finalization and winding, prepare the high-strength ultralow miniature polyester industrial fiber of high uniformity, the temperature wherein extruded is 280 DEG C, cooling Pathogenic wind-warm be 20 DEG C, GR-1 speed 480m/min；Temperature is room temperature；GR-2 speed 500m/min；Temperature 80 DEG C；GR-3 speed 1800m/min；Temperature 100 DEG C；GR-4 speed 2800m/min；Temperature 200 DEG C；GR-5 speed 2800m/min；Temperature 200 DEG C； GR-6 speed 2600m/min；Temperature 150 DEG C；The speed of winding is 2600m/min.
The fracture strength of the high-strength ultralow miniature polyester industrial fiber of high uniformity prepared is 7.8cN/dtex；Line density deviation Rate is 0.7%, and fracture strength CV value is 1.7%, and extension at break CV value is 4.8%, and extension at break is 19.0, at 260 DEG C, molten Body viscosity declines 11%, and under the test condition that temperature is 177 DEG C × 10min × 0.05cN/dtex, dry-hot shrinkage is 1.9%.
Comparative example 1
A kind of preparation method of the high-strength ultralow miniature polyester industrial fiber of high uniformity, the high-strength ultralow miniature polyester of high uniformity Industrial yarn uses porous spinneret to prepare, and on spinneret, the arrangement mode of spinneret orifice is circular arrangement, and circular arrangement refers to spray webbing The hole in hole is centrally located on concentric circular, and concentric circular is that series is circular.As in figure 2 it is shown, the spacing of adjacent spinneret orifice is equal to spinneret orifice Guide hole diameter plus 1.5mm, spinneret is circular jetting filament plate, the diameter that the diameter of circular jetting filament plate is maximum with series circle Difference is 11mm, a diameter of 2.0mm of guide hole of spinneret orifice, and the spray webbing hole count of spinneret is 370, the horizontal stroke of the spinneret orifice of spinneret Cross sectional shape is circular.
The modified poly ester that embodiment 1 prepares is extruded through solid phase polycondensation thickening, metering, porous spinneret, cool down, oils, is drawn Stretch, thermal finalization and winding, prepare the high-strength ultralow miniature polyester industrial fiber of high uniformity, the temperature wherein extruded is 280 DEG C, cooling Pathogenic wind-warm be 20 DEG C, GR-1 speed 480m/min；Temperature is room temperature；GR-2 speed 500m/min；Temperature 80 DEG C；GR-3 speed 1800m/min；Temperature 100 DEG C；GR-4 speed 2800m/min；Temperature 200 DEG C；GR-5 speed 2800m/min；Temperature 200 DEG C； GR-6 speed 2600m/min；Temperature 150 DEG C；The speed of winding is 2600m/min.
The fracture strength of the high-strength ultralow miniature polyester industrial fiber of high uniformity prepared is 7.6cN/dtex；Line density deviation Rate is 1%, and fracture strength CV value is 1.9%, and extension at break CV value is 5.3%, and extension at break is 20.1, at 260 DEG C, and melt Viscosity declines 11%, and under the test condition that temperature is 177 DEG C × 10min × 0.05cN/dtex, dry-hot shrinkage is 1.75%.
When contrasting it can be seen that the effective area of spinneret is identical with embodiment 29, (circular arrangement when spray webbing hole count is close Spray webbing hole count is 370, and oval shaped arrangements spray webbing 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 contrasting it can be seen that the effective area of spinneret is identical with embodiment 30, 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 spray webbing 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, Embodiment 29 and the prepared fiber linear density deviation ratio of embodiment 30, fracture strength CV value, extension at break CV value are less than comparative example 1, under the conditions of same process is described, the fibre property using the spinneret of spinneret orifice oval shaped arrangements to prepare is better than using spinneret The spinneret of circular arrangement.
Embodiment 31～33
The preparation method of the high-strength ultralow miniature polyester industrial fiber of a kind of high uniformity, uses porous spinneret to prepare.
Be arranged as long axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.4, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.6mm, spinneret is circular jetting filament plate, and the diameter of circular jetting filament plate 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, spray webbing The shape of cross section of the spinneret orifice of plate is square.
The high-strength ultralow miniature polyester industrial fiber of high uniformity extrude through metering, porous spinneret, cool down, oils, stretches, hot Sizing and winding, prepare the high-strength ultralow miniature polyester industrial fiber of high uniformity, and the temperature wherein extruded is 300 DEG C, the wind of cooling Temperature is 25 DEG C；Stretch, heat setting process parameter is: GR-1 speed 600m/min；Temperature is room temperature；GR-2 speed 1000m/min； Temperature 100 DEG C；GR-3 speed 2500m/min；Temperature 150 DEG C；GR-4 speed 3500m/min；Temperature 250 DEG C；GR-5 speed 3500m/min；Temperature 250 DEG C；GR-6 speed 3400m/min；Temperature 220 DEG C；The speed of winding is 3400m/min.
The high-strength ultralow miniature polyester industrial fiber of high uniformity prepared is at 280 DEG C, and melt viscosity declines percent, room temperature The mechanical performance data of lower industrial yarn, and under the test condition that temperature is 177 DEG C × 10min × 0.05cN/dtex, industry The dry-hot shrinkage such as following table of silk.
Embodiment 34～36
The preparation method of the high-strength ultralow miniature polyester industrial fiber of a kind of high uniformity, uses porous spinneret to prepare.
Be arranged as long axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.4, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.6mm, spinneret is circular jetting filament plate, and the diameter of circular jetting filament plate 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, spray webbing The shape of cross section of the spinneret orifice of plate is square.
The high-strength ultralow miniature polyester industrial fiber of high uniformity extrude through metering, porous spinneret, cool down, oils, stretches, hot Sizing and winding, prepare the high-strength ultralow miniature polyester industrial fiber of high uniformity, and the temperature wherein extruded is 310 DEG C, the wind of cooling Temperature is 30 DEG C；Stretch, heat setting process parameter is: GR-1 speed 500m/min；Temperature is room temperature；GR-2 speed 600m/min； Temperature 90 DEG C；GR-3 speed 2200m/min；Temperature 130 DEG C；GR-4 speed 2900m/min；Temperature 230 DEG C；GR-5 speed 3200m/min；Temperature 230 DEG C；GR-6 speed 3000m/min；Temperature 200 DEG C；The speed of winding is 2800m/min.
The high-strength ultralow miniature polyester industrial fiber of high uniformity prepared melt viscosity at 290 DEG C declines percentage ratio, room temperature The mechanical performance data of lower industrial yarn, and under the test condition that temperature is 177 DEG C × 10min × 0.05cN/dtex, industry The dry-hot shrinkage such as following table of silk.
Embodiment 37～39
The preparation method of the high-strength ultralow miniature polyester industrial fiber of a kind of high uniformity, uses porous spinneret to prepare.
Be arranged as long axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.4, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.6mm, spinneret is circular jetting filament plate, and the diameter of circular jetting filament plate 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, spray webbing The shape of cross section of the spinneret orifice of plate is square.
The high-strength ultralow miniature polyester industrial fiber of high uniformity extrude through metering, porous spinneret, cool down, oils, stretches, hot Sizing and winding, prepare the high-strength ultralow miniature polyester industrial fiber of high uniformity, and the temperature wherein extruded is 290 DEG C, the wind of cooling Temperature is 20 DEG C；Stretch, heat setting process parameter is: GR-1 speed 500m/min；Temperature is room temperature；GR-2 speed 800m/min； Temperature 85 DEG C；GR-3 speed 2300m/min；Temperature 120 DEG C；GR-4 speed 3200m/min；Temperature 210 DEG C；GR-5 speed 3200m/min；Temperature 230 DEG C；GR-6 speed 3200m/min；Temperature 200 DEG C；The speed of winding is 3200m/min.
The high-strength ultralow miniature polyester industrial fiber of high uniformity prepared melt viscosity at 270 DEG C declines percent, room temperature The mechanical performance data of lower industrial yarn, and under the test condition that temperature is 177 DEG C × 10min × 0.05cN/dtex, industry The dry-hot shrinkage such as following table of silk.
Embodiment 40～42
The preparation method of the high-strength ultralow miniature polyester industrial fiber of a kind of high uniformity, uses porous spinneret to prepare.
Be arranged as long axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.4, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.6mm, spinneret is circular jetting filament plate, and the diameter of circular jetting filament plate 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, spray webbing The shape of cross section of the spinneret orifice of plate is square.
The high-strength ultralow miniature polyester industrial fiber of high uniformity extrude through metering, porous spinneret, cool down, oils, stretches, hot Sizing and winding, prepare the high-strength ultralow miniature polyester industrial fiber of high uniformity, and the temperature wherein extruded is 300 DEG C, the wind of cooling Temperature is 25 DEG C；Stretch, heat setting process parameter is: GR-1 speed 600m/min；Temperature is room temperature；GR-2 speed 900m/min； Temperature 100 DEG C；GR-3 speed 2100m/min；Temperature 120 DEG C；GR-4 speed 3200m/min；Temperature 240 DEG C；GR-5 speed 3100m/min；Temperature 230 DEG C；GR-6 speed 3200m/min；Temperature 200 DEG C；The speed of winding is 3200m/min.
The high-strength ultralow miniature polyester industrial fiber of high uniformity prepared melt viscosity at 260 DEG C declines percentage ratio, room temperature The mechanical performance data of lower industrial yarn, and under the test condition that temperature is 177 DEG C × 10min × 0.05cN/dtex, industry The dry-hot shrinkage such as following table of silk.
Embodiment 43～45
The preparation method of the high-strength ultralow miniature polyester industrial fiber of a kind of high uniformity, uses porous spinneret to prepare.
Be arranged as long axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.4, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.6mm, spinneret is circular jetting filament plate, and the diameter of circular jetting filament plate 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, spray webbing The shape of cross section of the spinneret orifice of plate is square.
The high-strength ultralow miniature polyester industrial fiber of high uniformity extrude through metering, porous spinneret, cool down, oils, stretches, hot Sizing and winding, prepare the high-strength ultralow miniature polyester industrial fiber of high uniformity, and the temperature wherein extruded is 290 DEG C, the wind of cooling Temperature is 30 DEG C；Stretch, heat setting process parameter is: GR-1 speed 480m/min；Temperature is room temperature；GR-2 speed 500m/min； Temperature 100 DEG C；GR-3 speed 1800m/min；Temperature 150 DEG C；GR-4 speed 3100m/min；Temperature 250 DEG C；GR-5 speed 3300m/min；Temperature 240 DEG C；GR-6 speed 3200m/min；Temperature 200 DEG C；The speed of winding is 3000m/min.
Prepare the high-strength ultralow miniature polyester industrial fiber of high uniformity at 280 DEG C, melt viscosity, industrial yarn under room temperature Mechanical performance data, and under the test condition that temperature is 177 DEG C × 10min × 0.05cN/dtex, the xeothermic receipts of industrial yarn Shrinkage such as following table.
Embodiment 46～48
The preparation method of the high-strength ultralow miniature polyester industrial fiber of a kind of high uniformity, uses porous spinneret to prepare, spray webbing On plate, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located on concentration ellipse, Concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear.
Be arranged as long axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.4, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.6mm, spinneret is circular jetting filament plate, and the diameter of circular jetting filament plate 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, spray webbing The shape of cross section of the spinneret orifice of plate is square.
The high-strength ultralow miniature polyester industrial fiber of high uniformity extrude through metering, porous spinneret, cool down, oils, stretches, hot Sizing and winding, prepare the high-strength ultralow miniature polyester industrial fiber of high uniformity, and the temperature wherein extruded is 310 DEG C, the wind of cooling Temperature is 25 DEG C；Stretch, heat setting process parameter is: GR-1 speed 580m/min；Temperature is room temperature；GR-2 speed 800m/min； Temperature 100 DEG C；GR-3 speed 2400m/min；Temperature 140 DEG C；GR-4 speed 3300m/min；Temperature 240 DEG C；GR-5 speed 3200m/min；Temperature 230 DEG C；GR-6 speed 2900m/min；Temperature 190 DEG C；The speed of winding is 3100m/min.
The high-strength ultralow miniature polyester industrial fiber of high uniformity prepared melt viscosity at 280 DEG C declines percent, room temperature The mechanical performance data of lower industrial yarn, and under the test condition that temperature is 177 DEG C × 10min × 0.05cN/dtex, industry The dry-hot shrinkage such as following table of silk.
Embodiment 49～51
The preparation method of the high-strength ultralow miniature polyester industrial fiber of a kind of high uniformity, uses porous spinneret to prepare, spray webbing On plate, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located on concentration ellipse, Concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear.
Be arranged as long axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.4, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.6mm, spinneret is circular jetting filament plate, and the diameter of circular jetting filament plate 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, spray webbing The shape of cross section of the spinneret orifice of plate is square.
The high-strength ultralow miniature polyester industrial fiber of high uniformity extrude through metering, porous spinneret, cool down, oils, stretches, hot Sizing and winding, prepare the high-strength ultralow miniature polyester industrial fiber of high uniformity, and the temperature wherein extruded is 310 DEG C, the wind of cooling Temperature is 30 DEG C；Stretch, heat setting process parameter is: GR-1 speed 480m/min；Temperature is room temperature；GR-2 speed 700m/min； Temperature 90 DEG C；GR-3 speed 2500m/min；Temperature 140 DEG C；GR-4 speed 3200m/min；Temperature 250 DEG C；GR-5 speed 2900m/min；Temperature 240 DEG C；GR-6 speed 2900m/min；Temperature 180 DEG C；The speed of winding is 2900m/min.
The high uniformity high-strength ultralow miniature polyester industrial fiber melt viscosity at 280 DEG C prepared, industrial yarn under room temperature Mechanical performance data, and under the test condition that temperature is 177 DEG C × 10min × 0.05cN/dtex, the xeothermic receipts of industrial yarn Shrinkage such as following table.
Embodiment 52～57
The preparation method of the high-strength ultralow miniature polyester industrial fiber of a kind of high uniformity, uses porous spinneret to prepare, spray webbing On plate, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located on concentration ellipse, Concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear.
Be arranged as long axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.4, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.6mm, spinneret is circular jetting filament plate, and the diameter of circular jetting filament plate 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, spray webbing The shape of cross section of the spinneret orifice of plate is square.
The high-strength ultralow miniature polyester industrial fiber of high uniformity extrude through metering, porous spinneret, cool down, oils, stretches, hot Sizing and winding, prepare the high-strength ultralow miniature polyester industrial fiber of high uniformity, and the temperature wherein extruded is 310 DEG C, the wind of cooling Temperature is 20 DEG C；Stretch, heat setting process parameter is: GR-1 speed 600m/min；Temperature is room temperature；GR-2 speed 1000m/min； Temperature 80 DEG C；GR-3 speed 1800～2500m/min；Temperature 100 DEG C；GR-4 speed 2800m/min；Temperature 200 DEG C；GR-5 speed Degree 3500m/min；Temperature 200 DEG C；GR-6 speed 3400m/min；Temperature 220 DEG C；The speed of winding is 3400m/min.
The high-strength ultralow miniature polyester industrial fiber of high uniformity prepared melt viscosity at 280 DEG C declines percentage ratio, room temperature The mechanical performance data of lower industrial yarn, and under the test condition that temperature is 177 DEG C × 10min × 0.05cN/dtex, industry The dry-hot shrinkage such as following table of silk.

Claims (10)

1. the high-strength ultralow miniature polyester industrial fiber of high uniformity, is characterized in that: the high-strength ultralow miniature of described high uniformity gathers Ester industrial yarn is obtained by modified poly ester spinning after solid-phase tack producing；The material of the high-strength ultralow miniature polyester industrial fiber of described high uniformity For modified poly ester, described modified poly ester is made up of p-phthalic acid segment, ethylene glycol segment and the dihydroxylic alcohols segment containing side chain, institute State on the non-end group carbon that the dihydroxylic alcohols segment containing side chain refers to that side chain is positioned in dihydroxylic alcohols segment and side chain is for containing 5-10 The dihydroxylic alcohols segment of the linear carbon chain of individual carbon atom；The fracture strength of the high-strength ultralow miniature polyester industrial fiber of described high uniformity >= 7.5cN/dtex, line density deviation ratio≤1.0%, fracture strength CV value≤2.0%, extension at break CV value≤5.5%；Described height The high-strength ultralow miniature polyester industrial fiber of uniformity is at 260～290 DEG C, and melt viscosity declines 10-20%, is 177 DEG C in temperature Under the test condition of × 10min × 0.05cN/dtex, dry-hot shrinkage is 1.8 ± 0.25%.
A kind of high-strength ultralow miniature polyester industrial fiber of high uniformity the most according to claim 1, it is characterised in that described height The extension at break of the high-strength ultralow miniature polyester industrial fiber of uniformity is 20.0 ± 1.5%, the number-average molecular weight of described modified poly ester For 15000-30000.
A kind of high-strength ultralow miniature polyester industrial fiber of high uniformity the most according to claim 1, it is characterised in that described contain The dihydroxylic alcohols segment of side chain is 2-amyl group-1,3 propylene glycol segment, 2-hexyl-1,3 propylene glycol segment, 2-heptyl-1,3 propylene glycol Segment, 2-octyl group-1,3 propylene glycol segment, 2-nonyl-1,3 propylene glycol segment, 2-decyl-1,3 propylene glycol segment, 2-amyl group-1, 4 butanediol segments, 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 hexanediol segment, 2-hexyl-1,6 hexanediol segment, 2-heptyl-1,6 hexanediol segment, 2- More than one in octyl group-1,6 hexanediol segment, 2-nonyl-1,6 hexanediol segment or 2-decyl-1,6 hexanediol segment；Institute The Mole percent ratio stating the dihydroxylic alcohols segment containing side chain and ethylene glycol segment is 2～5%.
4. the preparation side of the high-strength ultralow miniature polyester industrial fiber of a kind of high uniformity as according to any one of claim 1-3 Method, is characterized in that: modified poly ester extrude through solid phase polycondensation thickening, metering, porous spinneret, cool down, oils, is stretched, heat calmly Type and winding, prepare the high-strength ultralow miniature polyester industrial fiber of high uniformity；
On described porous spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and described oval shaped arrangements refers to the hole of spinneret orifice Being centrally located on concentration ellipse, described concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear；
The preparation process of modified poly ester comprises the following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
After p-phthalic acid is made into slurry with the dihydroxylic alcohols containing side chain, under the catalytic action of concentrated sulphuric acid, carry out esterification, Obtain p-phthalic acid binary alcohol esters；The described dihydroxylic alcohols containing side chain is the non-end group carbon that side chain is positioned in dihydroxylic alcohols segment Upper and that side chain is the linear carbon chain containing 5-10 carbon atom dihydroxylic alcohols；
(2) preparation of ethylene glycol terephthalate:
After p-phthalic acid and ethylene glycol are made into slurry, carry out esterification, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, adding the p-phthalic acid binary alcohol esters of preparation in step (1), stirring is mixed Close, under the effect of catalyst and stabilizer, under conditions of negative pressure, carry out polycondensation reaction and the Gao Zhen in coarse vacuum stage successively The polycondensation reaction in empty stage, prepares modified poly ester.
The preparation method of the high-strength ultralow miniature polyester industrial fiber of high uniformity the most according to claim 4, it is characterised in that Prepared by described modified poly ester concretely comprises the following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
P-phthalic acid and the dihydroxylic alcohols containing side chain are made into slurry add in reactor, under the catalytic action of concentrated sulphuric acid, enter Row esterification, esterification is compressive reaction in nitrogen atmosphere, and 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 p-phthalic acid Binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Adding in reactor after p-phthalic acid and ethylene glycol are made into slurry, carry out esterification, esterification is in blanket of nitrogen Enclosing 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% time be esterification terminal, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, adding the p-phthalic acid binary alcohol esters of preparation in step (1), stirring is mixed Close 15-20 minute, under the effect of catalyst and stabilizer, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, This staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, and temperature controls at 260～270 DEG C, the response time be 30～ 50 minutes；Then proceed to evacuation, 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, response time 50～90 minutes, prepares modified poly ester；
Again through pelletizing, modified poly ester being obtained Modified polyester chips, obtained polyester slice is viscosified by solid phase polycondensation, makes polyester The intrinsic viscosity of section brings up to 1.0～1.2dL/g, is high viscous section；Again through metering, porous spinneret extrusion, cooling, on Oil, stretching, thermal finalization and winding, prepare the high-strength ultralow miniature polyester industrial fiber of high uniformity；
Spinning main technologic parameters is:
The temperature of described extrusion is 290～310 DEG C；
The pathogenic wind-warm of described cooling is 20～30 DEG C；
Described stretching, heat setting process parameter be:
GR-1 speed 480～600m/min；Temperature is room temperature；
GR-2 speed 500～1000m/min；Temperature 80～100 DEG C；
GR-3 speed 1800～2500m/min；Temperature 100～150 DEG C；
GR-4 speed 2800～3500m/min；Temperature 200～250 DEG C；
GR-5 speed 2800～3500m/min；Temperature 200～250 DEG C；
GR-6 speed 2600～3400m/min；Temperature 150～220 DEG C；
The speed of described winding is 2600～3400m/min.
The preparation method of the high-strength ultralow miniature polyester industrial fiber of a kind of high uniformity the most according to claim 5, its feature Being, in described step (1), p-phthalic acid is 1:1.3-1.5 with the mol ratio of the dihydroxylic alcohols containing side chain；Concentrated sulphuric acid addition 0.3-0.5% for p-phthalic acid weight；The concentration of described concentrated sulphuric acid is 50-60wt%；In described step (2), to benzene two Formic acid is 1:1.2～2.0 with the mol ratio of ethylene glycol；In described step (3), described p-phthalic acid binary alcohol esters with to benzene two The Mole percent ratio of formic acid glycol ester is 2～5%；Described catalyst is antimony oxide, antimony glycol or antimony acetate, urges Agent addition is the 0.01%～0.05% of p-phthalic acid gross weight；Described stabilizer is triphenyl phosphate, tripotassium phosphate Ester or NSC 6513, stabilizer addition is the 0.01%～0.05% of described p-phthalic acid gross weight.
The preparation method of the high-strength ultralow miniature polyester industrial fiber of a kind of high uniformity the most according to claim 5, its feature Being, the described dihydroxylic alcohols containing side chain is 2-amyl group-1,3 propylene glycol, 2-hexyl-1,3 propylene glycol, 2-heptyl-1,3 propylene glycol, 2-octyl group-1,3 propylene glycol, 2-nonyl-1,3 propylene glycol, 2-decyl-1,3 propylene glycol, 2-amyl group-1,4 butanediol, 2-hexyl-1, 4 butanediols, 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 pentanediols, 2-decyl-1,5 pentanediols, 2-amyl group-1,6 hexanediol, 2-hexyl-1,6 hexanediol, 2-heptyl-1,6 hexanediol, More than one in 2-octyl group-1,6 hexanediol, 2-nonyl-1,6 hexanediol or 2-decyl-1,6 hexanediol.
The preparation method of the high-strength ultralow miniature polyester industrial fiber of a kind of high uniformity the most according to claim 4, its feature Being, described porous spinneret is circular jetting filament plate or elliptical spinneret plate；The diameter of described circular jetting filament plate is oval with series The difference of maximum long axis length is more than 10mm, and the difference of the long axis length that described elliptical spinneret plate is maximum with series ellipse is big In 10mm.
The preparation method of the high-strength ultralow miniature polyester industrial fiber of a kind of high uniformity the most according to claim 4, its feature Be, on described porous spinneret spinneret orifice be arranged as major axis and/or short axial symmetry, the spacing of adjacent spinneret orifice is more than or equal to The guide hole diameter of spinneret orifice adds 1.5mm；Oval major axis is 1.3～1.8 with the ratio of minor axis length.
The preparation method of the high-strength ultralow miniature polyester industrial fiber of a kind of high uniformity the most according to claim 4, its feature It is, the guide hole a diameter of 1.5～2.5mm of described spinneret orifice；The spray webbing hole count of described spinneret is more than or equal to 192, described spray The shape of cross section of the spinneret orifice of filament plate is circle, square, rhombus, yi word pattern, triangular form, trilobal cross, hollow type or flat Flat pattern.
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CN109750381A (en) * 2018-12-27 2019-05-14 江苏恒力化纤股份有限公司 The preparation method of polyester industrial yarn for TGXG

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