CN106350889A - High-uniformity, high-strength and moderate-shrinkage polyester industrial yarns and preparation method thereof - Google Patents

High-uniformity, high-strength and moderate-shrinkage polyester industrial yarns and preparation method thereof Download PDF

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Publication number
CN106350889A
CN106350889A CN201610778339.3A CN201610778339A CN106350889A CN 106350889 A CN106350889 A CN 106350889A CN 201610778339 A CN201610778339 A CN 201610778339A CN 106350889 A CN106350889 A CN 106350889A
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phthalic acid
segment
preparation
esterification
temperature
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CN106350889B (en
Inventor
李文刚
王山水
邓丽娜
杨大矛
王彦芳
赵慧荣
范晓兵
宋光坤
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Jiangsu Hengli Chemical Fiber Co Ltd
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Jiangsu Hengli Chemical Fiber Co Ltd
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D7/00—Collecting the newly-spun products

Abstract

The invention relates to high-uniformity, high-strength and moderate-shrinkage polyester industrial yarns and a preparation method thereof. The high-uniformity, high-strength and moderate-shrinkage polyester industrial yarns are prepared from modified polyester consisting of a terephthalic acid chain section, an ethylene glycol chain section and a branch-containing dihydric alcohol chain section. The preparation method of the high-uniformity, high-strength and moderate-shrinkage polyester industrial yarns comprises the following steps: performing esterification reaction on terephthalic acid and branch-containing dihydric alcohol under the catalysis of concentrated sulfuric acid to obtain phthalic acid dihydric alcohol ester; then matching the terephthalic acid and dihydric alcohol for esterification reaction to obtain terephthalate; finally, stirring and mixing the phthalic acid dihydric alcohol ester and the terephthalate, performing condensation polymerization in a low-vacuum stage and a high-vacuum stage under the action of a catalyst and a stabilizer to prepare modified polyester, and performing metering, extrusion by a multihole spinneret plate, cooling, oiling, drawing, thermal sizing and winding on the modified polyester to prepare the high-uniformity, high-strength and moderate-shrinkage polyester industrial yarns.

Description

High-strength middle shrinkage type polyester industrial fiber of a kind of high uniformity and preparation method thereof
Technical field
The invention belongs to polyester fiber technical field, it is related to a kind of high-strength middle shrinkage type polyester industrial fiber of high uniformity and its system Preparation Method.
Background technology
Polyethylene terephthalate (pet fiber or polyester fiber) fiber since the advent of the world, have fracture strength and Elastic modelling quantity is high, and resilience is moderate, and thermal finalization is excellent, and heat-resisting light resistance is good and acid-fast alkali-proof corrosion resistance etc. is a series of excellent Performance, and fabric have crease-resistant exempt to provide, the advantages of stiffness is good, be widely used in the fields such as 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 relatively special physicalchemical structure, performance and purposes, or has the chemical fibre of specific function, major embodiment Being able to bear strong corrosion, low abrasion, high temperature resistant, radiation hardness, fire-retardant, fire-resistant, high voltage withstanding, high strength and modulus and plurality of medical work( Energy.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 applied to various uses, flexible body advertising lamp box material, inflatable structure material, fluffy lid architectural fabrics sunshade account Paulin etc..Based on high-strength low-shrinkage industrial yarn, textile material obtains in terms of the military supplies such as special protective garment, camouflage, covering, knapsack To application.One kind as earth working material has the advantages that light, soft, high-strength, wear-resisting, anticorrosive, non-conductive, damping.Make Used time safe ready, efficiency high, and lifting object will not be damaged.The application of Pet Industrial Fiber is expanded and is driven application The whole competitiveness lifting in field, no matter in the weight mitigating composite, the durability of use and minimizing are keeped in repair, are raised cost Etc. all many-sides, polyesters high-performance fiber has increasingly given play to its synthetic competitive advantages.Following many decades, high-performance polyester The development of fiber not only has considerable progress in quantity, more in the expansion of application and carrying of industrial chain whole competitiveness Go up the substantial effect of acquirement.
High intensity, middle contraction will be the Main way of Pet Industrial Fiber development, and affect fiber quality is polyester High molecular collection state structure, is mainly concerned with the active force between polyester molecule, the form of crystallization and structure, orientation structure etc., And the form crystallizing and structure are emphasis therein.
Have many parameters during melt spinning, these parameters determine fiberizing course and spin fiber structure and Performance, production is exactly the fiber of desired properties is obtained by controlling these parameters.Experimental branch line all adopts side for a long time As the type of cooling, energy resource consumption accounts for the significant portion of long filament production cost, with people to chemical fibre performance and quality for blowing Require increasingly to improve, the exploitation of chemical-fibres filaments new product develops it is desirable to higher is cold to the fibre in differentiation direction of high added value But blowing condition, then proposes ring blowing device.Ring blowing device not only possesses the uniform advantage of every synnema wind-engaging, Er Qieneng Consumption is compared relatively low, effectively solves the wind energy loss problem that cross air blasting causes because blowing area is big.
In spinning process, although ring blowing has obvious advantage, but still the cooling of porous yarn cannot be solved well Uneven problem: because spun silk is after circular spinneret is extruded, by ring wind quenching, due to the circular spinneret number of turns relatively Many lead to that the silk of innermost layer may be also uncolled after cooling in outermost silk so that ring blowing hardly enters innermost layer, Thus the problems such as fiber number is irregular, and intensity is irregular in the silk of gained, cause follow-up to silk be processed further difficulty occurs.
Content of the invention
The technical problem to be solved in the present invention is for the deficiencies in the prior art, provides a kind of high uniformity high-strength middle contraction Type polyester industrial fiber and preparation method thereof, the raw material of the high-strength middle shrinkage type polyester industrial fiber of high uniformity of the present invention is modified poly- Ester, introduces the dihydroxylic alcohols segment containing side chain in the strand of modified poly ester, the modified high uniformity of modified polyester preparation is high-strength Middle shrinkage type polyester industrial fiber, under the conditions of uniform temperature, the high-strength middle shrinkage type polyester industrial fiber interior molecules interchain of high uniformity The increasing degree of spatial joint clearance be far longer than the high-strength middle shrinkage type polyester industrial fiber of unbranched high uniformity at equal temperature, The melt viscosity of the high-strength middle shrinkage type polyester industrial fiber of high uniformity reduces, and reduces processing temperature, reduces degradation rate, is conducive to Processing.The arrangement mode of spinneret orifice on the porous spinneret of the high-strength middle shrinkage type polyester industrial fiber of high uniformity of the other present invention For oval shaped arrangements, oval shaped arrangements refer to that the hole of spinneret orifice is centrally located on concentration ellipse, and concentration ellipse is that series is oval, institute There is the major axis of ellipse conllinear, and short axle is conllinear；Higher cooling effectiveness and preferable cooling effect can be reached.
A kind of high-strength middle shrinkage type polyester industrial fiber of high uniformity, the high-strength middle shrinkage type polyester industrial fiber of described high uniformity By modified poly ester, after solid-phase tack producing, spinning obtains；The material of the high-strength middle shrinkage type polyester industrial fiber of described high uniformity is modified poly- Ester, described modified poly ester form by p-phthalic acid segment, ethylene glycol segment and containing the dihydroxylic alcohols segment of side chain, described containing side chain Dihydroxylic alcohols segment refer to that side chain is located on one of dihydroxylic alcohols segment non-end group carbon and side chain is containing 5-10 carbon atom Linear carbon chain dihydroxylic alcohols segment；The high-strength middle shrinkage type polyester industrial fiber of described high uniformity at 260～290 DEG C, melt Viscosity declines 10-20%, and under the test condition for 177 DEG C × 10min × 0.05cn/dtex for the temperature, dry-hot shrinkage is 6.0 ± 0.5%, the fracture strength >=8.1cn/dtex of the high-strength middle shrinkage type polyester industrial fiber of described high uniformity, line density deviation ratio ≤ 1.0%, fracture strength cv value≤2.0%, extension at break cv value≤5.5%.
A kind of high-strength middle shrinkage type polyester industrial fiber of high uniformity is modified poly ester, draws on modified poly ester macromole long-chain Enter the dihydroxylic alcohols segment containing side chain, and the impact to the crystal property of modified poly ester and flow behavior of the length of side chain and quantity is relatively Greatly, the too short purpose not reaching polyester modification of branch lengths, length is oversize to cause new entanglement, affect its flow behavior, when When side chain is located on one of dihydroxylic alcohols segment non-end group carbon and side chain is the linear carbon chain containing 5-10 carbon atom, through changing Property polyester preparation a kind of high-strength middle shrinkage type polyester industrial fiber of high uniformity, under the conditions of uniform temperature, industrial yarn interior part The increasing degree of the spatial joint clearance between subchain is far longer than unbranched industrial yarn at equal temperature, is conducive to industrial yarn melt to glue Degree reduces, and is easy to further process.
As preferred technical scheme:
The high-strength middle shrinkage type polyester industrial fiber of a kind of high uniformity as above, the high-strength middle shrinkage type of described high uniformity The extension at break of polyester industrial fiber is 13.0 ± 1.5%, network 6 ± 2；The number-average molecular weight of described modified poly ester is 15000- 30000.
The high-strength middle shrinkage type polyester industrial fiber of a kind 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, One or more of 2- nonyl -1,6 hexanediol segment or 2- decyl -1,6 hexanediol segment；The described dihydroxylic alcohols segment containing side chain Mole percent ratio with ethylene glycol segment is 2～5%.
A kind of preparation method of the high-strength middle shrinkage type polyester industrial fiber of high uniformity of the present invention, by modified poly ester through solid phase Condensation viscosity enhancing, metering, porous spinneret are extruded, cool down, oiling, stretching, thermal finalization and winding, the high-strength middle receipts of prepared high uniformity Miniature polyester industrial fiber；
On described porous spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and described oval shaped arrangements refer to spinneret orifice Hole be centrally located on concentration ellipse, described concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear；
The preparation process of modified poly ester comprises the following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
P-phthalic acid is made into after slurry with the dihydroxylic alcohols containing side chain, under the catalytic action of concentrated sulphuric acid, is esterified Reaction, obtains p-phthalic acid binary alcohol esters；It is non-that the described dihydroxylic alcohols containing side chain are that side chain is located at one of dihydroxylic alcohols segment On end group carbon and side chain is the dihydroxylic alcohols of the linear carbon chain containing 5-10 carbon atom；
For the dihydroxylic alcohols containing side chain, its side chain is alkyl, is electron withdraw group, in the presence of side chain, makes strand Spatial volume increases, and solvation diminishes, and in dihydroxylic alcohols, proton is difficult to dissociate so that containing dihydroxylic alcohols and the terephthaldehyde of side chain The reactivity of acid is less than ethylene glycol, according to the mixing of same ethylene glycol and terephthaldehyde's acid reaction, can cause the binary containing side chain Alcohol reaction is imperfect, thus ratio in polyester macromolecule for the dihydroxylic alcohols containing side chain for the impact, and then affect the performance of polyester.This Using first the dihydroxylic alcohols containing side chain being carried out esterification with p-phthalic acid under the catalytic action of sulphuric acid, its product exists for invention Ethylene glycol and p phthalic acid esterification add it is ensured that containing the stability of the dihydroxylic alcohols proportioning of side chain after terminating.
(2) preparation of ethylene glycol terephthalate:
P-phthalic acid and ethylene glycol are made into after slurry, carry out esterification, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), stir Mix mixing, in the presence of catalyst and stabilizer, under conditions of negative pressure, carry out successively the coarse vacuum stage polycondensation reaction and The polycondensation reaction of high vacuum stage of Fig, prepared modified poly ester.
The preparation method of the high-strength middle shrinkage type 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, carry out esterification, esterification compressive reaction in nitrogen atmosphere, moulding pressure is normal pressure～0.3mpa, temperature is 180 ～240 DEG C, be esterification terminal when the water quantity of distillate in esterification reaches more than the 90% of theoretical value；Obtain to benzene two Formic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
P-phthalic acid and ethylene glycol are made into after slurry and add in reactor, carry out esterification, esterification is in nitrogen Atmosphere encloses middle compressive reaction, and moulding pressure is normal pressure～0.3mpa, and temperature is 250～260 DEG C, when the water in esterification distillates It is esterification terminal that amount reaches during more than the 90% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), stir Mix mixing 15-20 minute, in the presence of catalyst and stabilizer, the polycondensation starting the 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 at 260～270 DEG C, the response time is temperature control 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, 50～90 minutes response time, prepared modified poly ester；
Again modified poly ester is obtained Modified polyester chips through pelletizing, obtained polyester slice is viscosified by solid phase polycondensation, makes The intrinsic viscosity of polyester slice brings up to 1.0～1.2dl/g, as high viscous section；Again through metering, porous spinneret extrusion, cold But, oil, stretch, thermal finalization and winding, the high-strength middle shrinkage type polyester industrial fiber of prepared high uniformity；
Spinning main technologic parameters are:
The temperature of described extrusion is 290～320 DEG C；
The pathogenic wind-warm of described cooling is 20～30 DEG C；
Described stretching, heat setting process:
Gr-1 speed 480～600m/min；Temperature is room temperature；
Gr-2 speed 500～1000m/min；80～100 DEG C of temperature；
Gr-3 speed 1800～2500m/min；100～150 DEG C of temperature；
Gr-4 speed 2800～3500m/min；200～250 DEG C of temperature；
Gr-5 speed 2800～3500m/min；200～250 DEG C of temperature；
Gr-6 speed 2600～3400m/min；150～220 DEG C of temperature；
The speed of described winding is 2600～3400m/min.
The preparation method of the high-strength middle shrinkage type 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 Than for 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 middle shrinkage type polyester industrial fiber of a kind of high uniformity as above, described containing side chain two First 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- One or more of nonyl -1,6 hexanediol or 2- decyl -1,6 hexanediol.
The preparation method of the high-strength middle shrinkage type polyester industrial fiber of a kind of high uniformity as above, described porous spinneret For circular spinneret or elliptical spinneret plate；The diameter of described circle spinneret and the difference of the oval maximum long axis length of series More than 10mm, described elliptical spinneret plate is more than 10mm with the difference of the oval maximum long axis length of series.
The preparation method of the high-strength middle shrinkage type polyester industrial fiber of a kind of high uniformity as above, described porous spinneret Upper spinneret orifice be arranged as that major axis and/or short axle are symmetrical, the guide hole diameter that the spacing of adjacent spinneret orifice is more than or equal to spinneret orifice adds 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, spinneret orifice is oval The number of plies of arrangement is less than the number of plies of circular arrangement, and the hole count of spinneret orifice oval shaped arrangements is more than the hole count of circular arrangement, therefore, spray Silk hole oval shaped arrangements are conducive to the cooling of ring blowing, improve the cooling effectiveness of ring blowing, the fibre property of preparation is also more excellent Good.Major axis is closer to 1 with the ratio of minor axis length, and ellipse is more similar to justify, and the difference of cooling effectiveness and cooling effect is little； When the ratio of major axis and minor axis length is 1.3, cooling effect significantly improves, and individual pen hole count is corresponding to increase by 16%；Major axis and short axle When the ratio of length is 1.8, cooling effect improves larger, the corresponding increase by 33% of individual pen hole count, in the case of identical hole count, the present invention Oval shaped arrangements reduce than the number of turns of conventional concentric circle best-fit it is easy to cooling wind thoroughly, makes the fiber cooling condition of Internal and external cycle Evenly；When the ratio of major axis and minor axis length is more than 1.8, ellipse is partial to form flat shape, is difficult to punch, simultaneously cold But effect no longer raises.Therefore, the oval major axis of series and the ratio of minor axis length are 1.3～1.8, can reach higher cold But efficiency and preferable cooling effect.
The preparation method of the high-strength middle shrinkage type polyester industrial fiber of a kind of high uniformity as above, the leading of described spinneret orifice Bore dia is 1.5～2.5mm；The spray webbing hole count of described spinneret be 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 middle shrinkage type 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, makes free volume Increasing degree be far longer than the characteristic of unbranched polyester macromolecule chain, the free volume of the industrial yarn of modified polyester preparation It is far longer than unbranched industrial yarn at equal temperature, advantageously reduce its melt viscosity.
On the spinneret of the present invention, the arrangement mode of spinneret orifice is oval shaped arrangements, when the effective area of spinneret is identical, The number of plies of spinneret orifice oval shaped arrangements is less than the number of plies of circular arrangement, and ring blowing is easier to blow through dynamic analysis of spinning, dynamic analysis of spinning More preferably, the industrial yarn of preparation is also more excellent for cooling effect.When the effective area of spinneret is identical, spinneret orifice oval shaped arrangements Hole count is more than the hole count of circular arrangement, and oval shaped arrangements are capable of greatly cooling down, and significantly improve cooling effectiveness.
Beneficial effect:
The raw material of the high-strength middle shrinkage type 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 containing 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 middle shrinkage type polyester industrial fiber of high uniformity of gained of the present invention is modified poly ester, two containing side chain The introducing of first alcohol segment to the structural regularity of modified poly ester there is no big destruction, maintain the premium properties of polyester fiber.
On the high-strength middle shrinkage type polyester industrial fiber spinneret of high uniformity of the present invention, the arrangement mode of spinneret orifice is ellipse Shape arranges, and when the effective area of spinneret is identical, the number of plies of spinneret orifice oval shaped arrangements is less than the number of plies of circular arrangement, and ring is dried It is easier to blow through dynamic analysis of spinning, more preferably, the fibre property of preparation is also more excellent for the cooling effect of dynamic analysis of spinning.
On the high-strength middle shrinkage type polyester industrial fiber spinneret of high uniformity of the present invention, the arrangement mode of spinneret orifice is ellipse 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 greatly cooling down, and significantly improves cooling effectiveness.
Brief description
Fig. 1 is the oval shaped arrangements figure of 374 spinneret orifices, and the aperture of spinneret orifice is 2.0mm, the length of transverse and short axle Degree ratio is 1.3；
Fig. 2 is the circular arrangement figure of 370 spinneret orifices, and the aperture of spinneret orifice is 2.0mm；
Fig. 3 is the oval shaped arrangements figure of 382 spinneret orifices, and the aperture of spinneret orifice is 2.0mm, the length of transverse and short axle Degree ratio is 1.6.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate this Bright rather than limit the scope of the present invention.In addition, it is to be understood that after having read the content of present invention instruction, art technology Personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited Fixed scope.
Embodiment 1
A kind of preparation method of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By the p-phthalic acid for 1:1.3 for the mol ratio 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 0.3% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is normal pressure, and temperature is 180 DEG C, when the water in esterification distillates It is esterification terminal that amount reaches during the 90% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:1.2 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is normal pressure, and temperature is 250 DEG C, when the water in esterification distillates It is esterification terminal that amount reaches during the 90% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 2% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 15 minutes is adding Measure for p-phthalic acid weight 0.01% the catalytic antimony trioxide and addition be p-phthalic acid weight 0.01% Stabilizer triphenyl phosphate in the presence of, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure Steadily being evacuated to absolute pressure by normal pressure is 500pa, and at 260 DEG C, the response time is 30 minutes to temperature control；Then proceed to take out very Sky, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 100pa, and reaction temperature controls 275 DEG C, 50 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 15000, 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.
Embodiment 2
A kind of preparation method of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By the p-phthalic acid for 1:1.38 for the mol ratio and 2- hexyl -1,3 propylene glycol are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of 0.32% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.13mpa, and temperature is 181 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 91% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:1.3 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.12mpa, and temperature is 251 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 91% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 2.1% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 16 minutes is adding Entering 0.011% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.02% stabilizer triphenyl phosphate, start the polycondensation reaction in coarse vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 490pa by normal pressure, and at 262 DEG C, the response time is 31 minutes to temperature control；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 99pa, and reaction temperature controls at 276 DEG C, 51 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 16000, 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
A kind of preparation method of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By the p-phthalic acid for 1:1.33 for the mol ratio and 2- heptyl -1,3 propylene glycol are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of 0.33% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.12mpa, and temperature is 183 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:1.31 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.31mpa, and temperature is 252 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 2.2% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 16 minutes is adding Entering 0.03% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.02% stabilizer triphenyl phosphate, start the polycondensation reaction in coarse vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 498pa by normal pressure, and at 263 DEG C, the response time is 32 minutes to temperature control；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 80pa, and reaction temperature controls at 277 DEG C, 57 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 15900, 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
A kind of preparation method of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By the p-phthalic acid for 1:1.34 for the mol ratio and 2- octyl group -1,3 propylene glycol are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of 0.34% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.13mpa, and temperature is 184 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 93% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:1.32 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.33mpa, and temperature is 253 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 93% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 2.3% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 17 minutes is adding Entering 0.033% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.023% stabilizer triphenyl phosphate, start the polycondensation reaction in coarse vacuum stage, this rank It is 497pa that section pressure is steadily evacuated to absolute pressure by normal pressure, and at 264 DEG C, the response time is 33 minutes to temperature control；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, 58 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 15800, 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
A kind of preparation method of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By the p-phthalic acid for 1:1.35 for the mol ratio and 2- nonyl -1,3 propylene glycol are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of 0.36% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.14mpa, and temperature is 185 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 93.2% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:1.33 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.14mpa, and temperature is 254 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 93.2% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 2.4% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 17 minutes is adding Entering 0.034% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.024% stabilizer triphenyl phosphate, start the polycondensation reaction in coarse vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 496pa by normal pressure, and at 265 DEG C, the response time is 34 minutes to temperature control；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 70pa, and reaction temperature controls 277 DEG C, 59 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 15900, 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
A kind of preparation method of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By the p-phthalic acid for 1:1.36 for the mol ratio and 2- decyl -1,3 propylene glycol are made into slurry and add in reactor, Concentration is 50wt%, and addition is under the catalytic action of 0.37% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.15mpa, and temperature is 186 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 93.3% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:1.34 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.15mpa, and temperature is 255 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 93.3% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 2.5% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Entering 0.035% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.025% stabilizer triphenyl phosphate, start the polycondensation reaction in coarse vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 495pa by normal pressure, and at 266 DEG C, the response time is 35 minutes to temperature control；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 70pa, and reaction temperature controls 278 DEG C, 60 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 16000, by p-phthalic acid segment, ethylene glycol segment and the 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
A kind of preparation method of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
The p-phthalic acid for 1:1.37 for the mol ratio and 2- amyl group-Isosorbide-5-Nitrae butanediol are made into slurry add in reactor, Concentration is 60wt%, and addition is under the catalytic action of 0.38% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.16mpa, and temperature is 187 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 93.4% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:1.36 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.16mpa, and temperature is 256 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 93.4% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 2.6% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 19 minutes is adding Entering 0.036% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.025% stabilizer triphenyl phosphate, start the polycondensation reaction in coarse vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 496pa by normal pressure, and at 267 DEG C, the response time is 36 minutes to temperature control；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 70pa, and reaction temperature controls 278 DEG C, 61 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 16000, by p-phthalic acid segment, ethylene glycol segment and 2- penta Base-Isosorbide-5-Nitrae butanediol segment composition, 2- amyl group-Isosorbide-5-Nitrae butanediol segment is 2.6% with the Mole percent ratio of ethylene glycol segment.
Embodiment 8
A kind of preparation method of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
The p-phthalic acid for 1:1.38 for the mol ratio and 2- hexyl-Isosorbide-5-Nitrae butanediol are made into slurry add in reactor, Concentration is 55wt%, and addition is under the catalytic action of 0.39% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.17mpa, and temperature is 188 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 93.5% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:1.37 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.17mpa, and temperature is 257 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 93.5% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 2.7% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 19 minutes is adding Entering 0.036% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.025% stabilizer triphenyl phosphate, start the polycondensation reaction in coarse vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 496pa by normal pressure, and at 267 DEG C, the response time is 36 minutes to temperature control；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 60pa, and reaction temperature controls 278 DEG C, 61 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 17000, 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
A kind of preparation method of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
The p-phthalic acid for 1:1.39 for the mol ratio and 2- heptyl-Isosorbide-5-Nitrae butanediol are made into slurry add in reactor, Concentration is 50wt%, and addition is under the catalytic action of 0.4% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.17mpa, and temperature is 188 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 93.5% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:1.37 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.17mpa, and temperature is 257 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 93.5% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 2.8% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 16 minutes is adding Entering 0.04% catalyst glycol antimony that amount is p-phthalic acid weight and addition is the 0.026% of p-phthalic acid weight Stabilizer trimethyl phosphate in the presence of, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure Absolute pressure 497pa is steadily evacuated to by normal pressure, at 268 DEG C, the response time is 38 minutes to temperature control；Then proceed to evacuation, Carry out the polycondensation reaction of high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 50pa, and reaction temperature controls at 279 DEG C, instead 62 minutes between seasonable, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 18000, 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
A kind of preparation method of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
The p-phthalic acid for 1:1.4 for the mol ratio and 2- octyl group-Isosorbide-5-Nitrae butanediol are made into slurry add in reactor, Concentration is 55wt%, and addition is under the catalytic action of 0.4% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.17mpa, and temperature is 188 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 93.5% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:1.38 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.18mpa, and temperature is 257.8 DEG C, when in esterification Water quantity of distillate reach theoretical value 93.6% when be esterification terminal, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 3% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 17 minutes is adding Measure for p-phthalic acid weight 0.03% catalyst glycol antimony and addition be the 0.027% of p-phthalic acid weight In the presence 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 at 269 DEG C, the response time is 39 minutes to temperature control；Then proceed to evacuation, enter The polycondensation reaction of row high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 50pa, and reaction temperature controls at 278 DEG C, reaction 64 minutes time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 19000, 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
A kind of preparation method of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
The p-phthalic acid for 1:1.4 for the mol ratio and 2- nonyl-Isosorbide-5-Nitrae butanediol are made into slurry add in reactor, Concentration is 55wt%, and addition is under the catalytic action of 0.4% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.18mpa, and temperature is 189 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 93.6% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:1.39 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.19mpa, and temperature is 258.8 DEG C, when in esterification Water quantity of distillate reach theoretical value 94% when be esterification terminal, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Measure for p-phthalic acid weight 0.04% catalyst glycol antimony and addition be the 0.03% of p-phthalic acid weight In the presence 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 at 260 DEG C, the response time is 40 minutes to temperature control；Then proceed to evacuation, enter The polycondensation reaction of row high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 40pa, and reaction temperature controls at 277 DEG C, reaction 63 minutes time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 20000, 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
A kind of preparation method of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
The p-phthalic acid for 1:1.4 for the mol ratio and 2- nonyl-Isosorbide-5-Nitrae butanediol are made into slurry add in reactor, Concentration is 55wt%, and addition is under the catalytic action of 0.4% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.2mpa, and temperature is 200 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 94% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:1.6 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.2mpa, and temperature is 256 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 94% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.5% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Enter that amount is 0.038% catalyst acetic acid antimony of p-phthalic acid weight and addition is p-phthalic acid weight 0.03% Under conditions of negative pressure, in the presence of stabilizer NSC 6513, start the polycondensation reaction in coarse vacuum stage, this staged pressure Absolute pressure 497pa is steadily evacuated to by normal pressure, at 265 DEG C, the response time is 42 minutes to temperature control；Then proceed to evacuation, Carry out the polycondensation reaction of high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 40pa, and reaction temperature controls at 277 DEG C, instead 70 minutes between seasonable, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 26000, by p-phthalic acid segment, ethylene glycol segment and the 2- last of the ten Heavenly stems Base-Isosorbide-5-Nitrae butanediol segment composition, 2- decyl-Isosorbide-5-Nitrae butanediol segment is 4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 13
A kind of preparation method of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By the p-phthalic acid for 1:1.5 for the mol ratio 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 0.5% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.3mpa, and temperature is 240 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:2.0 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.3mpa, and temperature is 260 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 5% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 20 minutes is adding Measure for p-phthalic acid weight 0.05% catalyst acetic acid antimony and addition be p-phthalic acid weight 0.05% steady In the presence of determining 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 at 270 DEG C, the response time is 50 minutes to temperature control；Then proceed to evacuation, Carry out the polycondensation reaction of high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 30pa, and reaction temperature controls at 280 DEG C, instead 90 minutes between seasonable, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 30000, by p-phthalic acid segment, ethylene glycol segment and the 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
A kind of preparation method of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By the p-phthalic acid for 1:1.47 for the mol ratio 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 0.47% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28mpa, and temperature is 220 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:1.8 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27mpa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Measure for p-phthalic acid weight 0.04% catalyst glycol antimony and addition be the 0.04% of p-phthalic acid weight In the presence 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 at 263 DEG C, the response time is 47 minutes to temperature control；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, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester 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
A kind of preparation method of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By the p-phthalic acid for 1:1.46 for the mol ratio 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 0.49% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28mpa, and temperature is 233 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:1.8 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28mpa, and temperature is 259 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.5% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 19 minutes is adding Entering 0.044% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.046% stabilizer triphenyl phosphate, start the polycondensation reaction in coarse vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 490pa by normal pressure, and at 269 DEG C, the response time is 48 minutes to temperature control；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40pa, and reaction temperature controls at 279 DEG C, 87 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester 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
A kind of preparation method of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By the p-phthalic acid for 1:1.49 for the mol ratio 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 0.48% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28mpa, and temperature is 230 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:1.8 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28mpa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.7% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 19 minutes is adding Entering 0.048% catalyst glycol antimony that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.047% stabilizer triphenyl phosphate, start the polycondensation reaction in coarse vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 460pa by normal pressure, and at 267 DEG C, the response time is 48 minutes to temperature control；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40pa, and reaction temperature controls at 279 DEG C, 83 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester 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
A kind of preparation method of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By the p-phthalic acid for 1:1.467 for the mol ratio and 2- hexyl -1,6 hexanediol are made into slurry and add in reactor, It is 60wt% in concentration, addition is under the catalytic action of 0.47% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27mpa, and temperature is 236 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:1.89 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28mpa, and temperature is 258 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.3% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Entering 0.04% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.041% stabilizer NSC 6513, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 490pa by normal pressure, and at 268 DEG C, the response time is 48 minutes to temperature control；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40pa, reaction temperature controls 278 DEG C, 85 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester 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
A kind of preparation method of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By the p-phthalic acid for 1:1.48 for the mol ratio 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 0.46% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28mpa, and temperature is 230 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:1.88 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28mpa, and temperature is 256 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.7% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Entering 0.047% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.047% stabilizer triphenyl phosphate, start the polycondensation reaction in coarse vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 480pa by normal pressure, and at 265 DEG C, the response time is 47 minutes to temperature control；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40pa, and reaction temperature controls at 279 DEG C, 85 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester 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
A kind of preparation method of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By the p-phthalic acid for 1:1.46 for the mol ratio and 2- decyl -1,5 pentanediols are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of 0.47% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28mpa, and temperature is 238 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:1.9 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28mpa, and temperature is 259 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during more than the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.7% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 19 minutes is adding Entering the 0.046% catalyst acetic acid antimony that amount is p-phthalic acid weight and addition is the 0.048% of p-phthalic acid weight Stabilizer NSC 6513 in the presence of, 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 at 267 DEG C, the response time is 49 minutes to temperature control；Then proceed to take out very Sky, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 40pa, and reaction temperature controls at 278 DEG C, 87 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 29000, by p-phthalic acid segment, ethylene glycol segment and the 2- last of the ten Heavenly stems Base -1,5 pentanediol segment compositions, 2- decyl -1,5 pentanediol segments are 4.7% with the Mole percent ratio of ethylene glycol segment.
Embodiment 20
A kind of preparation method of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By the p-phthalic acid for 1:1.46 for the mol ratio and 2- nonyl -1,5 pentanediols are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of 0.46% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.26mpa, and temperature is 221 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:1.89 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.25mpa, and temperature is 259 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.1% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Entering 0.041% catalyst glycol antimony that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.042% stabilizer trimethyl phosphate, start the polycondensation reaction in coarse vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 460pa by normal pressure, and at 265 DEG C, the response time is 47 minutes to temperature control；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40pa, and reaction temperature controls at 278 DEG C, 85 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester 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
A kind of preparation method of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By the p-phthalic acid for 1:1.43 for the mol ratio and 2- octyl group -1,5 pentanediols are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of 0.47% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27mpa, and temperature is 235 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:1.78 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.26mpa, and temperature is 255 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.3% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 17 minutes is adding Entering 0.043% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.049% stabilizer triphenyl phosphate, start the polycondensation reaction in coarse vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 490pa by normal pressure, and at 268 DEG C, the response time is 46 minutes to temperature control；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40pa, and reaction temperature controls at 275 DEG C, 85 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester 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
A kind of preparation method of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By the p-phthalic acid for 1:1.43 for the mol ratio and 2- heptyl -1,5 pentanediols are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of 0.45% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.29mpa, and temperature is 235 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:1.87 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27mpa, and temperature is 255 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.6% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Entering 0.047% catalyst glycol antimony that amount is p-phthalic acid weight and addition is the 0.04% of p-phthalic acid weight Stabilizer triphenyl phosphate in the presence of, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure Absolute pressure 470pa is steadily evacuated to by normal pressure, at 268 DEG C, the response time is 45 minutes to temperature control；Then proceed to evacuation, Carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 40pa, reaction temperature controls at 279 DEG C, reaction 83 minutes time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 29000, by 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
A kind of preparation method of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By the p-phthalic acid for 1:1.457 for the mol ratio and 2- hexyl -1,5 pentanediols are made into slurry and add in reactor, It is 55% in concentration, addition is under the catalytic action of 0.46% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28mpa, and temperature is 239 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:1.81 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27mpa, and temperature is 255 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.41% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 19 minutes, Addition is 0.042% the catalytic antimony trioxide of p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.048% stabilizer NSC 6513, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 495pa by normal pressure, and at 265 DEG C, the response time is 45 minutes to temperature control；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50pa, reaction temperature controls 275 DEG C, 85 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester 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
A kind of preparation method of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By the p-phthalic acid for 1:1.47 for the mol ratio and 2- amyl group -1,5 pentanediols are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of 0.48% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27mpa, and temperature is 245 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:1.81 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27mpa, and temperature is 259 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.67% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 19 minutes, Addition is 0.041% the catalytic antimony trioxide of p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.042% stabilizer triphenyl phosphate, start the polycondensation reaction in coarse vacuum stage, this rank Section pressure is steadily evacuated to absolute pressure 485pa by normal pressure, and at 268 DEG C, the response time is 46 minutes to temperature control；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50pa, and reaction temperature controls at 275 DEG C, 89 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester 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
A kind of preparation method of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
The p-phthalic acid for 1:1.45 for the mol ratio and 2- hexyl -1,5 pentanediol and 2- amyl group -1,4 butanediol is mixed Compound is made into slurry and adds in reactor, wherein 2- hexyl -1, and the mol ratio of 5 pentanediols and 2- amyl group-Isosorbide-5-Nitrae butanediol is 3:1, It is 55% in concentration, addition is under the catalytic action of 0.49% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.26mpa, and temperature is 236 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:1.8 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28mpa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.4% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Entering 0.042% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.047% stabilizer NSC 6513, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 495pa by normal pressure, and at 265 DEG C, the response time is 49 minutes to temperature control；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50pa, reaction temperature controls 278 DEG C, 88 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester be 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
A kind of preparation method 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 the p-phthalic acid sum for 1:1.45 for the mol ratio 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 0.45% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28mpa, and temperature is 239 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:1.84 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification anti- Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.29mpa, and temperature is 255 DEG C, when in esterification It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.6% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Entering 0.0423% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.045% stabilizer NSC 6513, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 495pa by normal pressure, and at 265 DEG C, the response time is 45 minutes to temperature control；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50pa, reaction temperature controls 278 DEG C, 85 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester be 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
A kind of preparation method of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
The p-phthalic acid for 1:1.45 for the mol ratio and 2- hexyl -1,5 pentanediol and 2- amyl group -1,4 butanediol is mixed Compound is made into slurry and adds in reactor, wherein 2- hexyl -1, and the mol ratio of 5 pentanediols and 2- amyl group-Isosorbide-5-Nitrae butanediol is 3:1, It is 55% in concentration, addition is under the catalytic action of 0.49% concentrated sulphuric acid of p-phthalic acid weight, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.26mpa, and temperature is 236 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 96% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:1.8 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28mpa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.4% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding Entering 0.042% the catalytic antimony trioxide that amount is p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.047% stabilizer NSC 6513, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 495pa by normal pressure, and at 265 DEG C, the response time is 49 minutes to temperature control；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50pa, reaction temperature controls 278 DEG C, 88 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester be 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
A kind of preparation method of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
The p-phthalic acid for 1:1.45 for the mol ratio is own with 2- octyl group -1,3 propylene glycol, 2- amyl group -1,4 butanediol and 2- 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 0.47% concentrated sulphuric acid, carry out esterification, esterification compressive reaction in nitrogen atmosphere, moulding pressure For 0.29mpa, temperature is 235 DEG C, is esterification terminal when the water quantity of distillate in esterification reaches the 92% of theoretical value, Obtain p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
By mol ratio be 1:1.8 p-phthalic acid and ethylene glycol is made into after slurry and adds in reactor, carries out esterification, Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27mpa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters are 4.71% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, Addition is 0.04% the catalytic antimony trioxide of p-phthalic acid weight and addition is p-phthalic acid weight Under conditions of negative pressure, in the presence of 0.041% stabilizer NSC 6513, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 490pa by normal pressure, and at 268 DEG C, the response time is 49 minutes to temperature control；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50pa, reaction temperature controls 277 DEG C, 84 minutes response time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 29000, by p-phthalic acid segment, ethylene glycol segment, band side chain Glycol segment composition, wherein branched glycol segment be 2- octyl group -1,3 propylene glycol segments, 2- amyl group-Isosorbide-5-Nitrae butanediol chain Section and 2- hexyl -1,6 hexanediol segments form, and branched glycol segment with the Mole percent ratio of ethylene glycol segment is 4.71%.
Embodiment 29
A kind of preparation method of the high-strength middle miniature polyester industrial fiber of high uniformity, the high-strength middle miniature polyester industrial of high uniformity Silk is obtained using porous spinneret, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to spray webbing The hole in hole is centrally located on concentration ellipse, and concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear.
As shown in figure 1, the major axis of ellipse is 1.3 with the ratio of minor axis length, the spacing of adjacent spinneret orifice is equal to spinneret orifice Guide hole diameter add 1.5mm, spinneret is circular spinneret, the diameter of circular spinneret oval maximum long axial length with series The difference of degree is 11mm, a diameter of 2.0mm of guide hole of spinneret orifice, and the spray webbing hole count of spinneret is 374, the spinneret orifice of spinneret Shape of cross section be circle.
The modified poly ester that embodiment 1 is obtained is extruded, cools down, oils, is drawn through solid phase polycondensation thickening, metering, porous spinneret Stretch, thermal finalization and winding, the high-strength middle miniature polyester industrial fiber of prepared high uniformity, the wherein temperature of extrusion is 280 DEG C, cooling Pathogenic wind-warm is 20 DEG C, gr-1 speed 480m/min；Temperature is room temperature；Gr-2 speed 500m/min；80 DEG C of temperature；Gr-3 speed 1800m/min；100 DEG C of temperature；Gr-4 speed 2800m/min；200 DEG C of temperature；Gr-5 speed 2800m/min；200 DEG C of temperature； Gr-6 speed 2600m/min；150 DEG C of temperature；The speed of winding is 2600m/min.
The fracture strength of the high-strength middle miniature polyester industrial fiber of prepared high uniformity is 8.4cn/dtex；Line density deviation ratio For 0.6%, fracture strength cv value is 1.8%, and extension at break cv value is 4.5%, and extension at break is 12.0, and network is 5,260 At DEG C, melt viscosity declines 11%, under the test condition for 177 DEG C × 10min × 0.05cn/dtex for the temperature, dry shrinkage Rate is 6%.
Embodiment 30
A kind of preparation method of the high-strength middle miniature polyester industrial fiber of high uniformity, the high-strength middle miniature polyester industrial of high uniformity Silk is obtained using porous spinneret, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to spray webbing The hole in hole is centrally located on concentration ellipse, and concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear.
As shown in figure 3, the major axis of ellipse is 1.6 with the ratio of minor axis length, the spacing of adjacent spinneret orifice is equal to spinneret orifice Guide hole diameter add 1.5mm, spinneret is circular spinneret, the diameter of circular spinneret oval maximum long axial length with series The difference of degree is 11mm, a diameter of 2.0mm of guide hole of spinneret orifice, and the spray webbing hole count of spinneret is 382, the spinneret orifice of spinneret Shape of cross section be circle.
The modified poly ester that embodiment 1 is obtained is extruded, cools down, oils, is drawn through solid phase polycondensation thickening, metering, porous spinneret Stretch, thermal finalization and winding, the high-strength middle miniature polyester industrial fiber of prepared high uniformity, the wherein temperature of extrusion is 280 DEG C, cooling Pathogenic wind-warm is 20 DEG C, gr-1 speed 480m/min；Temperature is room temperature；Gr-2 speed 500m/min；80 DEG C of temperature；Gr-3 speed 1800m/min；100 DEG C of temperature；Gr-4 speed 2800m/min；200 DEG C of temperature；Gr-5 speed 2800m/min；200 DEG C of temperature； Gr-6 speed 2600m/min；150 DEG C of temperature；The speed of winding is 2600m/min.
The fracture strength of the high-strength middle miniature polyester industrial fiber of prepared high uniformity is 8.4cn/dtex；Line density deviation ratio For 0.7%, fracture strength cv value is 1.7%, and extension at break cv value is 4.8%, and extension at break is 13.0, and network is 5,260 At DEG C, melt viscosity declines 11%, under the test condition for 177 DEG C × 10min × 0.05cn/dtex for the temperature, dry shrinkage Rate is 5.9%.
Comparative example 1
A kind of preparation method of the high-strength middle miniature polyester industrial fiber of high uniformity, the high-strength middle miniature polyester industrial of high uniformity Silk is obtained using porous spinneret, and on spinneret, the arrangement mode of spinneret orifice is circular arrangement, and circular arrangement refers to spinneret orifice Hole is centrally located on concentric circular, and concentric circular is that series is circular.As shown in Fig. 2 the spacing of adjacent spinneret orifice is equal to leading of spinneret orifice Bore dia adds 1.5mm, and spinneret is circular spinneret, the difference of the diameter of circular spinneret and the circular maximum diameter of series For 11mm, a diameter of 2.0mm of guide hole of spinneret orifice, the spray webbing hole count of spinneret is 370, the cross section of the spinneret orifice of spinneret Generally circular in shape.
The modified poly ester that embodiment 1 is obtained is extruded, cools down, oils, is drawn through solid phase polycondensation thickening, metering, porous spinneret Stretch, thermal finalization and winding, the high-strength middle miniature polyester industrial fiber of prepared high uniformity, the wherein temperature of extrusion is 280 DEG C, cooling Pathogenic wind-warm is 20 DEG C, gr-1 speed 480m/min；Temperature is room temperature；Gr-2 speed 500m/min；80 DEG C of temperature；Gr-3 speed 1800m/min；100 DEG C of temperature；Gr-4 speed 2800m/min；200 DEG C of temperature；Gr-5 speed 2800m/min；200 DEG C of temperature； Gr-6 speed 2600m/min；150 DEG C of temperature；The speed of winding is 2600m/min.
The fracture strength of the high-strength middle miniature polyester industrial fiber of prepared high uniformity is 8.6cn/dtex；Line density deviation ratio For 1%, fracture strength cv value is 1.9%, and extension at break cv value is 5.3%, and extension at break is 13.1, and network is 5, at 260 DEG C Under, melt viscosity declines 11%, under the test condition for 177 DEG C × 10min × 0.05cn/dtex for the temperature, dry-hot shrinkage For 6.35%.
When identical with the effective area that embodiment 29 contrast can be seen that spinneret, (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 identical with the effective area that embodiment 30 contrast can be seen that spinneret, oval The spinneret orifice number of plies of shape arrangement is 5, and less than the spinneret orifice number of plies 8 of circular arrangement, cooling effect is more preferable, the 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, Fiber linear density deviation ratio that embodiment 29 and embodiment 30 are obtained, fracture strength cv value, extension at break cv value are less than comparative example 1, under the conditions of same process is described, it is better than adopting spinneret using the fibre property that the spinneret of spinneret orifice oval shaped arrangements is obtained The spinneret of circular arrangement.
Embodiment 31～33
A kind of preparation method of the high-strength middle miniature polyester industrial fiber of high uniformity, is obtained using porous spinneret, spinneret The arrangement mode of upper spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located on concentration ellipse, with The heart is oval oval for series, and all oval major axis are conllinear, and short axle is conllinear.
Spinneret orifice be arranged as long axial symmetry, oval major axis is 1.4 with the ratio of minor axis length, between adjacent spinneret orifice Add 1.6mm away from the guide hole diameter equal to spinneret orifice, spinneret is circular spinneret, the diameter of circular spinneret is oval with series The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 244 of spinneret, spray webbing The shape of cross section of the spinneret orifice of plate is square.
The high-strength middle miniature polyester industrial fiber of high uniformity is extruded, cools down, oiling, stretching through metering, porous spinneret, heat is fixed Type and winding, the high-strength middle miniature polyester industrial fiber of prepared high uniformity, the wherein temperature of extrusion are 300 DEG C, and the pathogenic wind-warm of cooling is 25℃；Stretching, heat setting process parameter are: gr-1 speed 600m/min；Temperature is room temperature；Gr-2 speed 1000m/min；Temperature 100℃；Gr-3 speed 2500m/min；150 DEG C of temperature；Gr-4 speed 3500m/min；250 DEG C of temperature；Gr-5 speed 3500m/ min；250 DEG C of temperature；Gr-6 speed 3400m/min；220 DEG C of temperature；The speed of winding is 3400m/min.
At 280 DEG C, melt viscosity declines percent to the high-strength middle miniature polyester industrial fiber of prepared high uniformity, under room temperature The mechanical performance data of industrial yarn, and under the test condition for 177 DEG C × 10min × 0.05cn/dtex for the temperature, industrial yarn Dry-hot shrinkage such as following table.
Embodiment 34～36
A kind of preparation method of the high-strength middle miniature polyester industrial fiber of high uniformity, is obtained using porous spinneret, spinneret The arrangement mode of upper spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located on concentration ellipse, with The heart is oval oval for series, and all oval major axis are conllinear, and short axle is conllinear.
Spinneret orifice be arranged as long axial symmetry, oval major axis is 1.4 with the ratio of minor axis length, between adjacent spinneret orifice Add 1.6mm away from the guide hole diameter equal to spinneret orifice, spinneret is circular spinneret, the diameter of circular spinneret is oval with series The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 288 of spinneret, spray webbing The shape of cross section of the spinneret orifice of plate is square.
The high-strength middle miniature polyester industrial fiber of high uniformity is extruded, cools down, oiling, stretching through metering, porous spinneret, heat is fixed Type and winding, the high-strength middle miniature polyester industrial fiber of prepared high uniformity, the wherein temperature of extrusion are 310 DEG C, and the pathogenic wind-warm of cooling is 30℃；Stretching, heat setting process parameter are: gr-1 speed 500m/min；Temperature is room temperature；Gr-2 speed 600m/min；Temperature 90℃；Gr-3 speed 2200m/min；130 DEG C of temperature；Gr-4 speed 2900m/min；230 DEG C of temperature；Gr-5 speed 3200m/ min；230 DEG C of temperature；Gr-6 speed 3000m/min；200 DEG C of temperature；The speed of winding is 2800m/min.
The high-strength middle miniature polyester industrial fiber of prepared high uniformity melt viscosity at 290 DEG C declines percentage ratio, under room temperature The mechanical performance data of industrial yarn, and under the test condition for 177 DEG C × 10min × 0.05cn/dtex for the temperature, industrial yarn Dry-hot shrinkage such as following table.
Embodiment 37～39
A kind of preparation method of the high-strength middle miniature polyester industrial fiber of high uniformity, is obtained using porous spinneret, spinneret The arrangement mode of upper spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located on concentration ellipse, with The heart is oval oval for series, and all oval major axis are conllinear, and short axle is conllinear.
Spinneret orifice be arranged as long axial symmetry, oval major axis is 1.4 with the ratio of minor axis length, between adjacent spinneret orifice Add 1.6mm away from the guide hole diameter equal to spinneret orifice, spinneret is circular spinneret, the diameter of circular spinneret is oval with series The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 192 of spinneret, spray webbing The shape of cross section of the spinneret orifice of plate is square.
The high-strength middle miniature polyester industrial fiber of high uniformity is extruded, cools down, oiling, stretching through metering, porous spinneret, heat is fixed Type and winding, the high-strength middle miniature polyester industrial fiber of prepared high uniformity, the wherein temperature of extrusion are 290 DEG C, and the pathogenic wind-warm of cooling is 20℃；Stretching, heat setting process parameter are: gr-1 speed 500m/min；Temperature is room temperature；Gr-2 speed 800m/min；Temperature 85℃；Gr-3 speed 2300m/min；120 DEG C of temperature；Gr-4 speed 3200m/min；210 DEG C of temperature；Gr-5 speed 3200m/ min；230 DEG C of temperature；Gr-6 speed 3200m/min；200 DEG C of temperature；The speed of winding is 3200m/min.
The high-strength middle miniature polyester industrial fiber of prepared high uniformity melt viscosity at 270 DEG C declines percent, under room temperature The mechanical performance data of industrial yarn, and under the test condition for 177 DEG C × 10min × 0.05cn/dtex for the temperature, industrial yarn Dry-hot shrinkage such as following table.
Embodiment 40～42
A kind of preparation method of the high-strength middle miniature polyester industrial fiber of high uniformity, is obtained using porous spinneret, spinneret The arrangement mode of upper spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located on concentration ellipse, with The heart is oval oval for series, and all oval major axis are conllinear, and short axle is conllinear.
Spinneret orifice be arranged as long axial symmetry, oval major axis is 1.4 with the ratio of minor axis length, between adjacent spinneret orifice Add 1.6mm away from the guide hole diameter equal to spinneret orifice, spinneret is circular spinneret, the diameter of circular spinneret is oval with series The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 384 of spinneret, spray webbing The shape of cross section of the spinneret orifice of plate is square.
The high-strength middle miniature polyester industrial fiber of high uniformity is extruded, cools down, oiling, stretching through metering, porous spinneret, heat is fixed Type and winding, the high-strength middle miniature polyester industrial fiber of prepared high uniformity, the wherein temperature of extrusion are 300 DEG C, and the pathogenic wind-warm of cooling is 25℃；Stretching, heat setting process parameter are: gr-1 speed 600m/min；Temperature is room temperature；Gr-2 speed 900m/min；Temperature 100℃；Gr-3 speed 2100m/min；120 DEG C of temperature；Gr-4 speed 3200m/min；240 DEG C of temperature；Gr-5 speed 3100m/ min；230 DEG C of temperature；Gr-6 speed 3200m/min；200 DEG C of temperature；The speed of winding is 3200m/min.
The high-strength middle miniature polyester industrial fiber of prepared high uniformity melt viscosity at 260 DEG C declines percentage ratio, under room temperature The mechanical performance data of industrial yarn, and under the test condition for 177 DEG C × 10min × 0.05cn/dtex for the temperature, industrial yarn Dry-hot shrinkage such as following table.
Embodiment 43～45
A kind of preparation method of the high-strength middle miniature polyester industrial fiber of high uniformity, is obtained using porous spinneret, spinneret The arrangement mode of upper spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located on concentration ellipse, with The heart is oval oval for series, and all oval major axis are conllinear, and short axle is conllinear.
Spinneret orifice be arranged as long axial symmetry, oval major axis is 1.4 with the ratio of minor axis length, between adjacent spinneret orifice Add 1.6mm away from the guide hole diameter equal to spinneret orifice, spinneret is circular spinneret, the diameter of circular spinneret is oval with series The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 192 of spinneret, spray webbing The shape of cross section of the spinneret orifice of plate is square.
The high-strength middle miniature polyester industrial fiber of high uniformity is extruded, cools down, oiling, stretching through metering, porous spinneret, heat is fixed Type and winding, the high-strength middle miniature polyester industrial fiber of prepared high uniformity, the wherein temperature of extrusion are 290 DEG C, and the pathogenic wind-warm of cooling is 30℃；Stretching, heat setting process parameter are: gr-1 speed 480m/min；Temperature is room temperature；Gr-2 speed 500m/min；Temperature 100℃；Gr-3 speed 1800m/min；150 DEG C of temperature；Gr-4 speed 3100m/min；250 DEG C of temperature；Gr-5 speed 3300m/ min；240 DEG C of temperature；Gr-6 speed 3200m/min；200 DEG C of temperature；The speed of winding is 3000m/min.
The high-strength middle miniature polyester industrial fiber of prepared high uniformity at 280 DEG C, melt viscosity, the power of industrial yarn under room temperature Learn performance data, and under the test condition for 177 DEG C × 10min × 0.05cn/dtex for the temperature, the dry shrinkage of industrial yarn Rate such as following table.
Embodiment 46～48
A kind of preparation method of the high-strength middle miniature polyester industrial fiber of high uniformity, is obtained using porous spinneret, spinneret The arrangement mode of upper spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located on concentration ellipse, with The heart is oval oval for series, and all oval major axis are conllinear, and short axle is conllinear.
Spinneret orifice be arranged as long axial symmetry, oval major axis is 1.4 with the ratio of minor axis length, between adjacent spinneret orifice Add 1.6mm away from the guide hole diameter equal to spinneret orifice, spinneret is circular spinneret, the diameter of circular spinneret is oval with series The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 192 of spinneret, spray webbing The shape of cross section of the spinneret orifice of plate is square.
The high-strength middle miniature polyester industrial fiber of high uniformity is extruded, cools down, oiling, stretching through metering, porous spinneret, heat is fixed Type and winding, the high-strength middle miniature polyester industrial fiber of prepared high uniformity, the wherein temperature of extrusion are 310 DEG C, and the pathogenic wind-warm of cooling is 25℃；Stretching, heat setting process parameter are: gr-1 speed 580m/min；Temperature is room temperature；Gr-2 speed 800m/min；Temperature 100℃；Gr-3 speed 2400m/min；140 DEG C of temperature；Gr-4 speed 3300m/min；240 DEG C of temperature；Gr-5 speed 3200m/ min；230 DEG C of temperature；Gr-6 speed 2900m/min；190 DEG C of temperature；The speed of winding is 3100m/min.
The high-strength middle miniature polyester industrial fiber of prepared high uniformity melt viscosity at 280 DEG C declines percent, under room temperature The mechanical performance data of industrial yarn, and under the test condition for 177 DEG C × 10min × 0.05cn/dtex for the temperature, industrial yarn Dry-hot shrinkage such as following table.
Embodiment 49～51
A kind of preparation method of the high-strength middle miniature polyester industrial fiber of high uniformity, is obtained using porous spinneret, spinneret The arrangement mode of upper spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located on concentration ellipse, with The heart is oval oval for series, and all oval major axis are conllinear, and short axle is conllinear.
Spinneret orifice be arranged as long axial symmetry, oval major axis is 1.4 with the ratio of minor axis length, between adjacent spinneret orifice Add 1.6mm away from the guide hole diameter equal to spinneret orifice, spinneret is circular spinneret, the diameter of circular spinneret is oval with series The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 192 of spinneret, spray webbing The shape of cross section of the spinneret orifice of plate is square.
The high-strength middle miniature polyester industrial fiber of high uniformity is extruded, cools down, oiling, stretching through metering, porous spinneret, heat is fixed Type and winding, the high-strength middle miniature polyester industrial fiber of prepared high uniformity, the wherein temperature of extrusion are 310 DEG C, and the pathogenic wind-warm of cooling is 30℃；Stretching, heat setting process parameter are: gr-1 speed 480m/min；Temperature is room temperature；Gr-2 speed 700m/min；Temperature 90℃；Gr-3 speed 2500m/min；140 DEG C of temperature；Gr-4 speed 3200m/min；250 DEG C of temperature；Gr-5 speed 2900m/ min；240 DEG C of temperature；Gr-6 speed 2900m/min；180 DEG C of temperature；The speed of winding is 2900m/min.
Prepared high uniformity high-strength middle miniature polyester industrial fiber melt viscosity at 280 DEG C, the power of industrial yarn under room temperature Learn performance data, and under the test condition for 177 DEG C × 10min × 0.05cn/dtex for the temperature, the dry shrinkage of industrial yarn Rate such as following table.
Embodiment 52～57
A kind of preparation method of the high-strength middle miniature polyester industrial fiber of high uniformity, is obtained using porous spinneret, spinneret The arrangement mode of upper spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located on concentration ellipse, with The heart is oval oval for series, and all oval major axis are conllinear, and short axle is conllinear.
Spinneret orifice be arranged as long axial symmetry, oval major axis is 1.4 with the ratio of minor axis length, between adjacent spinneret orifice Add 1.6mm away from the guide hole diameter equal to spinneret orifice, spinneret is circular spinneret, the diameter of circular spinneret is oval with series The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 192 of spinneret, spray webbing The shape of cross section of the spinneret orifice of plate is square.
The high-strength middle miniature polyester industrial fiber of high uniformity is extruded, cools down, oiling, stretching through metering, porous spinneret, heat is fixed Type and winding, the high-strength middle miniature polyester industrial fiber of prepared high uniformity, the wherein temperature of extrusion are 310 DEG C, and the pathogenic wind-warm of cooling is 20℃；Stretching, heat setting process parameter are: gr-1 speed 600m/min；Temperature is room temperature；Gr-2 speed 1000m/min；Temperature 80℃；Gr-3 speed 1800～2500m/min；100 DEG C of temperature；Gr-4 speed 2800m/min；200 DEG C of temperature；Gr-5 speed 3500m/min；200 DEG C of temperature；Gr-6 speed 3400m/min；220 DEG C of temperature；The speed of winding is 3400m/min.
The high-strength middle miniature polyester industrial fiber of prepared high uniformity melt viscosity at 280 DEG C declines percentage ratio, under room temperature The mechanical performance data of industrial yarn, and under the test condition for 177 DEG C × 10min × 0.05cn/dtex for the temperature, industrial yarn Dry-hot shrinkage such as following table.

Claims (10)

1. the high-strength middle shrinkage type polyester industrial fiber of a kind of high uniformity, is characterized in that: the high-strength middle shrinkage type of described high uniformity gathers By modified poly ester, spinning after solid-phase tack producing obtains ester industrial yarn；The material of the high-strength middle shrinkage type 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 the dihydroxylic alcohols segment containing side chain and refer to that side chain is located on one of dihydroxylic alcohols segment non-end group carbon and side chain is containing 5-10 The dihydroxylic alcohols segment of the linear carbon chain of individual carbon atom；The high-strength middle shrinkage type polyester industrial fiber of described high uniformity is at 260～290 DEG C Under, melt viscosity declines 10-20%, under the test condition for 177 DEG C × 10min × 0.05cn/dtex for the temperature, dry shrinkage Rate is 6.0 ± 0.5%, the fracture strength >=8.1cn/dtex of the high-strength middle shrinkage type polyester industrial fiber of described high uniformity, and line is close Degree deviation ratio≤1.0%, fracture strength cv value≤2.0%, extension at break cv value≤5.5%, described melt viscosity decline refers to Modified poly ester and normal polyester are in the contrast of mutually synthermal melt viscosity.
2. the high-strength middle shrinkage type polyester industrial fiber of a kind of high uniformity according to claim 1 is it is characterised in that described height The extension at break of the high-strength middle shrinkage type polyester industrial fiber of uniformity is 13.0 ± 1.5%, network 6 ± 2；The number of described modified poly ester Average molecular weight is 15000-30000.
3. a kind of high-strength middle shrinkage type polyester industrial fiber of high uniformity according to claim 1 is 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- One or more of octyl group -1,6 hexanediol segment, 2- nonyl -1,6 hexanediol segment or 2- decyl -1,6 hexanediol segment；Institute The dihydroxylic alcohols segment stated containing side chain is 2～5% with the Mole percent ratio of ethylene glycol segment.
4. the preparation side of the high-strength middle shrinkage type polyester industrial fiber of a kind of high uniformity as any one of claim 1-3 Method, is characterized in that: modified poly ester is viscosified through solid phase polycondensation, measures, porous spinneret is extruded, cools down, oiling, stretching, heat fixed Type and winding, the high-strength middle shrinkage type polyester industrial fiber of prepared high uniformity；
On described porous spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and described oval shaped arrangements refer to the hole of spinneret orifice It is centrally located on concentration ellipse, described concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear；
The preparation process of modified poly ester comprises the following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
P-phthalic acid is made into after slurry with the dihydroxylic alcohols containing side chain, under the catalytic action of concentrated sulphuric acid, carries out esterification, Obtain p-phthalic acid binary alcohol esters；The described dihydroxylic alcohols containing side chain are that side chain is located at one of dihydroxylic alcohols segment non-end group carbon Upper and side chain is the dihydroxylic alcohols of the linear carbon chain containing 5-10 carbon atom；
(2) preparation of ethylene glycol terephthalate:
P-phthalic acid and ethylene glycol are made into after slurry, carry out esterification, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), stirring is mixed Close, in the presence of catalyst and stabilizer, under conditions of negative pressure, carry out polycondensation reaction and the Gao Zhen in coarse vacuum stage successively The polycondensation reaction in empty stage, prepared modified poly ester.
5. the high-strength middle shrinkage type polyester industrial fiber of high uniformity according to claim 4 preparation method 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 compressive reaction in nitrogen atmosphere, moulding pressure is normal pressure～0.3mpa, and temperature is 180～240 DEG C, it is esterification terminal when the water quantity of distillate in esterification reaches more than the 90% of theoretical value；Obtain p-phthalic acid Binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
P-phthalic acid and ethylene glycol are made into after slurry and add in reactor, carry out esterification, esterification is in blanket of nitrogen Enclose middle compressive reaction, moulding pressure is normal pressure～0.3mpa, and temperature is 250～260 DEG C, when the water quantity of distillate in esterification reaches To theoretical value more than 90% when be esterification terminal, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After the esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), stirring is mixed Close 15-20 minute, under conditions of negative pressure, in the presence of catalyst and stabilizer, start the polycondensation reaction in coarse vacuum stage, This staged pressure is steadily evacuated to below absolute pressure 500pa by normal pressure, temperature control 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, 50～90 minutes response time, prepared modified poly ester；
Again modified poly ester is obtained Modified polyester chips through pelletizing, obtained polyester slice is viscosified by solid phase polycondensation, makes polyester The intrinsic viscosity of section brings up to 1.0～1.2dl/g, as high viscous section；Again through metering, porous spinneret extrusion, cooling, on Oil, stretching, thermal finalization and winding, the high-strength middle shrinkage type polyester industrial fiber of prepared high uniformity；
Spinning main technologic parameters are:
The temperature of described extrusion is 290～320 DEG C；
The pathogenic wind-warm of described cooling is 20～30 DEG C；
Described stretching, heat setting process:
Gr-1 speed 480～600m/min；Temperature is room temperature；
Gr-2 speed 500～1000m/min；80～100 DEG C of temperature；
Gr-3 speed 1800～2500m/min；100～150 DEG C of temperature；
Gr-4 speed 2800～3500m/min；200～250 DEG C of temperature；
Gr-5 speed 2800～3500m/min；200～250 DEG C of temperature；
Gr-6 speed 2600～3400m/min；150～220 DEG C of temperature；
The speed of described winding is 2600～3400m/min.
6. the preparation method of the high-strength middle shrinkage type polyester industrial fiber of a kind of high uniformity according to claim 5, its feature It is, 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.
7. the preparation method of the high-strength middle shrinkage type polyester industrial fiber of a kind of high uniformity according to claim 5, its feature It is, the described dihydroxylic alcohols containing side chain are 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, One or more of 2- octyl group -1,6 hexanediol, 2- nonyl -1,6 hexanediol or 2- decyl -1,6 hexanediol.
8. the preparation method of the high-strength middle shrinkage type polyester industrial fiber of a kind of high uniformity according to claim 4, its feature It is, described porous spinneret is circular spinneret or elliptical spinneret plate；The diameter of described circle spinneret is oval with series The difference of maximum long axis length is more than 10mm, and described elliptical spinneret plate is big with the difference of the oval maximum long axis length of series In 10mm.
9. the preparation method of the high-strength middle shrinkage type polyester industrial fiber of a kind of high uniformity according to claim 4, its feature Be, on described porous spinneret spinneret orifice be arranged as that major axis and/or short axle are symmetrical, the spacing of adjacent spinneret orifice is more than or equal to 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.
10. the preparation method of the high-strength middle shrinkage type polyester industrial fiber of a kind of high uniformity according to claim 4, its feature It is, a diameter of 1.5～2.5mm of guide hole 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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