CN106319676A - High-uniformity activation type industrial polyester yarn and preparation method thereof - Google Patents

High-uniformity activation type industrial polyester yarn and preparation method thereof Download PDF

Info

Publication number
CN106319676A
CN106319676A CN201610776880.0A CN201610776880A CN106319676A CN 106319676 A CN106319676 A CN 106319676A CN 201610776880 A CN201610776880 A CN 201610776880A CN 106319676 A CN106319676 A CN 106319676A
Authority
CN
China
Prior art keywords
segment
phthalic acid
preparation
esterification
ethylene glycol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610776880.0A
Other languages
Chinese (zh)
Other versions
CN106319676B (en
Inventor
范红卫
王山水
宋光坤
赵慧荣
杨大矛
范晓兵
杨超明
刘千涵
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Hengli Chemical Fiber Co Ltd
Original Assignee
Jiangsu Hengli Chemical Fiber Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Hengli Chemical Fiber Co Ltd filed Critical Jiangsu Hengli Chemical Fiber Co Ltd
Priority to CN201610776880.0A priority Critical patent/CN106319676B/en
Publication of CN106319676A publication Critical patent/CN106319676A/en
Application granted granted Critical
Publication of CN106319676B publication Critical patent/CN106319676B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • 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
    • C08G63/80—Solid-state polycondensation
    • 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
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • D01D5/247—Discontinuous hollow structure or microporous structure
    • 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
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
    • D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Abstract

The invention relates to high-uniformity activation type industrial polyester yarn and a preparation method thereof. A raw material of the high-uniformity activation type industrial polyester yarn is modified polyester consisting of a terephthalic acid chain segment, an ethylene glycol chain segment and a glycol chain segment containing branch chains. The preparation method of the high-uniformity activation type industrial polyester yarn comprises steps as follows: terephthalic acid and glycol containing the branch chains are subjected to an esterification reaction under the catalytic action of concentrated sulfuric acid, and glycol phthalate is obtained; then, phthalic acid and ethylene glycol are subjected to an esterification reaction, and ethylene glycol terephthalate is obtained; finally, glycol phthalate and ethylene glycol terephthalate are stirred, mixed and subjected to a condensation reaction at a low-vacuum stage and a high-vacuum stage under the action of a catalyst and a stabilizer, modified polyester is prepared, the modified polyester is treated through steps including metering, porous spinneret plate extrusion, cooling, oiling, stretching, heat setting, application of an activating oiling agent, winding and preactivation, and the high-uniformity activation type industrial polyester yarn is prepared.

Description

A kind of high uniformity activated polyester industrial filament and preparation method thereof
Technical field
The invention belongs to polyester fiber technical field, relate to a kind of high uniformity activated polyester industrial filament and preparation side thereof Method.
Background technology
Polyethylene terephthalate (PET or polyester fiber) fiber from come out since, have fracture strength and Elastic modelling quantity is high, and resilience is moderate, and thermal finalization is excellent, and heat-resisting light resistance is good and acid-fast alkali-proof corrosion resistance etc. is a series of excellent Performance, and fabric have crease-resistant exempt from money, the advantages such as stiffness is good, be widely used in the field such as clothing, home textile.
Activated form polyester industrial filament has all features of polyester industrial filament: fracture strength is high, and elongation at break is little, Dry-hot shrinkage is stable；But compared with viscose glue and nylon, its bond properties is poor.Therefore, in process of production, typically Will first carry out pretreatment makes polyester industrial fiber activate.The feature high with rubber bonding force is possessed after activated, maturation operation, The shortcoming poor with rubber adhesion power that polyester causes can be overcome due to molecular structure.The bonding force with rubber can be improved High.It is mainly used on dipped type cord fabric, canvas apron and as the primary raw material of automobile tire cord fabric.
Activator and the main reaction of polyester industrial fiber are to send out between the epoxide group of epoxy resin and the end carboxyl of polyester Raw reaction introduces the hydroxyl of activity, blocked isocyanate at high temperature unseal produce activity the strongest-NCO group ,-NCO is with poly- -OH in ester industrial yarn reacts or resterification direct reaction.In polyester molecule, the-OH that activity is stronger is introduced by reaction With-NH, and form resinoid coating on polyester industrial fiber surface, make the polarity of polyester strengthen, improve the reaction with RFL Property.Owing to surface of polyester is smooth, surface active groups is little, though activation is effective, but exists between polyester industrial fiber and rubber Serious delamination, and the life-span is short.
Have many parameters during melt spinning, these parameters determine fiberizing course and spin fiber structure and Performance, production is through the fiber controlling these parameters to prepare desired properties.Experimental branch line all uses side for a long time Blowing is as the type of cooling, and energy resource consumption accounts for the significant portion of long filament production cost, along with people are to chemical fibre performance and quality Requiring day by day to improve, the exploitation of chemical-fibres filaments new product develops to the fibre in differentiation direction of high added value, it is desirable to higher cold But dry condition, then propose ring blowing device.Ring blowing device not only possesses every uniform advantage of synnema wind-engaging, Er Qieneng Consumption is compared relatively low, effectively solves the wind energy loss problem that cross air blasting causes owing to blowing area is big.
In spinning process, although ring blowing has obvious advantage, but still the cooling of porous yarn cannot be solved well Uneven problem: owing to spun silk is after circular jetting filament plate is extruded, by ring quenching, due to the circular jetting filament plate number of turns relatively It is many so that ring blowing hardly enters innermost layer, causes the silk at outermost silk innermost layer the most after cooling may be the most uncolled, Thus the problem such as the silk of gained occurs that fiber number is irregular, and intensity is irregular, cause and follow-up silk is processed further difficulty occur.
Summary of the invention
The technical problem to be solved in the present invention is for the deficiencies in the prior art, it is provided that a kind of high uniformity activated form polyester Industrial yarn and preparation method thereof, the raw material of high uniformity activated polyester industrial filament of the present invention is modified poly ester, modified poly ester Strand introduces the dihydroxylic alcohols segment containing side chain, is modified modified high uniformity activated polyester industrial filament prepared by polyester, Under the conditions of uniform temperature, the increasing degree of the spatial joint clearance of high uniformity activated polyester industrial filament interior molecules interchain is the biggest Unbranched high uniformity activated polyester industrial filament, beneficially high uniformity activated polyester industrial filament at equal temperature Intermolecular space increases, and makes partial activation agent molecule diffuse in fiber gap, improve activation in activation process The service efficiency of agent, makes melt viscosity reduce simultaneously, reduces processing temperature, reduces degradation rate, is conducive to processing.Additionally this On the porous spinneret of bright high uniformity activated polyester industrial filament, the arrangement mode of spinneret orifice is oval shaped arrangements, oval Arrangement refers to that the hole of spinneret orifice is centrally located on concentration ellipse, and concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and Short axle conllinear；Higher cooling effectiveness and preferable cooling effect can be reached.
A kind of high uniformity activated polyester industrial filament, described high uniformity activated polyester industrial filament refers to Surface coating The polyester industrial fiber of activator coating layers, is obtained by modified poly ester spinning after solid-phase tack producing；Described high uniformity activated form polyester work The material of industry silk is modified poly ester, and described modified poly ester is by p-phthalic acid segment, ethylene glycol segment and the dihydroxylic alcohols containing side chain Segment forms, and the described dihydroxylic alcohols segment containing side chain refers on the non-end group carbon that side chain is positioned in dihydroxylic alcohols segment and side chain For the dihydroxylic alcohols segment of the linear carbon chain containing 5-10 carbon atom, described high uniformity activated polyester industrial filament in temperature is At 70～80 DEG C, the spatial joint clearance of interior molecules interchain increases 5～15v/v%；At 260～290 DEG C, melt viscosity declines 10-20%, line density deviation ratio≤1.0% of described high uniformity activated polyester industrial filament, fracture strength CV value≤ 2.0%, extension at break CV value≤5.5%；Described high uniformity activated polyester industrial filament temperature be 177 DEG C × 10min × Under the test condition of 0.05cN/dtex, dry-hot shrinkage is 2.5 ± 0.5%, measure wicking height≤5mm；
The spatial joint clearance increase of described molecule interchain refers to that modified poly ester and normal polyester are at mutually synthermal strand Between the contrast of spatial joint clearance；The decline of described melt viscosity refers to that modified poly ester and normal polyester are in mutually synthermal melt viscosity Contrast.
A kind of high uniformity activated polyester industrial filament is modified poly ester, introduces containing propping up on modified poly ester macromole long-chain The dihydroxylic alcohols segment of chain, and the length of side chain and quantity are relatively big on the crystal property of modified poly ester and the impact of flow behavior, The shortest purpose not reaching polyester modification of chain length, the oversize meeting of length causes new entanglement, affects its flow behavior, when side chain position On a non-end group carbon in dihydroxylic alcohols segment and when side chain is the linear carbon chain containing 5-10 carbon atom, it is modified polyester A kind of high uniformity activated polyester industrial filament of preparation, under the conditions of uniform temperature, the space of industrial yarn interior molecules interchain The increasing degree in gap is far longer than unbranched industrial yarn at equal temperature, makes partial activation agent molecule expand in activation process Dissipating enters in fiber gap, improves the service efficiency of activator, the most beneficially industrial yarn melt viscosity and reduces, it is simple to enters The processing of one step.
As preferred technical scheme:
A kind of high uniformity activated polyester industrial filament as above, described high uniformity activated polyester industrial filament Extension at break is 12.0 ± 1.5%, fracture strength >=7.0cN/dtex；The number-average molecular weight of described modified poly ester is 15000- 30000。
A kind of high uniformity activated polyester industrial filament as above, the described dihydroxylic alcohols segment containing side chain is 2-penta Base-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 chain Section, 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 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 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, 2- More than one in nonyl-1,6 hexanediol segment or 2-decyl-1,6 hexanediol segment；The described dihydroxylic alcohols segment containing side chain with The Mole percent ratio of ethylene glycol segment is 2～5%.
The preparation method of a kind of high uniformity activated polyester industrial filament of the present invention, increases modified poly ester through solid phase polycondensation Viscous, metering, porous spinneret extrudes, cool down, oil, are stretched, thermal finalization, activating finish oil, wind and pre-activate processes and walks Suddenly, high uniformity activated polyester industrial filament is prepared；
On described porous spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and described oval shaped arrangements refers to spinneret orifice Hole be centrally located on concentration ellipse, described concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear；
The preparation process of modified poly ester comprises the following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
After p-phthalic acid is made into slurry with the dihydroxylic alcohols containing side chain, under the catalytic action of concentrated sulphuric acid, it is esterified Reaction, obtains p-phthalic acid binary alcohol esters；The described dihydroxylic alcohols containing side chain is that be positioned in dihydroxylic alcohols segment one of side chain is non- On end group carbon and dihydroxylic alcohols that side chain is the linear carbon chain containing 5-10 carbon atom；
For the dihydroxylic alcohols containing side chain, its side chain is alkyl, is electron withdraw group, in the existence of side chain, makes strand Spatial volume increases, and solvation diminishes, and in dihydroxylic alcohols, proton is difficult to dissociation so that the dihydroxylic alcohols containing side chain and terephthaldehyde The reactivity of acid, less than ethylene glycol, according to the mixing of same ethylene glycol and terephthaldehyde's acid reaction, can cause the binary containing side chain Alcohol reaction is imperfect, thus the ratio that the dihydroxylic alcohols that impact is containing side chain is in polyester macromolecule, and then affect the performance of polyester.This Invention uses and first with p-phthalic acid, the dihydroxylic alcohols containing side chain is carried out esterification under the catalytic action of sulphuric acid, and its product exists Ethylene glycol and p phthalic acid esterification add after terminating, it is ensured that the stability of the dihydroxylic alcohols proportioning containing side chain.
(2) preparation of ethylene glycol terephthalate:
After p-phthalic acid and ethylene glycol are made into slurry, carry out esterification, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), stir Mix mixing, under the effect of catalyst and stabilizer, under conditions of negative pressure, carry out successively the coarse vacuum stage polycondensation reaction and The polycondensation reaction of high vacuum stage of Fig, prepares modified poly ester.
The preparation method of a kind of high uniformity activated polyester industrial filament as above, tool prepared by described modified poly ester Body step is:
(1) preparation of p-phthalic acid binary alcohol esters:
P-phthalic acid and the dihydroxylic alcohols containing side chain are made into slurry and add in reactor, in the catalytic action of concentrated sulphuric acid Under, carrying out esterification, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is normal pressure～0.3MPa, and temperature is 180 ～240 DEG C, it is esterification terminal when the water quantity of distillate in esterification reaches more than the 90% of theoretical value；Obtain benzene two Formic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Adding in reactor after p-phthalic acid and ethylene glycol are made into slurry, carry out esterification, esterification is at nitrogen Atmosphere encloses middle compressive reaction, and moulding pressure is normal pressure～0.3MPa, and temperature is 250～260 DEG C, when the water in esterification distillates Amount reach theoretical value more than 90% time be esterification terminal, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), stir Mixing mixing 15-20 minute, under the effect of catalyst and stabilizer, the polycondensation starting the coarse vacuum stage under conditions of negative pressure is anti- Should, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, and temperature controls at 260～270 DEG C, and the response time is 30～50 minutes；Then proceed to evacuation, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure and be less than 100Pa, reaction temperature controls at 275～280 DEG C, response time 50～90 minutes, prepares modified poly ester；
Again through pelletizing, modified poly ester being obtained Modified polyester chips, obtained polyester slice is viscosified by solid phase polycondensation, makes The intrinsic viscosity of polyester slice brings up to 1.0～1.2dL/g, is high viscous section；Again through metering, porous spinneret extrusion, cold But, oil, stretch, thermal finalization, activating finish oil, wind and pre-activate processes step, prepare high uniformity activated form polyester Industrial yarn；
Spinning main technologic parameters is:
The temperature of described extrusion is 290～320 DEG C；
The pathogenic wind-warm of described cooling is 20～30 DEG C；
The speed of described winding is 4000～4600m/min；
The oil applying rate that described activating finish oils is 0.4～0.5wt%；
The condition that described pre-activate processes is: temperature 70～80 DEG C, standing time is 20～30h.
The preparation method of a kind of high uniformity activated polyester industrial filament as above, in described step (1), to benzene two Formic acid is 1:1.3-1.5 with the mol ratio of the dihydroxylic alcohols containing side chain；Concentrated sulphuric acid addition is the 0.3-of p-phthalic acid weight 0.5%；The concentration of described concentrated sulphuric acid is 50-60wt%；In described step (2), p-phthalic acid with the mol ratio of ethylene glycol is 1:1.2～2.0；In described step (3), described p-phthalic acid binary alcohol esters and the Mole percent of ethylene glycol terephthalate Ratio is 2～5%；Described catalyst is antimony oxide, antimony glycol or antimony acetate, and catalyst charge is p-phthalic acid The 0.01%～0.05% of gross weight；Described stabilizer is triphenyl phosphate, trimethyl phosphate or NSC 6513, stabilizer Addition is the 0.01%～0.05% of described p-phthalic acid gross weight.
The preparation method of a kind of high uniformity activated polyester industrial filament as above, the described dihydroxylic alcohols containing side chain is 2-amyl group-1,3 propylene glycol, 2-hexyl-1,3 propylene glycol, 2-heptyl-1,3 propylene glycol, 2-octyl group-1,3 propylene glycol, 2-nonyl-1, 3 propylene glycol, 2-decyl-1,3 propylene glycol, 2-amyl group-1,4 butanediol, 2-hexyl-1,4 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 pentanediols, 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-nonyl-1, More than one in 6 hexanediol or 2-decyl-1,6 hexanediol.
The preparation method of a kind of high uniformity activated polyester industrial filament as above, described porous spinneret is circular Spinneret or elliptical spinneret plate；The difference of the long axis length that the diameter of described circular jetting filament plate is maximum with series ellipse is more than 10mm, the difference of the long axis length that described elliptical spinneret plate is maximum with series ellipse is more than 10mm.
The preparation method of a kind of high uniformity activated polyester industrial filament as above, spray webbing on described porous spinneret Hole be arranged as major axis and/or short axial symmetry, the spacing of adjacent spinneret orifice adds more than or equal to the guide hole diameter of spinneret orifice 1.5mm；Oval major axis is 1.3～1.8 with the ratio of minor axis length.
When the effective area phase of spinneret is simultaneously as the girth of ellipse is more than circular girth, and spinneret orifice is oval The number of plies of arrangement is less than the number of plies of circular arrangement, and the hole count of spinneret orifice oval shaped arrangements is more than the hole count of circular arrangement, therefore, and spray Silk hole oval shaped arrangements is conducive to the cooling that ring is dried, and improves the cooling effectiveness of ring blowing, and the fibre property of preparation is the most excellent Good.Major axis is closer to 1 with the ratio of minor axis length, and ellipse is more similar to circle, and the difference of cooling effectiveness and cooling effect is little； When the ratio of major axis and minor axis length is 1.3, cooling effect significantly improves, and individual pen hole count increases by 16% accordingly；Major axis and short axle When the ratio of length is 1.8, cooling effect improves relatively big, and individual pen hole count increases by 33%, in the case of identical hole count, the present invention accordingly Oval shaped arrangements reduce than the number of turns of conventional concentric circle best-fit, it is easy to cooling wind is saturating, makes the fiber cooling condition of Internal and external cycle Evenly；When the ratio of major axis and minor axis length is more than 1.8, ellipse is partial to form flat shape, is difficult to punching, the coldest But effect no longer raises.Therefore, the major axis that series is oval is 1.3～1.8 with the ratio of minor axis length, it is possible to reach higher cold But efficiency and preferable cooling effect.
The preparation method of a kind of high uniformity activated polyester industrial filament as above, the guide hole diameter of described spinneret orifice It is 1.5～2.5mm；The spray webbing hole count of described spinneret is more than or equal to 192, the shape of cross section of the spinneret orifice of described spinneret For circle, square, rhombus, yi word pattern, triangular form, trilobal cross, hollow type or platypelloid type
The principle of the present invention is:
The raw material of the high uniformity activated polyester industrial filament of the present invention is modified poly ester, contains in modified poly ester macromole The dihydroxylic alcohols segment containing side chain, when temperature higher than vitrification point time, side chain, prior to backbone motion, makes the increase of free volume Amplitude is far longer than the characteristic of unbranched polyester macromolecule chain, and the increase of free volume improves molecule and enters in polyester The degree in portion, the free volume being modified industrial yarn prepared by polyester is far longer than unbranched industrial yarn at equal temperature, has The intermolecular space being beneficial to high uniformity activated polyester industrial filament increases, and makes partial activation agent molecule expand in activation process Dissipating enters in fiber gap, improves the service efficiency of activator, makes melt viscosity reduce simultaneously, reduces processing temperature, subtracts Few degradation rate, is conducive to processing.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 easier to blow through dynamic analysis of spinning less than the number of plies of circular arrangement, ring blowing, dynamic analysis of spinning Cooling effect is more preferable, and the industrial yarn of preparation is the most more excellent.When the effective area of spinneret is identical, spinneret orifice oval shaped arrangements Hole count is more than the hole count of circular arrangement, and oval shaped arrangements is capable of cooling down greatly, significantly improves cooling effectiveness.
Beneficial effect:
The raw material of the high uniformity activated polyester industrial filament of gained of the present invention is modified poly ester, in modified poly ester macromole The dihydroxylic alcohols segment containing side chain contained, when temperature is higher than vitrification point, side chain, prior to backbone motion, makes free volume Increasing degree is far longer than the characteristic of unbranched polyester macromolecule chain, and the increase of free volume advantageously reduces melt viscosity, Improve its processing characteristics.
The raw material of the high uniformity activated polyester industrial filament of gained of the present invention is modified poly ester, in modified poly ester macromole The dihydroxylic alcohols segment containing side chain contained, when temperature is higher than vitrification point, side chain, prior to backbone motion, makes free volume Increasing degree is far longer than the characteristic of unbranched polyester macromolecule chain, and the increase of free volume is conducive to high uniformity activated form The intermolecular space of polyester industrial fiber increases, and makes partial activation agent molecule diffuse into fiber gap in activation process In, improve the service efficiency of activator.
The raw material of the high uniformity activated polyester industrial filament of gained of the present invention is modified poly ester, the dihydroxylic alcohols chain containing side chain Section introduce to the structural regularity of modified poly ester there is no big destruction, maintain the premium properties of polyester fiber.
On the high uniformity activated polyester industrial filament spinneret of the present invention, the arrangement mode of spinneret orifice is oval shaped arrangements, When the effective area of spinneret is identical, the number of plies of spinneret orifice oval shaped arrangements is easier to less than the number of plies of circular arrangement, ring blowing Blowing through dynamic analysis of spinning, the cooling effect of dynamic analysis of spinning is more preferable, and the fibre property of preparation is the most more excellent.
On the high uniformity activated polyester industrial filament spinneret of the present invention, the arrangement mode of spinneret orifice is oval shaped arrangements, 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 shaped arrangements energy Enough realizations cool down greatly, significantly improve cooling effectiveness.
Accompanying drawing explanation
Fig. 1 is the oval shaped arrangements figure of 374 spinneret orifices, and the aperture of spinneret orifice is 2.0mm, transverse and the length of short axle Degree ratio is 1.3；
Fig. 2 is the circular arrangement figure of 370 spinneret orifices, and the aperture of spinneret orifice is 2.0mm；
Fig. 3 is the oval shaped arrangements figure of 382 spinneret orifices, and the aperture of spinneret orifice is 2.0mm, transverse and the length of short axle Degree ratio is 1.6.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate this Bright rather than limit the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, art technology The present invention can be made various changes or modifications by personnel, and these equivalent form of values fall within the application appended claims equally and limited Fixed scope.
Embodiment 1
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.3 and 2-amyl group-1,3 propylene glycol are made into slurry and add in reactor, Concentration is 50wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.3% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is normal pressure, and temperature is 180 DEG C, when the water in esterification distillates Amount reach theoretical value 90% time be esterification terminal, obtain p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.2 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is normal pressure, and temperature is 250 DEG C, when the water in esterification distillates Amount reach theoretical value 90% time be esterification terminal, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 2% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 15 minutes, is adding The catalytic antimony trioxide and addition that amount is the 0.01% of p-phthalic acid gross weight are p-phthalic acid gross weight Under the effect of the stabilizer triphenyl phosphate of 0.01%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank It is 500Pa that section pressure is steadily evacuated to absolute pressure by normal pressure, and temperature controls at 260 DEG C, and the response time is 30 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 100Pa, and reaction temperature controls 275 DEG C, in 50 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 15000, and modified poly ester is by p-phthalic acid segment, ethylene glycol segment and 2-penta Base-1,3 propylene glycol segment compositions, the dihydroxylic alcohols segment containing side chain is 2% with the Mole percent ratio of ethylene glycol segment.
Table 1: embodiment 2-12 important technological parameters
Embodiment 2
The preparation method of the modified poly ester of embodiment 2, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 16 minutes, in addition be The catalytic antimony trioxide of the 0.011% of p-phthalic acid gross weight and addition is p-phthalic acid gross weight 0.02% Stabilizer triphenyl phosphate effect under, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure Steadily be evacuated to absolute pressure 490Pa by normal pressure, temperature controls at 262 DEG C, and the response time is 31 minutes；Then proceed to evacuation, Carrying out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 90Pa, reaction temperature controls at 276 DEG C, reaction 51 minutes time, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 16000, and modified poly ester is own by p-phthalic acid segment, ethylene glycol segment and 2- Base-1,3 propylene glycol segment compositions, 2-hexyl-1,3 propylene glycol segments are 2.1% with the Mole percent ratio of ethylene glycol segment.
Embodiment 3
The preparation method of the modified poly ester of embodiment 3, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 16 minutes, in addition be The catalytic antimony trioxide of the 0.03% of p-phthalic acid gross weight and addition is p-phthalic acid gross weight 0.02% Stabilizer triphenyl phosphate effect under, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure Steadily be evacuated to absolute pressure 498Pa by normal pressure, temperature controls at 263 DEG C, and the response time is 32 minutes；Then proceed to evacuation, Carrying out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 90Pa, reaction temperature controls at 277 DEG C, reaction 57 minutes time, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 15900, and modified poly ester is by p-phthalic acid segment, ethylene glycol segment and 2-heptan Base-1,3 propylene glycol segment compositions, 2-heptyl-1,3 propylene glycol segments are 2.2% with the Mole percent ratio of ethylene glycol segment.
Embodiment 4
The preparation method of the modified poly ester of embodiment 4, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 17 minutes, in addition be The catalytic antimony trioxide of the 0.033% of p-phthalic acid gross weight and addition are p-phthalic acid gross weight Under the effect of the stabilizer triphenyl phosphate of 0.023%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank It is 497Pa that section pressure is steadily evacuated to absolute pressure by normal pressure, and temperature controls at 264 DEG C, and the response time is 33 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 80Pa, and reaction temperature controls 278 DEG C, in 58 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 15800, and modified poly ester is pungent by p-phthalic acid segment, ethylene glycol segment and 2- Base-1,3 propylene glycol segment compositions, 2-octyl group-1,3 propylene glycol segments are 2.3% with the Mole percent ratio of ethylene glycol segment.
Embodiment 5
The preparation method of the modified poly ester of embodiment 5, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 17 minutes, in addition be The catalytic antimony trioxide of the 0.034% of p-phthalic acid gross weight and addition are p-phthalic acid gross weight Under the effect of the stabilizer triphenyl phosphate of 0.024%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 34 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 80Pa, and reaction temperature controls 277 DEG C, in 59 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 15900, and modified poly ester is by p-phthalic acid segment, ethylene glycol segment and 2-nonyl Base-1,3 propylene glycol segment compositions, 2-nonyl-1,3 propylene glycol segments are 2.4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 6
The preparation method of the modified poly ester of embodiment 6, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 18 minutes, in addition be The catalytic antimony trioxide of the 0.035% of p-phthalic acid gross weight and addition are p-phthalic acid gross weight Under the effect of the stabilizer triphenyl phosphate of 0.025%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and temperature controls at 266 DEG C, and the response time is 35 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 70Pa, and reaction temperature controls 278 DEG C, in 60 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 16000, and modified poly ester is by p-phthalic acid segment, ethylene glycol segment and 2-last of the ten Heavenly stems Base-1,3 propylene glycol segment compositions, 2-decyl-1,3 propylene glycol segments are 2.5% with the Mole percent ratio of ethylene glycol segment.
Embodiment 7
The preparation method of the modified poly ester of embodiment 7, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 19 minutes, in addition be The catalytic antimony trioxide of the 0.036% of p-phthalic acid gross weight and addition are p-phthalic acid gross weight Under the effect of the stabilizer triphenyl phosphate of 0.025%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and temperature controls at 267 DEG C, and the response time is 36 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 70Pa, and reaction temperature controls 278 DEG C, in 61 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 16000, and the number-average molecular weight of modified poly ester is 16000, and modified poly ester is by right Phthalic acid segment, ethylene glycol segment and 2-amyl group-Isosorbide-5-Nitrae butanediol segment composition, 2-amyl group-Isosorbide-5-Nitrae butanediol segment and second two The Mole percent ratio of alcohol segment is 2.6%.
Embodiment 8
The preparation method of the modified poly ester of embodiment 8, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 19 minutes, in addition be The catalytic antimony trioxide of the 0.036% of p-phthalic acid gross weight and addition are p-phthalic acid gross weight Under the effect of the stabilizer triphenyl phosphate of 0.025%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and temperature controls at 267 DEG C, and the response time is 36 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 70Pa, and reaction temperature controls 278 DEG C, in 61 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 17000, and modified poly ester is own by p-phthalic acid segment, ethylene glycol segment and 2- Base-Isosorbide-5-Nitrae butanediol segment composition, 2-hexyl-Isosorbide-5-Nitrae butanediol segment is 2.7% with the Mole percent ratio of ethylene glycol segment.
Embodiment 9
The preparation method of the modified poly ester of embodiment 9, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 16 minutes, in addition be The catalyst glycol antimony of the 0.04% of p-phthalic acid gross weight and addition is p-phthalic acid gross weight 0.026% Under the effect of stabilizer trimethyl phosphate, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure by Normal pressure is steadily evacuated to absolute pressure 497Pa, and temperature controls at 268 DEG C, and the response time is 38 minutes；Then proceed to evacuation, enter The polycondensation reaction of row high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 60Pa, and reaction temperature controls at 279 DEG C, reaction 62 minutes time, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 17000, and modified poly ester is by p-phthalic acid segment, ethylene glycol segment and 2-heptan Base-Isosorbide-5-Nitrae butanediol segment composition, 2-heptyl-Isosorbide-5-Nitrae butanediol segment is 2.8% with the Mole percent ratio of ethylene glycol segment.
Embodiment 10
The preparation method of the modified poly ester of embodiment 10, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 17 minutes, in addition be The catalyst glycol antimony of the 0.03% of p-phthalic acid gross weight and addition is p-phthalic acid gross weight 0.027% Under the effect of stabilizer trimethyl phosphate, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure by Normal pressure is steadily evacuated to absolute pressure 498Pa, and temperature controls at 269 DEG C, and the response time is 39 minutes；Then proceed to evacuation, enter The polycondensation reaction of row high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 60Pa, and reaction temperature controls at 278 DEG C, reaction 64 minutes time, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 17000, and modified poly ester is pungent by p-phthalic acid segment, ethylene glycol segment and 2- Base-Isosorbide-5-Nitrae butanediol segment composition, 2-octyl group-Isosorbide-5-Nitrae butanediol segment is 3% with the Mole percent ratio of ethylene glycol segment.
Embodiment 11
The preparation method of the modified poly ester of embodiment 11, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 18 minutes, in addition be The catalyst glycol antimony of the 0.04% of p-phthalic acid gross weight and addition is p-phthalic acid gross weight 0.03% Under the effect of stabilizer trimethyl phosphate, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure by Normal pressure is steadily evacuated to absolute pressure 497Pa, and temperature controls at 260 DEG C, and the response time is 40 minutes；Then proceed to evacuation, enter The polycondensation reaction of row high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 60Pa, and reaction temperature controls at 277 DEG C, reaction 63 minutes time, prepare modified poly ester.
The number-average molecular weight of modified poly ester is 18000, and modified poly ester is by p-phthalic acid segment, ethylene glycol segment and 2-nonyl Base-Isosorbide-5-Nitrae butanediol segment composition, 2-nonyl-Isosorbide-5-Nitrae butanediol segment is 4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 12
The preparation method of the modified poly ester of embodiment 12, wherein the preparation process of modified poly ester is with embodiment 1, mainly Technical parameter see table 1；After step (3) adds p-phthalic acid binary alcohol esters, stirring mixing 18 minutes, in addition be The catalyst acetic acid antimony of the 0.038% of p-phthalic acid weight and addition is p-phthalic acid weight 0.03% stabilizer Under the effect of NSC 6513, starting the polycondensation reaction in coarse vacuum stage under conditions of negative pressure, this staged pressure is by normal pressure Steadily being evacuated to absolute pressure 497Pa, temperature controls at 265 DEG C, and the response time is 42 minutes；Then proceed to evacuation, carry out height The polycondensation reaction of vacuum stages, making reaction pressure be down to absolute pressure is 40Pa, and reaction temperature controls at 277 DEG C, the response time 70 minutes, prepare modified poly ester.
The number-average molecular weight of modified poly ester prepared is 26000, by p-phthalic acid segment, ethylene glycol segment and 2-last of the ten Heavenly stems Base-Isosorbide-5-Nitrae butanediol segment composition, 2-decyl-Isosorbide-5-Nitrae butanediol segment is 4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 13
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.5 and 2-decyl-1,6 hexanediol are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.5% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.3MPa, and temperature is 240 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:2.0 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.3MPa, and temperature is 260 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 5% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 20 minutes, is adding The catalyst acetic acid antimony of 0.05% that amount is p-phthalic acid weight and addition is p-phthalic acid weight 0.05% steady Determine under the effect of agent NSC 6513, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure by It is 450Pa that normal pressure is steadily evacuated to absolute pressure, and temperature controls at 270 DEG C, and the response time is 50 minutes；Then proceed to evacuation, Carrying out the polycondensation reaction of high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 30Pa, and reaction temperature controls at 280 DEG C, instead Between Ying Shi 90 minutes, prepare modified poly ester.
The number-average molecular weight of modified poly ester prepared is 30000, by p-phthalic acid segment, ethylene glycol segment and 2-last of the ten Heavenly stems Base-1,6 hexanediol segment compositions, 2-decyl-1,6 hexanediol segments are 5% with the Mole percent ratio of ethylene glycol segment.
Embodiment 14
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.47 and 2-nonyl-1,6 hexanediol are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.47% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 220 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.8 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.27MPa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, is adding The catalyst glycol antimony of 0.04% that amount is p-phthalic acid weight and addition is p-phthalic acid weight 0.04% Under the effect of stabilizer trimethyl phosphate, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure by Normal pressure is steadily evacuated to absolute pressure 460Pa, and temperature controls at 263 DEG C, and the response time is 47 minutes；Then proceed to evacuation, enter The polycondensation reaction of row high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 278 DEG C, during reaction Between 85 minutes, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 28000, by p-phthalic acid segment, ethylene glycol segment and 2-nonyl Base-1,6 hexanediol segment compositions, 2-nonyl-1,6 hexanediol segments are 4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 15
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.46 and 2-octyl group-1,6 hexanediol are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.49% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 233 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.8 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 259 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.5% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 19 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.044% are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.046%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and temperature controls at 269 DEG C, and the response time is 48 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 279 DEG C, In 87 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 29000, pungent by p-phthalic acid segment, ethylene glycol segment and 2- Base-1,6 hexanediol segment compositions, 2-octyl group-1,6 hexanediol segments are 4.5% with the Mole percent ratio of ethylene glycol segment.
Embodiment 16
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.49 and 2-heptyl-1,6 hexanediol are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.48% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 230 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.8 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.7% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 19 minutes, is adding The catalyst glycol antimony and the addition that enter amount is p-phthalic acid weight 0.048% are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.047%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 460Pa by normal pressure, and temperature controls at 267 DEG C, and the response time is 48 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 279 DEG C, In 83 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester prepared is 27000, by p-phthalic acid segment, ethylene glycol segment and 2-heptan Base-1,6 hexanediol segment compositions, 2-heptyl-1,6 hexanediol segments are 4.7% with the Mole percent ratio of ethylene glycol segment.
Embodiment 17
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.467 and 2-hexyl-1,6 hexanediol are made into slurry and add in reactor, Being 60wt% in concentration, addition is under the catalytic action of the concentrated sulphuric acid of the 0.47% of p-phthalic acid weight, carries out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.27MPa, and temperature is 236 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.89 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 258 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.3% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.04% are p-phthalic acid weight Under the effect of the stabilizer NSC 6513 of 0.041%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and temperature controls at 268 DEG C, and the response time is 48 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls 278 DEG C, in 85 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 29000, own by p-phthalic acid segment, ethylene glycol segment and 2- Base-1,6 hexanediol segment compositions, 2-hexyl-1,6 hexanediol segments are 4.3% with the Mole percent ratio of ethylene glycol segment.
Embodiment 18
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.48 and 2-amyl group-1,6 hexanediol are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.46% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 230 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.88 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 256 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.7% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.047% are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.047%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 480Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 47 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 279 DEG C, In 85 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 28000, by p-phthalic acid segment, ethylene glycol segment and 2-penta Base-1,6 hexanediol segment compositions, 2-amyl group-1,6 hexanediol segments are 4.7% with the Mole percent ratio of ethylene glycol segment.
Embodiment 19
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.46 and 2-decyl-1,5 pentanediols are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.47% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 238 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.9 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 259 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches more than the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.7% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 19 minutes, is adding Enter the catalyst acetic acid antimony of amount is p-phthalic acid weight 0.046% and addition is p-phthalic acid weight 0.048% Stabilizer NSC 6513 effect under, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this stage press It is 446Pa that power is steadily evacuated to absolute pressure by normal pressure, and temperature controls at 267 DEG C, and the response time is 49 minutes；Then proceed to take out very Sky, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 40Pa, and reaction temperature controls at 278 DEG C, In 87 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester prepared is 29000, by p-phthalic acid segment, ethylene glycol segment and 2-last of the ten Heavenly stems Base-1,5 pentanediol segment compositions, 2-decyl-1,5 pentanediol segments are 4.7% with the Mole percent ratio of ethylene glycol segment.
Embodiment 20
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.46 and 2-nonyl-1,5 pentanediols are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.46% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.26MPa, and temperature is 221 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.89 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.25MPa, and temperature is 259 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.1% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, is adding The catalyst glycol antimony and the addition that enter amount is p-phthalic acid weight 0.041% are p-phthalic acid weight Under the effect of the stabilizer trimethyl phosphate of 0.042%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 460Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 47 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 278 DEG C, In 85 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 28000, by p-phthalic acid segment, ethylene glycol segment and 2-nonyl Base-1,5 pentanediol segment compositions, 2-nonyl-1,5 pentanediol segments are 4.1% with the Mole percent ratio of ethylene glycol segment.
Embodiment 21
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.43 and 2-octyl group-1,5 pentanediols are made into slurry and add in reactor, Concentration is 60wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.47% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.27MPa, and temperature is 235 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.78 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.26MPa, and temperature is 255 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.3% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 17 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.043% are p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.049%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and temperature controls at 268 DEG C, and the response time is 46 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 275 DEG C, In 85 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 28000, pungent by p-phthalic acid segment, ethylene glycol segment and 2- Base-1,5 pentanediol segment compositions, 2-octyl group-1,5 pentanediol segments are 4.3% with the Mole percent ratio of ethylene glycol segment.
Embodiment 22
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.43 and 2-heptyl-1,5 pentanediols are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.45% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.29MPa, and temperature is 235 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.87 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.27MPa, and temperature is 255 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.6% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, is adding Enter the catalyst glycol antimony of amount is p-phthalic acid weight 0.047% and addition is p-phthalic acid weight 0.04% Stabilizer triphenyl phosphate effect under, under conditions of negative pressure start the coarse vacuum stage polycondensation reaction, this staged pressure Steadily be evacuated to absolute pressure 470Pa by normal pressure, temperature controls at 268 DEG C, and the response time is 45 minutes；Then proceed to evacuation, Carrying out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 40Pa, reaction temperature controls at 279 DEG C, reaction 83 minutes time, prepare modified poly ester.
The number-average molecular weight of modified poly ester prepared is 29000, by p-phthalic acid segment, ethylene glycol segment and 2-heptan Base-1,5 pentanediol segment compositions, 2-heptyl-1,5 pentanediol segments are 4.6% with the Mole percent ratio of ethylene glycol segment.
Embodiment 23
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.457 and 2-hexyl-1,5 pentanediols are made into slurry and add in reactor, Being 55% in concentration, addition is under the catalytic action of the concentrated sulphuric acid of the 0.46% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 239 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.81 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.27MPa, and temperature is 255 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.41% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 19 minutes, Addition is the catalytic antimony trioxide of the 0.042% of p-phthalic acid weight and addition is p-phthalic acid weight Under the effect of the stabilizer NSC 6513 of 0.048%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 45 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50Pa, and reaction temperature controls 275 DEG C, in 85 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 28000, own by p-phthalic acid segment, ethylene glycol segment and 2- Base-1,5 pentanediol segment compositions, 2-hexyl-1,5 pentanediol segments are 4.41% with the Mole percent ratio of ethylene glycol segment.
Embodiment 24
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.47 and 2-amyl group-1,5 pentanediols are made into slurry and add in reactor, Concentration is 55wt%, and addition is under the catalytic action of the concentrated sulphuric acid of the 0.48% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.27MPa, and temperature is 245 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.81 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.27MPa, and temperature is 259 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.67% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 19 minutes, Addition is the catalytic antimony trioxide of the 0.041% of p-phthalic acid weight and addition is p-phthalic acid weight Under the effect of the stabilizer triphenyl phosphate of 0.042%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, these rank Section pressure is steadily evacuated to absolute pressure 485Pa by normal pressure, and temperature controls at 268 DEG C, and the response time is 46 minutes；Then proceed to take out Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50Pa, and reaction temperature controls at 275 DEG C, In 89 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 29000, by p-phthalic acid segment, ethylene glycol segment and 2-penta Base-1,5 pentanediol segment compositions, 2-amyl group-1,5 pentanediol segments are 4.67% with the Mole percent ratio of ethylene glycol segment.
Embodiment 25
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
Mixed by p-phthalic acid that mol ratio is 1:1.45 and 2-hexyl-1,5 pentanediol and 2-amyl group-1,4 butanediol Compound is made into slurry and adds in reactor, wherein 2-hexyl-1, and the mol ratio of 5 pentanediols and 2-amyl group-Isosorbide-5-Nitrae butanediol is 3:1, Being 55% in concentration, addition is under the catalytic action of the concentrated sulphuric acid of the 0.49% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.26MPa, and temperature is 236 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.8 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.4% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.042% are p-phthalic acid weight Under the effect of the stabilizer NSC 6513 of 0.047%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 49 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50Pa, and reaction temperature controls 278 DEG C, in 88 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester prepared is 29000, by p-phthalic acid segment, ethylene glycol segment, 2-hexyl- 1,5 pentanediol segment and 2-amyl group-Isosorbide-5-Nitrae butanediol segment composition, 2-hexyl-1,5 pentanediol segments and 2-amyl group-Isosorbide-5-Nitrae fourth two The summation of alcohol segment is 4.4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 26
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By 2-octyl group-1,6 hexanediol of p-phthalic acid sum that mol ratio is 1:1.45 and 2-amyl group-1,5 pentanediol Mixture is made into slurry and adds in reactor, wherein 2-octyl group-1,6 hexanediol and 2-amyl group-1, and the mol ratio of 5 pentanediols is 3: 2, it is 60% in concentration, addition is under the catalytic action of the concentrated sulphuric acid of the 0.45% of p-phthalic acid weight, carries out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 239 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.84 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification anti- Should, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.29MPa, and temperature is 255 DEG C, when in esterification It is esterification terminal when water quantity of distillate reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.6% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.0423% are p-phthalic acid weight Under the effect of the stabilizer NSC 6513 of 0.045%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 45 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50Pa, and reaction temperature controls 278 DEG C, in 85 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester prepared is 28000, by p-phthalic acid segment, ethylene glycol segment, 2-octyl group- 1,6 hexanediol segment and 2-amyl group-1,5 pentanediol segment compositions, 2-octyl group-1,6 hexanediol segments and 2-amyl group-1,5 penta 2 Alcohol segment is 4.6% with the Mole percent ratio of ethylene glycol segment.
Embodiment 27
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
Mixed by p-phthalic acid that mol ratio is 1:1.45 and 2-hexyl-1,5 pentanediol and 2-amyl group-1,4 butanediol Compound is made into slurry and adds in reactor, wherein 2-hexyl-1, and the mol ratio of 5 pentanediols and 2-amyl group-Isosorbide-5-Nitrae butanediol is 3:1, Being 55% in concentration, addition is under the catalytic action of the concentrated sulphuric acid of the 0.49% of p-phthalic acid weight, carries out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.26MPa, and temperature is 236 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 96% of theoretical value, obtains p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.8 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.28MPa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.4% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, is adding The catalytic antimony trioxide and the addition that enter amount is p-phthalic acid weight 0.042% are p-phthalic acid weight Under the effect of the stabilizer NSC 6513 of 0.047%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and temperature controls at 265 DEG C, and the response time is 49 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50Pa, and reaction temperature controls 278 DEG C, in 88 minutes response time, prepare modified poly ester.
The number-average molecular weight of modified poly ester prepared is 29000, by p-phthalic acid segment, ethylene glycol segment, 2-hexyl- 1,5 pentanediol segment and 2-amyl group-Isosorbide-5-Nitrae butanediol segment composition, 2-hexyl-1,5 pentanediol segments and 2-amyl group-Isosorbide-5-Nitrae fourth two The summation of alcohol segment is 4.4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 28
The preparation method of a kind of modified poly ester, specifically includes following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
By p-phthalic acid that mol ratio is 1:1.45 and 2-octyl group-1,3 propylene glycol, 2-amyl group-1,4 butanediol and 2-oneself Base-1, the mixture of 6 hexanediol is made into slurry and adds in reactor, wherein 2-octyl group-1,3 propylene glycol, 2-amyl group-Isosorbide-5-Nitrae fourth two Alcohol and 2-hexyl-1, the mol ratio of 6 hexanediol is 3:2:1, is 60% in concentration, and addition is p-phthalic acid weight Under the catalytic action of the concentrated sulphuric acid of 0.47%, carrying out esterification, esterification is compressive reaction in nitrogen atmosphere, moulding pressure For 0.29MPa, temperature is 235 DEG C, is esterification terminal when the water quantity of distillate in esterification reaches the 92% of theoretical value, Obtain p-phthalic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Mol ratio is 1:1.8 p-phthalic acid and ethylene glycol be made into slurry after add in reactor, carry out esterification, Esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is 0.27MPa, and temperature is 258 DEG C, when the water in esterification evaporates It is esterification terminal when output reaches the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, add the p-phthalic acid binary alcohol esters of preparation in step (1), right Phthalic acid binary alcohol esters is 4.71% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes, Addition is the catalytic antimony trioxide of the 0.04% of p-phthalic acid weight and addition is p-phthalic acid weight Under the effect of the stabilizer NSC 6513 of 0.041%, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, should Staged pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and temperature controls at 268 DEG C, and the response time is 49 minutes；Then proceed to Evacuation, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50Pa, and reaction temperature controls 277 DEG C, in 84 minutes response time, prepare modified poly ester.
The number-average molecular weight of the modified poly ester prepared is 29000, by p-phthalic acid segment, ethylene glycol segment, band side chain Glycol segment composition, the most branched glycol segment is 2-octyl group-1,3 propylene glycol segments, 2-amyl group-Isosorbide-5-Nitrae butanediol chain Section and 2-hexyl-1,6 hexanediol segment compositions, branched glycol segment with the Mole percent ratio of ethylene glycol segment is 4.71%.
Embodiment 29
The preparation method of a kind of high uniformity activated polyester industrial filament, high uniformity activated polyester industrial filament uses many Hole spinneret prepares, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers in the hole of spinneret orifice The heart is positioned on concentration ellipse, and concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear.
As it is shown in figure 1, the ratio of the major axis of ellipse and minor axis length is 1.3, the spacing of adjacent spinneret orifice is equal to spinneret orifice Guide hole diameter plus 1.5mm, spinneret is circular jetting filament plate, the long axial length that the diameter of circular jetting filament plate is maximum with series ellipse The difference of degree is 11mm, and a diameter of 2.0mm of guide hole of spinneret orifice, the spray webbing hole count of spinneret is 374, the spinneret orifice of spinneret Shape of cross section be circular.
The modified poly ester that embodiment 1 prepares is extruded through solid phase polycondensation thickening, metering, porous spinneret, cool down, oils, is drawn Stretch, thermal finalization, activating finish oil, wind and pre-activate processes step, prepare high uniformity activated polyester industrial filament, wherein The temperature of extrusion is 290 DEG C；The pathogenic wind-warm of cooling is 20 DEG C；The speed of winding is 4000m/min；The oil applying rate that activating finish oils For 0.4wt%；The condition that greenhouse processes is temperature 80 DEG C, and standing time is 20h.
The high uniformity activated polyester industrial filament prepared refers to the polyester industrial fiber of Surface coating activator coating layers, Gao Jun The fracture strength of even property activated polyester industrial filament is 7.3cN/dtex；Line density deviation ratio is 0.6%, and fracture strength CV value is 1.8%, extension at break CV value is 4.5%, and extension at break is 11.0, and at 260 DEG C, melt viscosity declines 11%, in temperature is Under the test condition of 177 DEG C × 10min × 0.05cN/dtex, dry-hot shrinkage is 2.5%；The a height of 0.7mm of wicking, in temperature Being at 100 DEG C, the spatial joint clearance of interior molecules interchain increases 14v/v%.
Embodiment 30
The preparation method of a kind of high uniformity activated polyester industrial filament, high uniformity activated polyester industrial filament uses many Hole spinneret prepares, and on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refers in the hole of spinneret orifice The heart is positioned on concentration ellipse, and concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear.
As it is shown on figure 3, the ratio of the major axis of ellipse and minor axis length is 1.6, the spacing of adjacent spinneret orifice is equal to spinneret orifice Guide hole diameter plus 1.5mm, spinneret is circular jetting filament plate, the long axial length that the diameter of circular jetting filament plate is maximum with series ellipse The difference of degree is 11mm, and a diameter of 2.0mm of guide hole of spinneret orifice, the spray webbing hole count of spinneret is 382, the spinneret orifice of spinneret Shape of cross section be circular.
The modified poly ester that embodiment 1 prepares is extruded through solid phase polycondensation thickening, metering, porous spinneret, cool down, oils, is drawn Stretch, thermal finalization, activating finish oil, wind and pre-activate processes step, prepare high uniformity activated polyester industrial filament, wherein The temperature of extrusion is 290 DEG C；The pathogenic wind-warm of cooling is 20 DEG C；The speed of winding is 4000m/min；The oil applying rate that activating finish oils For 0.4wt%；The condition that greenhouse processes is temperature 80 DEG C, and standing time is 20h.
The high uniformity activated polyester industrial filament prepared refers to the polyester industrial fiber of Surface coating activator coating layers, Gao Jun The fracture strength of even property activated polyester industrial filament is 7.2cN/dtex；Line density deviation ratio is 0.7%, and fracture strength CV value is 1.7%, extension at break CV value is 4.8%, and extension at break is 11.0, and at 260 DEG C, melt viscosity declines 11%, in temperature is Under the test condition of 177 DEG C × 10min × 0.05cN/dtex, dry-hot shrinkage is 2.5%, and measure wicking height is 0.65mm, in temperature Degree is at 100 DEG C, and the spatial joint clearance of interior molecules interchain increases 14v/v%.
Comparative example 1
The preparation method of a kind of high uniformity activated polyester industrial filament, high uniformity activated polyester industrial filament uses many Hole spinneret prepares, and on spinneret, the arrangement mode of spinneret orifice is circular arrangement, and circular arrangement refers to the hole centre bit of spinneret orifice On concentric circular, concentric circular is that series is circular.As in figure 2 it is shown, the spacing of adjacent spinneret orifice adds equal to the guide hole diameter of spinneret orifice Upper 1.5mm, spinneret is circular jetting filament plate, and the difference of the diameter that the diameter of circular jetting filament plate is maximum with series circle is 11mm, The a diameter of 2.0mm of guide hole of spinneret orifice, the spray webbing hole count of spinneret is 370, and the shape of cross section of the spinneret orifice of spinneret is Circular.
The modified poly ester that embodiment 1 prepares is extruded through solid phase polycondensation thickening, metering, porous spinneret, cool down, oils, is drawn Stretch, thermal finalization, activating finish oil, wind and pre-activate processes step, prepare high uniformity activated polyester industrial filament, wherein The temperature of extrusion is 290 DEG C；The pathogenic wind-warm of cooling is 20 DEG C；The speed of winding is 4000m/min；The oil applying rate that activating finish oils For 0.4wt%；The condition that greenhouse processes is temperature 80 DEG C, and standing time is 20h.
The high uniformity activated polyester industrial filament prepared refers to the polyester industrial fiber of Surface coating activator coating layers, Gao Jun The fracture strength of even property activated polyester industrial filament is 7.6cN/dtex；Line density deviation ratio is 1%, and fracture strength CV value is 1.9%, extension at break CV value is 5.3%, and extension at break is 12.1, and at 260 DEG C, melt viscosity declines 11%, in temperature is Under the test condition of 177 DEG C × 10min × 0.05cN/dtex, dry-hot shrinkage is 2.75%, and measure wicking height is 0.67mm, Temperature is at 100 DEG C, and the spatial joint clearance of interior molecules interchain increases 14v/v%.
When contrasting it can be seen that the effective area of spinneret is identical with embodiment 29, (circular arrangement when spray webbing hole count is close Spray webbing hole count is 370, and oval shaped arrangements spray webbing hole count is 374), the spinneret orifice number of plies of oval shaped arrangements is 6, less than circular arrangement The spinneret orifice number of plies 8, cooling effect is more preferable；When contrasting it can be seen that the effective area of spinneret is identical with embodiment 30, oval The spinneret orifice number of plies of shape arrangement is 5, and less than the spinneret orifice number of plies 8 of circular arrangement, cooling effect is more preferable, the spray webbing of oval shaped arrangements The hole count 382 in hole is more than the hole count 370 of the spinneret orifice of circular arrangement, and cooling effectiveness is higher.The comparing result of fibre property shows, Embodiment 29 and the prepared fiber linear density deviation ratio of embodiment 30, fracture strength CV value, extension at break CV value are less than comparative example 1, under the conditions of same process is described, the fibre property using the spinneret of spinneret orifice oval shaped arrangements to prepare is better than using spinneret The spinneret of circular arrangement.
Embodiment 31～33
The preparation method of a kind of high uniformity activated polyester industrial filament, uses porous spinneret to prepare, spinneret sprays The arrangement mode in silk hole is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located on concentration ellipse, the most ellipse Circle is oval for series, the major axis conllinear of all ellipses, and short axle conllinear.
Be arranged as long axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.4, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.6mm, spinneret is circular jetting filament plate, and the diameter of circular jetting filament plate is oval with series The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 192 of spinneret, spray webbing The shape of cross section of the spinneret orifice of plate is square.
High uniformity activated polyester industrial filament is extruded through metering, porous spinneret, cool down, oils, is stretched, thermal finalization, Activating finish oils, winds and pre-activate process step, prepares high uniformity activated polyester industrial filament, the temperature wherein extruded It it is 290 DEG C；The pathogenic wind-warm of cooling is 30 DEG C；The speed of winding is 4600m/min；The oil applying rate that activating finish oils is 0.5wt%； The condition that greenhouse processes is temperature 80 DEG C, and standing time is 30h.
The high uniformity activated polyester industrial filament prepared refers to the polyester industrial fiber of Surface coating activator coating layers, Gao Jun Even property activated polyester industrial filament, at 280 DEG C, melt viscosity declines percent, at temperature is 80 DEG C, interior molecules interchain Spatial joint clearance increase percent, the mechanical performance data of industrial yarn under room temperature, and temperature be 177 DEG C × 10min × Under the test condition of 0.05cN/dtex, the dry-hot shrinkage of industrial yarn such as following table.
Embodiment 34～36
The preparation method of a kind of high uniformity activated polyester industrial filament, uses porous spinneret to prepare, spinneret sprays The arrangement mode in silk hole is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located on concentration ellipse, the most ellipse Circle is oval for series, the major axis conllinear of all ellipses, and short axle conllinear.
Be arranged as long axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.4, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.6mm, spinneret is circular jetting filament plate, and the diameter of circular jetting filament plate is oval with series The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 192 of spinneret, spray webbing The shape of cross section of the spinneret orifice of plate is square.
High uniformity activated polyester industrial filament is extruded through metering, porous spinneret, cool down, oils, is stretched, thermal finalization, Activating finish oils, winds and pre-activate process step, prepares high uniformity activated polyester industrial filament, and the temperature of extrusion is 290℃；The pathogenic wind-warm of cooling is 22 DEG C；The speed of winding is 4500m/min；The oil applying rate that activating finish oils is 0.5wt%；Warm The condition that room processes is temperature 80 DEG C, and standing time is 24h.
The high uniformity activated polyester industrial filament prepared refers to the polyester industrial fiber of Surface coating activator coating layers, Gao Jun Even property activated polyester industrial filament, at 290 DEG C, melt viscosity declines percentage ratio, at temperature is 80 DEG C, interior molecules interchain Spatial joint clearance increase percent, the mechanical performance data of industrial yarn under room temperature, and temperature be 177 DEG C × 10min × Under the test condition of 0.05cN/dtex, the dry-hot shrinkage of industrial yarn such as following table.
Embodiment 37～39
The preparation method of a kind of high uniformity activated polyester industrial filament, uses porous spinneret to prepare, spinneret sprays The arrangement mode in silk hole is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located on concentration ellipse, the most ellipse Circle is oval for series, the major axis conllinear of all ellipses, and short axle conllinear.
Be arranged as long axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.4, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.6mm, spinneret is circular jetting filament plate, and the diameter of circular jetting filament plate is oval with series The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 192 of spinneret, spray webbing The shape of cross section of the spinneret orifice of plate is square.
High uniformity activated polyester industrial filament is extruded through metering, porous spinneret, cool down, oils, is stretched, thermal finalization, Activating finish oils, winds and pre-activate process step, prepares high uniformity activated polyester industrial filament, the temperature wherein extruded It it is 310 DEG C；The pathogenic wind-warm of cooling is 28 DEG C；The speed of winding is 4000m/min；The oil applying rate that activating finish oils is 0.5wt%； The condition that greenhouse processes is temperature 80 DEG C, and standing time is 20h.
The high uniformity activated polyester industrial filament prepared refers to the polyester industrial fiber of Surface coating activator coating layers, Gao Jun Even property activated polyester industrial filament, at 270 DEG C, melt viscosity declines percent, at temperature is 80 DEG C, interior molecules interchain Spatial joint clearance increase percent, the mechanical performance data of industrial yarn under room temperature, and temperature be 177 DEG C × 10min × Under the test condition of 0.05cN/dtex, the dry-hot shrinkage of industrial yarn such as following table.
Embodiment 40～42
The preparation method of a kind of high uniformity activated polyester industrial filament, uses porous spinneret to prepare, spinneret sprays The arrangement mode in silk hole is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located on concentration ellipse, the most ellipse Circle is oval for series, the major axis conllinear of all ellipses, and short axle conllinear.
Be arranged as long axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.4, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.6mm, spinneret is circular jetting filament plate, and the diameter of circular jetting filament plate is oval with series The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 192 of spinneret, spray webbing The shape of cross section of the spinneret orifice of plate is square.
High uniformity activated polyester industrial filament is extruded through metering, porous spinneret, cool down, oils, is stretched, thermal finalization, Activating finish oils, winds and pre-activate process step, prepares high uniformity activated polyester industrial filament, the temperature wherein extruded It it is 300 DEG C；The pathogenic wind-warm of cooling is 28 DEG C；The speed of winding is 4100m/min；The oil applying rate that activating finish oils is 0.43wt%；The condition that greenhouse processes is temperature 75 DEG C, and standing time is 26h.
The high uniformity activated polyester industrial filament prepared refers to the polyester industrial fiber of Surface coating activator coating layers, Gao Jun Even property activated polyester industrial filament, at 260 DEG C, melt viscosity declines percentage ratio, at temperature is 75 DEG C, interior molecules interchain Spatial joint clearance increase percent, the mechanical performance data of industrial yarn under room temperature, and temperature be 177 DEG C × 10min × Under the test condition of 0.05cN/dtex, the dry-hot shrinkage of industrial yarn such as following table.
Embodiment 43～45
The preparation method of a kind of high uniformity activated polyester industrial filament, uses porous spinneret to prepare, spinneret sprays The arrangement mode in silk hole is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located on concentration ellipse, the most ellipse Circle is oval for series, the major axis conllinear of all ellipses, and short axle conllinear.
Be arranged as long axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.4, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.6mm, spinneret is circular jetting filament plate, and the diameter of circular jetting filament plate is oval with series The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 192 of spinneret, spray webbing The shape of cross section of the spinneret orifice of plate is square.
High uniformity activated polyester industrial filament is extruded through metering, porous spinneret, cool down, oils, is stretched, thermal finalization, Activating finish oils, winds and pre-activate process step, prepares high uniformity activated polyester industrial filament, the temperature wherein extruded It it is 290 DEG C；The pathogenic wind-warm of cooling is 30 DEG C；The speed of winding is 4200m/min；The oil applying rate that activating finish oils is 0.42wt%；The condition that greenhouse processes is temperature 76 DEG C, and standing time is 28h.
The high uniformity activated polyester industrial filament prepared refers to the polyester industrial fiber of Surface coating activator coating layers, Gao Jun Even property activated polyester industrial filament, at 280 DEG C, melt viscosity, at temperature is 76 DEG C, the spatial joint clearance of interior molecules interchain Increase percent, the mechanical performance data of industrial yarn under room temperature, and be 177 DEG C × 10min × 0.05cN/dtex's in temperature Under test condition, the dry-hot shrinkage of industrial yarn such as following table.
Embodiment 46～48
The preparation method of a kind of high uniformity activated polyester industrial filament, uses porous spinneret to prepare, spinneret sprays The arrangement mode in silk hole is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located on concentration ellipse, the most ellipse Circle is oval for series, the major axis conllinear of all ellipses, and short axle conllinear.
Be arranged as long axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.4, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.6mm, spinneret is circular jetting filament plate, and the diameter of circular jetting filament plate is oval with series The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 192 of spinneret, spray webbing The shape of cross section of the spinneret orifice of plate is square.
High uniformity activated polyester industrial filament is extruded through metering, porous spinneret, cool down, oils, is stretched, thermal finalization, Activating finish oils, winds and pre-activate process step, prepares high uniformity activated polyester industrial filament, the temperature wherein extruded It it is 310 DEG C；The pathogenic wind-warm of cooling is 30 DEG C；The speed of winding is 4400m/min；The oil applying rate that activating finish oils is 0.46wt%；The condition that greenhouse processes is temperature 74 DEG C, and standing time is 27h.
The high uniformity activated polyester industrial filament prepared refers to the polyester industrial fiber of Surface coating activator coating layers, Gao Jun Even property activated polyester industrial filament, at 280 DEG C, melt viscosity declines percent, at temperature is 74 DEG C, interior molecules interchain Spatial joint clearance increase percent, the mechanical performance data of industrial yarn under room temperature, and temperature be 177 DEG C × 10min × Under the test condition of 0.05cN/dtex, the dry-hot shrinkage of industrial yarn such as following table.
Embodiment 49～51
The preparation method of a kind of high uniformity activated polyester industrial filament, uses porous spinneret to prepare, spinneret sprays The arrangement mode in silk hole is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located on concentration ellipse, the most ellipse Circle is oval for series, the major axis conllinear of all ellipses, and short axle conllinear.
Be arranged as long axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.4, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.6mm, spinneret is circular jetting filament plate, and the diameter of circular jetting filament plate is oval with series The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 192 of spinneret, spray webbing The shape of cross section of the spinneret orifice of plate is square.
High uniformity activated polyester industrial filament is extruded through metering, porous spinneret, cool down, oils, is stretched, thermal finalization, Activating finish oils, winds and pre-activate process step, prepares high uniformity activated polyester industrial filament, the temperature wherein extruded It it is 300 DEG C；The pathogenic wind-warm of cooling is 25 DEG C；The speed of winding is 4500m/min；The oil applying rate that activating finish oils is 0.45wt%；The condition that greenhouse processes is temperature 70 C, and standing time is 28h.
The high uniformity activated polyester industrial filament prepared refers to the polyester industrial fiber of Surface coating activator coating layers, Gao Jun Even property activated polyester industrial filament, melt viscosity at 280 DEG C, at temperature is 70 DEG C, the spatial joint clearance of interior molecules interchain Increase percent, the mechanical performance data of industrial yarn under room temperature, and be 177 DEG C × 10min × 0.05cN/dtex's in temperature Under test condition, the dry-hot shrinkage of industrial yarn such as following table.
Embodiment 52～57
The preparation method of a kind of high uniformity activated polyester industrial filament, uses porous spinneret to prepare, spinneret sprays The arrangement mode in silk hole is oval shaped arrangements, and oval shaped arrangements refers to that the hole of spinneret orifice is centrally located on concentration ellipse, the most ellipse Circle is oval for series, the major axis conllinear of all ellipses, and short axle conllinear.
Be arranged as long axial symmetry, the major axis of ellipse and the ratio of minor axis length of spinneret orifice are 1.4, between adjacent spinneret orifice Away from the guide hole diameter equal to spinneret orifice plus 1.6mm, spinneret is circular jetting filament plate, and the diameter of circular jetting filament plate is oval with series The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 192 of spinneret, spray webbing The shape of cross section of the spinneret orifice of plate is square.
High uniformity activated polyester industrial filament is extruded through metering, porous spinneret, cool down, oils, is stretched, thermal finalization, Activating finish oils, winds and pre-activate process step, prepares high uniformity activated polyester industrial filament, the temperature wherein extruded It it is 320 DEG C；The pathogenic wind-warm of cooling is 30 DEG C, and the speed of winding is 4000m/min；The oil applying rate that activating finish oils is 0.44wt%；The condition that greenhouse processes is temperature 75 DEG C, and standing time is 22h.
The high uniformity activated polyester industrial filament prepared refers to the polyester industrial fiber of Surface coating activator coating layers, Gao Jun Even property activated polyester industrial filament, at 280 DEG C, melt viscosity declines percentage ratio, at temperature is 75 DEG C, interior molecules interchain Spatial joint clearance increase percent, the mechanical performance data of industrial yarn under room temperature, and temperature be 177 DEG C × 10min × Under the test condition of 0.05cN/dtex, the dry-hot shrinkage of industrial yarn such as following table.

Claims (10)

1. a high uniformity activated polyester industrial filament, is characterized in that: described high uniformity activated polyester industrial filament refers to The polyester industrial fiber of Surface coating activator coating layers, is obtained by modified poly ester spinning after solid-phase tack producing；Described high uniformity activates The material of type polyester industrial fiber is modified poly ester, and described modified poly ester is by p-phthalic acid segment, ethylene glycol segment with containing side chain Dihydroxylic alcohols segment composition, the described dihydroxylic alcohols segment containing side chain refers to the non-end group carbon that side chain is positioned in dihydroxylic alcohols segment Upper and that side chain is the linear carbon chain containing 5-10 carbon atom dihydroxylic alcohols segment；Described high uniformity activated polyester industrial filament At temperature is 70～80 DEG C, the spatial joint clearance of interior molecules interchain increases 5～15v/v%；At 260～290 DEG C, melt glues Degree declines 10-20%, line density deviation ratio≤1.0% of described high uniformity activated polyester industrial filament, fracture strength CV value ≤ 2.0%, extension at break CV value≤5.5%；Described high uniformity activated polyester industrial filament is 177 DEG C × 10min in temperature Under the test condition of × 0.05cN/dtex, dry-hot shrinkage is 2.5 ± 0.5%, measure wicking height≤5mm.
A kind of high uniformity activated polyester industrial filament the most according to claim 1, it is characterised in that described high uniformity The extension at break of activated polyester industrial filament is 12.0 ± 1.5%, fracture strength >=7.0cN/dtex；The number of described modified poly ester Average molecular weight is 15000-30000.
A kind of high uniformity activated polyester industrial filament the most according to claim 1, it is characterised in that described containing side chain Dihydroxylic alcohols segment 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 Segment, 2-hexyl-1,4 butanediol segment, 2-heptyl-1,4 butanediol segment, 2-octyl group-1,4 butanediol segment, 2-nonyl-1, 4 butanediol segments, 2-decyl-1,4 butanediol segment, 2-amyl group-1,5 pentanediol segment, 2-hexyl-1,5 pentanediol segment, 2- Heptyl-1,5 pentanediol segment, 2-octyl group-1,5 pentanediol segment, 2-nonyl-1,5 pentanediol segment, 2-decyl-1,5 pentanediol Segment, 2-amyl group-1,6 hexanediol segment, 2-hexyl-1,6 hexanediol segment, 2-heptyl-1,6 hexanediol segment, 2-octyl group-1, More than one in 6 hexanediol segments, 2-nonyl-1,6 hexanediol segment or 2-decyl-1,6 hexanediol segment；Described containing side chain The Mole percent ratio of dihydroxylic alcohols segment and ethylene glycol segment be 2～5%.
4. the preparation method of a kind of high uniformity activated polyester industrial filament as according to any one of claim 1-3, it is special Levy and be: modified poly ester is extruded through solid phase polycondensation thickening, metering, porous spinneret, cool down, oils, is stretched, thermal finalization, activation Oil preparation oils, winds and pre-activate process step, prepares high uniformity activated polyester industrial filament；
On described porous spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and described oval shaped arrangements refers to the hole of spinneret orifice Being centrally located on concentration ellipse, described concentration ellipse is that series is oval, the major axis conllinear of all ellipses, and short axle conllinear；
The preparation process of modified poly ester comprises the following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
After p-phthalic acid is made into slurry with the dihydroxylic alcohols containing side chain, under the catalytic action of concentrated sulphuric acid, carry out esterification, Obtain p-phthalic acid binary alcohol esters；The described dihydroxylic alcohols containing side chain is the non-end group carbon that side chain is positioned in dihydroxylic alcohols segment Upper and that side chain is the linear carbon chain containing 5-10 carbon atom dihydroxylic alcohols；
(2) preparation of ethylene glycol terephthalate:
After p-phthalic acid and ethylene glycol are made into slurry, carry out esterification, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, adding the p-phthalic acid binary alcohol esters of preparation in step (1), stirring is mixed Close, under the effect of catalyst and stabilizer, under conditions of negative pressure, carry out polycondensation reaction and the Gao Zhen in coarse vacuum stage successively The polycondensation reaction in empty stage, prepares modified poly ester.
The preparation method of high uniformity activated polyester industrial filament the most according to claim 4, it is characterised in that described in change Prepared by property polyester concretely comprises the following steps:
(1) preparation of p-phthalic acid binary alcohol esters:
P-phthalic acid and the dihydroxylic alcohols containing side chain are made into slurry add in reactor, under the catalytic action of concentrated sulphuric acid, enter Row esterification, esterification is compressive reaction in nitrogen atmosphere, and moulding pressure is normal pressure～0.3MPa, and temperature is 180～240 DEG C, it is esterification terminal when the water quantity of distillate in esterification reaches more than the 90% of theoretical value；Obtain p-phthalic acid Binary alcohol esters；
(2) preparation of ethylene glycol terephthalate:
Adding in reactor after p-phthalic acid and ethylene glycol are made into slurry, carry out esterification, esterification is in blanket of nitrogen Enclosing middle compressive reaction, moulding pressure is normal pressure～0.3MPa, and temperature is 250～260 DEG C, when the water quantity of distillate in esterification reaches To theoretical value more than 90% time be esterification terminal, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester:
After esterification in step (2) terminates, adding the p-phthalic acid binary alcohol esters of preparation in step (1), stirring is mixed Close 15-20 minute, under the effect of catalyst and stabilizer, under conditions of negative pressure, start the polycondensation reaction in coarse vacuum stage, This staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, and temperature controls at 260～270 DEG C, the response time be 30～ 50 minutes；Then proceed to evacuation, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure and be less than 100Pa, reaction temperature controls at 275～280 DEG C, response time 50～90 minutes, prepares modified poly ester；
Again through pelletizing, modified poly ester being obtained Modified polyester chips, obtained polyester slice is viscosified by solid phase polycondensation, makes polyester The intrinsic viscosity of section brings up to 1.0～1.2dL/g, is high viscous section；Again through metering, porous spinneret extrusion, cooling, on Oil, stretching, thermal finalization, activating finish oil, wind and pre-activate process step, prepare high uniformity activated form polyester industrial Silk；
Spinning main technologic parameters is:
The temperature of described extrusion is 290～320 DEG C；
The pathogenic wind-warm of described cooling is 20～30 DEG C；
The speed of described winding is 4000～4600m/min；
The oil applying rate that described activating finish oils is 0.4～0.5wt%；
The condition that described pre-activate processes is: temperature 70～80 DEG C, standing time is 20～30h.
The preparation method of a kind of high uniformity activated polyester industrial filament the most according to claim 5, it is characterised in that institute Stating in 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 to benzene The 0.3-0.5% of dioctyl phthalate weight；The concentration of described concentrated sulphuric acid is 50-60wt%；In described step (2), p-phthalic acid with The mol ratio of ethylene glycol is 1:1.2～2.0；In described step (3), described p-phthalic acid binary alcohol esters and p-phthalic acid second The Mole percent ratio of diol ester is 2～5%；Described catalyst is antimony oxide, antimony glycol or antimony acetate, and catalyst adds Enter that amount is p-phthalic acid gross weight 0.01%～0.05%；Described stabilizer is triphenyl phosphate, trimethyl phosphate or Asia Trimethyl phosphate, stabilizer addition is the 0.01%～0.05% of described p-phthalic acid gross weight.
The preparation method of a kind of high uniformity activated polyester industrial filament the most according to claim 5, it is characterised in that institute State the dihydroxylic alcohols containing side chain be 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 fourth two Alcohol, 2-heptyl-1,4 butanediol, 2-octyl group-1,4 butanediol, 2-nonyl-1,4 butanediol, 2-decyl-1,4 butanediol, 2-penta Base-1,5 pentanediol, 2-hexyl-1,5 pentanediol, 2-heptyl-1,5 pentanediol, 2-octyl group-1,5 pentanediol, 2-nonyl-1,5 penta Glycol, 2-decyl-1,5 pentanediols, 2-amyl group-1,6 hexanediol, 2-hexyl-1,6 hexanediol, 2-heptyl-1,6 hexanediol, 2-are pungent More than one in base-1,6 hexanediol, 2-nonyl-1,6 hexanediol or 2-decyl-1,6 hexanediol.
The preparation method of a kind of high uniformity activated polyester industrial filament the most according to claim 4, it is characterised in that institute Stating porous spinneret is circular jetting filament plate or elliptical spinneret plate；The length that the diameter of described circular jetting filament plate is maximum with series ellipse The difference of shaft length is more than 10mm, and the difference of the long axis length that described elliptical spinneret plate is maximum with series ellipse is more than 10mm.
The preparation method of a kind of high uniformity activated polyester industrial filament the most according to claim 4, it is characterised in that institute That states spinneret orifice on porous spinneret is arranged as major axis and/or short axial symmetry, and the spacing of adjacent spinneret orifice is more than or equal to spinneret orifice Guide hole diameter plus 1.5mm；Oval major axis is 1.3～1.8 with the ratio of minor axis length.
The preparation method of a kind of high uniformity activated polyester industrial filament the most according to claim 4, it is characterised in that The guide hole a diameter of 1.5～2.5mm of described spinneret orifice；The spray webbing hole count of described spinneret is more than or equal to 192, described spinneret The shape of cross section of spinneret orifice is circle, square, rhombus, yi word pattern, triangular form, trilobal cross, hollow type or platypelloid type.
CN201610776880.0A 2016-08-31 2016-08-31 A kind of high uniformity activated polyester industrial filament and preparation method thereof Active CN106319676B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610776880.0A CN106319676B (en) 2016-08-31 2016-08-31 A kind of high uniformity activated polyester industrial filament and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610776880.0A CN106319676B (en) 2016-08-31 2016-08-31 A kind of high uniformity activated polyester industrial filament and preparation method thereof

Publications (2)

Publication Number Publication Date
CN106319676A true CN106319676A (en) 2017-01-11
CN106319676B CN106319676B (en) 2018-09-14

Family

ID=57788999

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610776880.0A Active CN106319676B (en) 2016-08-31 2016-08-31 A kind of high uniformity activated polyester industrial filament and preparation method thereof

Country Status (1)

Country Link
CN (1) CN106319676B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107893264A (en) * 2017-12-14 2018-04-10 江苏恒力化纤股份有限公司 A kind of preparation method of the military soft type polyester industrial fiber of high uniformity
CN107904694A (en) * 2017-12-14 2018-04-13 江苏恒力化纤股份有限公司 A kind of preparation method of high-strength activated polyester industrial filament
CN108385188A (en) * 2017-12-14 2018-08-10 江苏恒力化纤股份有限公司 A kind of low-shrinkage activated polyester industrial filament and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102648231A (en) * 2009-09-29 2012-08-22 东丽纤维研究所（中国）有限公司 Copolyester and preparation method and use thereof
CN102851757A (en) * 2011-06-30 2013-01-02 江苏华亚化纤有限公司 Special-shaped spinneret plate for spinning heavy denier yarns
CN102797054B (en) * 2012-09-03 2014-10-01 江苏恒力化纤股份有限公司 Manufacturing method of high-strength, high-modulus and low-shrinkage polyester industrial yarn
JP2014189933A (en) * 2013-03-28 2014-10-06 Toray Ind Inc Normal pressure dispersion-dyeable polyester ultra-fine fiber
CN104499080A (en) * 2014-12-31 2015-04-08 江苏恒力化纤股份有限公司 High-strength activated polyester industry yarn and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102648231A (en) * 2009-09-29 2012-08-22 东丽纤维研究所（中国）有限公司 Copolyester and preparation method and use thereof
CN102851757A (en) * 2011-06-30 2013-01-02 江苏华亚化纤有限公司 Special-shaped spinneret plate for spinning heavy denier yarns
CN102797054B (en) * 2012-09-03 2014-10-01 江苏恒力化纤股份有限公司 Manufacturing method of high-strength, high-modulus and low-shrinkage polyester industrial yarn
JP2014189933A (en) * 2013-03-28 2014-10-06 Toray Ind Inc Normal pressure dispersion-dyeable polyester ultra-fine fiber
CN104499080A (en) * 2014-12-31 2015-04-08 江苏恒力化纤股份有限公司 High-strength activated polyester industry yarn and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107893264A (en) * 2017-12-14 2018-04-10 江苏恒力化纤股份有限公司 A kind of preparation method of the military soft type polyester industrial fiber of high uniformity
CN107904694A (en) * 2017-12-14 2018-04-13 江苏恒力化纤股份有限公司 A kind of preparation method of high-strength activated polyester industrial filament
CN108385188A (en) * 2017-12-14 2018-08-10 江苏恒力化纤股份有限公司 A kind of low-shrinkage activated polyester industrial filament and preparation method thereof
CN108385188B (en) * 2017-12-14 2020-07-07 江苏恒力化纤股份有限公司 Low-shrinkage activated polyester industrial yarn and preparation method thereof

Also Published As

Publication number Publication date
CN106319676B (en) 2018-09-14

Similar Documents

Publication Publication Date Title
CN106245150B (en) A kind of high uniformity coloured polyester industrial yarn and preparation method thereof
CN106381557B (en) A kind of high uniformity safety belt polyester industrial fiber and preparation method thereof
CN106245149B (en) A kind of high uniformity vehicle mould polyester industrial fiber and preparation method thereof
CN106381558B (en) A kind of abnormal contraction composite filament and preparation method thereof
CN106400162B (en) A kind of high uniformity high intensity low shrinkage type polyester industrial fiber and preparation method thereof
CN106283251B (en) A kind of porous ptt fiber HOY and preparation method thereof
CN106283250A (en) A kind of high-strength ultralow miniature polyester industrial fiber of high uniformity and preparation method thereof
CN106283260B (en) Porous super flexible polyester fiber FDY of one kind and preparation method thereof
CN106319676A (en) High-uniformity activation type industrial polyester yarn and preparation method thereof
CN106350886B (en) A kind of high uniformity high-strength polyester industrial fiber and preparation method thereof
CN106283261B (en) Porous super soft super fine denier polyester fiber of one kind and preparation method thereof
CN106149396A (en) A kind of high uniformity Coated Fabrics and preparation method thereof
CN106319678A (en) Super-soft wool-like porous polyester and preparation method thereof
CN106381546B (en) A kind of high uniformity air bag polyester industrial fiber and preparation method thereof
CN107059152B (en) A kind of high mould lower shrinkage type polyester industrial fiber of high uniformity and preparation method thereof
CN106400165B (en) A kind of military soft type polyester industrial fiber of high uniformity and preparation method thereof
CN106319677A (en) Porous PTT (polytrimethylene terephthalate) fiber FDY (fully drawn yarn) and preparation method thereof
CN106283262A (en) A kind of porous polyester fiber FDY silk and preparation method thereof
CN106350885B (en) A kind of high uniformity high-tenacity low-elongation polyester industrial fiber and preparation method thereof
CN106350889B (en) A kind of high-strength middle shrinkage type polyester industrial fiber of high uniformity and preparation method thereof
CN106381549B (en) A kind of porous super fine denier polyester fiber and preparation method thereof
CN106397745B (en) A kind of high uniformity polyester heavy caliber conveyer belt and preparation method thereof
CN106835330B (en) A kind of anti-core suction type polyester industrial fiber of high uniformity and preparation method thereof
CN106337210B (en) A kind of high uniformity high-grade highway protective fence framework material polyester industrial fiber and preparation method thereof
CN106283264A (en) A kind of porous surpasses flexible polyester fiber POY silk and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant