CN107059152B - A kind of high mould lower shrinkage type polyester industrial fiber of high uniformity and preparation method thereof - Google Patents
A kind of high mould lower shrinkage type polyester industrial fiber of high uniformity and preparation method thereof Download PDFInfo
- Publication number
- CN107059152B CN107059152B CN201610781240.9A CN201610781240A CN107059152B CN 107059152 B CN107059152 B CN 107059152B CN 201610781240 A CN201610781240 A CN 201610781240A CN 107059152 B CN107059152 B CN 107059152B
- Authority
- CN
- China
- Prior art keywords
- segment
- tpa
- terephthalic acid
- spinneret
- modified poly
- 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.)
- Active
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
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
Abstract
The present invention relates to high mould lower shrinkage type polyester industrial fiber of a kind of high uniformity and preparation method thereof, the raw material of the high mould lower shrinkage type polyester industrial fiber of high uniformity is the modified poly ester being made of terephthalic acid (TPA) segment, ethylene glycol segment and dihydric alcohol segment containing branch.The preparation method of the high mould lower shrinkage type polyester industrial fiber of high uniformity is to carry out esterification and obtain terephthalic acid (TPA) binary alcohol esters terephthalic acid (TPA) in the catalysis of the concentrated sulfuric acid with containing the dihydric alcohol of branch；Then terephthalic acid (TPA) and ethylene glycol are made into carry out esterification, obtain ethylene glycol terephthalate；Finally the two is stirred, under the action of catalyst and stabilizer, carry out the polycondensation reaction of low vacuum stage and high vacuum stage of Fig, modified poly ester is made, modified poly ester squeezes out, cools down, oils, stretches through metering, porous spinneret, thermal finalization and winding, the high mould lower shrinkage type polyester industrial fiber of obtained high uniformity.
Description
Technical field
The invention belongs to polyester fiber technical field, it is related to a kind of high mould lower shrinkage type polyester industrial fiber of high uniformity and its system
Preparation Method.
Background technology
Polyethylene terephthalate (PET fiber or polyester fiber) fiber since the advent of the world, have fracture strength and
Elasticity modulus is high, and resilience is moderate, and thermal finalization is excellent, and heat-resisting light resistance is good and acid-fast alkali-proof corrosion resistance etc. is a series of excellent
Performance, and fabric have many advantages, such as it is crease-resistant exempt to provide, stiffness is good, is widely used in the fields such as clothes, home textile.
Pet Industrial Fiber is primarily referred to as mostly being applied to industry, national defence, medical treatment, environmental protection and most advanced branches of science each side
Face is that have relatively special physicalchemical structure, performance and purposes, or the chemical fibre with specific function, major embodiment
Be able to bear strong corrosion, low abrasion, high temperature resistant, radiation hardness, fire-retardant, fire-resistant, high voltage withstanding, high strength and modulus and plurality of medical work(
Energy.The PVC shelter cloths produced using high-strength low-shrinkage polyester industrial filament yarn as raw material have higher peel strength and tearing strong
Degree makes shelter cloth be suitable for various uses, flexible body advertising lamp box material, inflatable structure material, fluffy lid architectural fabrics sunshade account
Paulin etc..It is that main textile material obtains in terms of the military supplies such as special protective garment, camouflage, covering, knapsack with high-strength low-shrinkage industrial yarn
To application.One kind as earth working material having many advantages, such as light, soft, high-strength, wear-resisting, anticorrosive, non-conductive, damping.Make
It is used time safe ready, efficient, and lifting object will not be damaged.The application field of Pet Industrial Fiber, which is expanded, drives application
The whole competitiveness in field is promoted, and no matter in the weight for mitigating composite material, cost is raised in the durability used and reduction repair
Etc. all various aspects, polyesters high-performance fiber increasingly plays its synthetic competitive advantages.Following many decades, high-performance polyester
The development of fiber not only has a considerable progress in quantity, more carrying in the expansion of application field and industrial chain whole competitiveness
It goes up and obtains substantive effect.
High-modulus, lower shrinkageTo be the Main way of Pet Industrial Fiber development, and influence fiber quality is polyester
High molecular collection state structure, the active force being mainly concerned between polyester molecule, the form and structure of crystallization, orientation structure etc.,
And the form and structure crystallized is emphasis therein.Low-shrinkage high-strength PET industrial yarn is the major class in polyester, since it is strong
Degree is high, and percent thermal shrinkage is low, and impact resistance is excellent, and fabric or manufactured rubber product have good dimensional stability and resistance to
Thermal stability can absorb impact load, and have the characteristics that polyamide fibre softness, therefore the field that is widely used.Low-shrinkage
High-strength polyester industrial yarns are mainly used for coated fabric (lamp house cloth, tent, shelter cloth, billboard, puggaree, waterproof cloth, Puffer-type
Swimming pool, roof drape, for building, agriculture use, aircushion vehicle, pneumatic boat etc.), canvas, soft water pipe, fire hose, tree
Fat pipe, sewing thread, Industry thread, geotextile, filter cloth etc..
There are many parameter during melt spinning, these parameters determine the course of fiberizing and spin fiber structure and
Performance, be exactly in production be made by controlling these parameters needed for performance fiber.Experimental branch line all uses side for a long time
Blowing is used as the type of cooling, and energy consumption accounts for the significant portion of long filament production cost, as people are to chemical fibre performance and quality
It is required that increasingly improving, the exploitation of chemical-fibres filaments new product develops to the fibre in differentiation direction of high added value, it is desirable that higher cold
But it dries condition, then proposes ring blowing device.Ring blowing device not only has the uniform advantage of every synnema wind-engaging, Er Qieneng
Consumption compared to relatively low, effective solution cross air blasting due to blowing area is big and caused by wind energy lose problem.
In spinning process, although ring blowing has apparent advantage, the cooling of porous yarn can not be well solved
Uneven problem：Since spun silk is after round spinneret extrusion, by ring wind quenching, due to the round spinneret number of turns compared with
It is more so that ring blowing hardly enters innermost layer, leads to that the silk of innermost layer may be also uncolled after cooling in outermost silk,
There is the problems such as fiber number is irregular, and intensity is irregular to the silk of gained, the further processing subsequently to silk is caused difficulty occur.
Invention content
The technical problem to be solved by the present invention is in view of the deficiencies of the prior art, provide a kind of high mould lower shrinkage of high uniformity
The raw material of type polyester industrial fiber and preparation method thereof, the high mould lower shrinkage type polyester industrial fiber of high uniformity of the present invention is modified poly-
Ester introduces the dihydric alcohol segment containing branch, modification high uniformity Gao Mo prepared by modified polyester in the strand of modified poly ester
Lower shrinkage type polyester industrial fiber, under the conditions of certain temperature, the high mould lower shrinkage type polyester industrial fiber interior molecules interchain of high uniformity
The increasing degree of spatial joint clearance be far longer than the high mould lower shrinkage type polyester industrial fiber of high uniformity unbranched at same temperature,
The melt viscosity of the high mould lower shrinkage type polyester industrial fiber of high uniformity reduces, and reduces processing temperature, reduces degradation rate, is conducive to
Processing.In addition on the porous spinneret of the high mould lower shrinkage type polyester industrial fiber of high uniformity of the invention spinneret orifice arrangement mode
For oval shaped arrangements, oval shaped arrangements refer to that the hole center of spinneret orifice is located on concentration ellipse, and concentration ellipse is that series is oval, institute
There is elliptical long axis conllinear, and short axle is conllinear；Higher cooling efficiency and preferable cooling effect can be reached.
A kind of high mould lower shrinkage type polyester industrial fiber of high uniformity, the high mould lower shrinkage type polyester industrial fiber of high uniformity
By modified poly ester, spinning obtains after solid-phase tack producing；The material of the high mould lower shrinkage type polyester industrial fiber of high uniformity is modified poly-
Ester, the modified poly ester are made of terephthalic acid (TPA) segment, ethylene glycol segment and dihydric alcohol segment containing branch, described to contain branch
Dihydric alcohol segment refer on a non-end group carbon that branch is located in dihydric alcohol segment and branch is containing 5-10 carbon atom
Linear carbon chain dihydric alcohol segment, high mould lower shrinkage type polyester industrial linear density deviation ratio≤1.0% of high uniformity,
Fracture strength CV value≤2.0%, extension at break CV value≤5.5%；The high mould lower shrinkage type polyester industrial fiber of high uniformity
Fiber modulus >=100cN/dtex；At 260~290 DEG C, melt viscosity declines 10-20%, is 177 DEG C × 10min in temperature
Under the test condition of × 0.05cN/dtex, dry-hot shrinkage is 2.0 ± 0.25%.
A kind of high mould lower shrinkage type polyester industrial fiber of high uniformity is modified poly ester, is drawn on modified poly ester macromolecular long-chain
Enter the dihydric alcohol segment containing branch, and the influence of the length of branch and quantity to the crystal property and flow behavior of modified poly ester compared with
Greatly, the too short purpose that polyester modification is not achieved of branch lengths, length is too long to cause new entanglement, influence its flow behavior, when
When branch is located on a non-end group carbon in dihydric alcohol segment and branch is the linear carbon chain containing 5-10 carbon atom, through changing
Property polyester prepare a kind of high mould lower shrinkage type polyester industrial fiber of high uniformity, under the conditions of certain temperature, industrial yarn inside points
The increasing degree of spatial joint clearance between subchain is far longer than industrial yarn unbranched at same temperature, and it is viscous to be conducive to industrial yarn melt
Degree reduces, convenient for further processing.
As preferred technical solution：
A kind of high mould lower shrinkage type polyester industrial fiber of high uniformity as described above, the high mould lower shrinkage type of high uniformity
The extension at break of polyester industrial fiber is 20.0 ± 1.5%, fracture strength >=7.0cN/dtex；The equal molecule of number of the modified poly ester
Amount is 15000-30000.
A kind of high mould lower shrinkage type polyester industrial fiber of high uniformity as described above, the dihydric alcohol segment containing branch are
- 1,3 propylene glycol segment of 2- amyls, -1,3 propylene glycol segment of 2- hexyls, -1,3 propylene glycol segment of 2- heptyl, 2- octyls -1,3 the third two
Alcohol segment, -1,3 propylene glycol segment of 2- nonyls, -1,3 propylene glycol segment of 2- decyls, -1,4 butanediol segment of 2- amyls, 2- hexyls -
1,4 butanediol segments, -1,4 butanediol segment of 2- heptyl, -1,4 butanediol segment of 2- octyls, -1,4 butanediol segment of 2- nonyls,
- 1,4 butanediol segment of 2- decyls, -1,5 pentanediol segment of 2- amyls, -1,5 pentanediol segment of 2- hexyls, 2- heptyl -1,5 penta 2
Alcohol segment, -1,5 pentanediol segment of 2- octyls, -1,5 pentanediol segment of 2- nonyls, -1,5 pentanediol segment of 2- decyls, 2- amyls -
1,6 hexylene glycol segments, -1,6 hexylene glycol segment of 2- hexyls, -1,6 hexylene glycol segment of 2- heptyl, -1,6 hexylene glycol segment of 2- octyls,
One or more of -1,6 hexylene glycol segment of -1,6 hexylene glycol segment of 2- nonyls or 2- decyls；The dihydric alcohol segment containing branch
Mole percent ratio with ethylene glycol segment is 2~5%.
The preparation method of the high mould lower shrinkage type polyester industrial fiber of a kind of high uniformity of the present invention, by modified poly ester through solid phase
Condensation viscosity enhancing, metering, porous spinneret squeeze out, cool down, oil, stretching, thermal finalization and winding, and the low receipts of the high mould of high uniformity are made
Miniature polyester industrial fiber；
The arrangement mode of spinneret orifice is oval shaped arrangements on the porous spinneret, and the oval shaped arrangements refer to spinneret orifice
Hole center be located on concentration ellipse, the concentration ellipse is that series is oval, and all elliptical long axis are conllinear, and short axle is conllinear；
The preparation process of modified poly ester includes the following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
After terephthalic acid (TPA) and the dihydric alcohol containing branch are made into slurry, under the catalytic action of the concentrated sulfuric acid, it is esterified
Reaction, obtains terephthalic acid (TPA) binary alcohol esters；The dihydric alcohol containing branch is that be located in dihydric alcohol segment one of branch is non-
On end group carbon and branch be the linear carbon chain containing 5-10 carbon atom dihydric alcohol；
For the dihydric alcohol containing branch, branch is alkyl, is electron-withdrawing group, in the presence of branch, makes strand
Spatial volume increases, and solvation becomes smaller, and proton is not easy to dissociate in dihydric alcohol so that the dihydric alcohol containing branch and terephthaldehyde
The reactivity of acid is less than ethylene glycol, mixes according to same ethylene glycol and is reacted with terephthalic acid (TPA), can cause the binary containing branch
Alcohol reaction is imperfect, to influence ratio of the dihydric alcohol containing branch in polyester macromolecule, and then influences the performance of polyester.This
Using the dihydric alcohol containing branch is first carried out esterification under the catalytic action of sulfuric acid with terephthalic acid (TPA), product exists for invention
It is added after ethylene glycol and p phthalic acid esterification, ensure that the stability of the dihydric alcohol proportioning containing branch.
(2) preparation of ethylene glycol terephthalate：
After terephthalic acid (TPA) and ethylene glycol are made into slurry, esterification is carried out, ethylene glycol terephthalate is obtained；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, stir
Mix mixing, under the action of catalyst and stabilizer, under conditions of negative pressure, successively carry out low vacuum stage polycondensation reaction and
Modified poly ester is made in the polycondensation reaction of high vacuum stage of Fig.
A kind of preparation method of the high mould lower shrinkage type polyester industrial fiber of high uniformity as described above, the modified poly ester system
It is standby the specific steps are：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Terephthalic acid (TPA) and the dihydric alcohol containing branch are made into slurry to be added in reactor, in the catalytic action of the concentrated sulfuric acid
Under, esterification, esterification compressive reaction in nitrogen atmosphere are carried out, moulding pressure is normal pressure~0.3MPa, temperature 180
~240 DEG C, be esterification terminal when the water quantity of distillate in esterification reaches 90% or more of theoretical value；It obtains to benzene two
Formic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is added in reactor after terephthalic acid (TPA) and ethylene glycol are made into slurry, carries out esterification, esterification is in nitrogen
Atmosphere encloses middle compressive reaction, and moulding pressure is normal pressure~0.3MPa, and temperature is 250~260 DEG C, when the water in esterification distillates
Amount is esterification terminal when reaching 90% of theoretical value or more, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, stir
Mixing 15-20 minutes is mixed, under the action of catalyst and stabilizer, the polycondensation for starting low vacuum stage under conditions of negative pressure is anti-
It answers, which by normal pressure is steadily evacuated to absolute pressure 500Pa hereinafter, temperature control is at 260~270 DEG C, and the reaction time is
30~50 minutes；It then proceedes to vacuumize, carries out the polycondensation reaction of high vacuum stage of Fig, so that reaction pressure is down to absolute pressure and be less than
Modified poly ester is made in 275~280 DEG C, 50~90 minutes reaction time in 100Pa, reaction temperature control；
Modified poly ester is obtained into Modified polyester chips through pelletizing again, acquired polyester slice is viscosified by solid phase polycondensation, made
The inherent viscosity of polyester slice is increased to 1.0~1.2dL/g, as high viscous slice；It is squeezed out again through metering, porous spinneret, is cold
But it, oils, stretch, thermal finalization and winding, the high mould lower shrinkage type polyester industrial fiber of high uniformity is made；
Spinning main technologic parameters are：
The temperature of the extrusion is 290~310 DEG C；
The wind-warm syndrome of the cooling is 20~30 DEG C；
The stretching, heat setting process parameter are：
3000~3600m/min of GR-1 speed；75~80 DEG C of temperature；
3800~4500m/min of GR-2 speed；85~95 DEG C of temperature；
5000~5600m/min of GR-3 speed；250~255 DEG C of temperature；
5500~5600m/min of GR-4 speed；250~255 DEG C of temperature；
5630~5650m/min of GR-5 speed；250~255 DEG C of temperature；
5500~5600m/min of GR-6 speed；250~255 DEG C of temperature；
The speed of the winding is 5450~5500m/min.
A kind of preparation method of the high mould lower shrinkage type polyester industrial fiber of high uniformity as described above, in the step (1),
The molar ratio of terephthalic acid (TPA) and the dihydric alcohol containing branch is 1:1.3-1.5；Concentrated sulfuric acid addition is terephthalic acid (TPA) weight
0.3-0.5%；A concentration of 50-60wt% of the concentrated sulfuric acid；In the step (2), mole of terephthalic acid (TPA) and ethylene glycol
Than being 1:1.2~2.0；In the step (3), mole of the terephthalic acid (TPA) binary alcohol esters and ethylene glycol terephthalate
Percent value is 2~5%；The catalyst is antimony oxide, antimony glycol or antimony acetate, and catalyst charge is to benzene two
The 0.01%~0.05% of formic acid total weight；The stabilizer be triphenyl phosphate, trimethyl phosphate or Trimethyl phosphite, surely
Determine 0.01%~0.05% that agent addition is the terephthalic acid (TPA) total weight.
A kind of preparation method of the high mould lower shrinkage type polyester industrial fiber of high uniformity as described above, it is described containing branch two
First alcohol is -1,3 propylene glycol of 2- amyls, -1,3 propylene glycol of 2- hexyls, -1,3 propylene glycol of 2- heptyl, -1,3 propylene glycol of 2- octyls, 2-
- 1,3 propylene glycol of nonyl, -1,3 propylene glycol of 2- decyls, -1,4 butanediol of 2- amyls, -1,4 butanediol of 2- hexyls, 2- heptyl -1,4
Butanediol, -1,4 butanediol of 2- octyls, -1,4 butanediol of 2- nonyls, -1,4 butanediol of 2- decyls, -1,5 pentanediol of 2- amyls, 2-
- 1,5 pentanediol of hexyl, -1,5 pentanediol of 2- heptyl, -1,5 pentanediol of 2- octyls, -1,5 pentanediol of 2- nonyls, 2- decyls -1,5
Pentanediol, 2- amyls -1,6 hexylene glycol, 2- hexyl -1,6 hexylene glycols, 2- heptyl -1,6 hexylene glycol, 2- octyls -1,6 hexylene glycol, 2-
One or more of -1,6 hexylene glycol of -1,6 hexylene glycol of nonyl or 2- decyls.
A kind of preparation method of the high mould lower shrinkage type polyester industrial fiber of high uniformity as described above, the porous spinneret
For round spinneret or elliptical spinneret plate；The difference of the diameter of the circle spinneret and the oval maximum long axis length of series
More than 10mm, the elliptical spinneret plate and the difference of the oval maximum long axis length of series are more than 10mm.
A kind of preparation method of the high mould lower shrinkage type polyester industrial fiber of high uniformity as described above, the porous spinneret
Upper spinneret orifice be arranged as long axis and/or short axle is symmetrical, the guide hole diameter that the spacing of adjacent spinneret orifice is more than or equal to spinneret orifice adds
Upper 1.5mm；Elliptical long axis and the ratio of minor axis length are 1.3~1.8.
When the effective area phase of spinneret is simultaneously as the perimeter of ellipse is more than circular perimeter, spinneret orifice ellipse
The number of plies of arrangement is less than the number of plies of circular arrangement, and the hole count of spinneret orifice oval shaped arrangements is more than the hole count of circular arrangement, therefore, spray
Wire hole oval shaped arrangements are conducive to the cooling of ring blowing, improve the cooling efficiency of ring blowing, and the fibre property of preparation is also more excellent
It is good.Long axis and the ratio of minor axis length are closer to 1, and ellipse is more similar to justify, and the difference of cooling efficiency and cooling effect is little；
When long axis and the ratio of minor axis length are 1.3, cooling effect significantly improves, and individual pen hole count accordingly increases by 16%；Long axis and short axle
When the ratio of length is 1.8, cooling effect raising is larger, the accordingly increase by 33% of individual pen hole count, in the case of identical hole count, the present invention
Oval shaped arrangements than conventional concentric circle best-fit the number of turns reduce, be easy to cooling wind and blow through, make the fiber cooling condition of Internal and external cycle
Evenly；When long axis and the ratio of minor axis length are more than 1.8, ellipse is partial to form flat shape, is not easy to punch, while cold
But effect no longer increases.Therefore, the elliptical long axis of series and the ratio of minor axis length are 1.3~1.8, can reach higher cold
But efficiency and preferable cooling effect.
A kind of preparation method of the high mould lower shrinkage type polyester industrial fiber of high uniformity as described above, the spinneret orifice are led
Bore dia is 1.5~2.5mm；The spinneret hole count of the spinneret be more than or equal to 192, the spinneret orifice of the spinneret it is transversal
Face shape is circle, square, diamond shape, "-" type, triangular form, trilobal cross, hollow type or platypelloid type
The principle of the present invention is：
The raw material of the high mould lower shrinkage type polyester industrial fiber of high uniformity of the present invention is modified poly ester, modified poly ester macromolecular
In the dihydric alcohol segment containing branch that contains, when temperature is higher than glass transition temperature, branch makes free volume prior to backbone motion
Increasing degree be far longer than the characteristic of unbranched polyester macromolecule chain, the free volume of industrial yarn prepared by modified polyester
It is far longer than industrial yarn unbranched at same temperature, advantageously reduces its melt viscosity.
The arrangement mode of spinneret orifice is oval shaped arrangements on the spinneret of the present invention, when the effective area of spinneret is identical,
The number of plies of spinneret orifice oval shaped arrangements is less than the number of plies of circular arrangement, and ring blowing is easier to blow through dynamic analysis of spinning, dynamic analysis of spinning
Cooling effect is more preferable, and the industrial yarn of preparation is also more excellent.When the effective area of spinneret is identical, spinneret orifice oval shaped arrangements
Hole count is more than the hole count of circular arrangement, and oval shaped arrangements can realize a greater degree of cooling, significantly improve cooling efficiency.
Advantageous effect：
The raw material of the high mould lower shrinkage type polyester industrial fiber of high uniformity of gained of the invention is modified poly ester, and modified poly ester is big
The dihydric alcohol segment containing branch contained in molecule, when temperature is higher than glass transition temperature, branch makes freedom prior to backbone motion
The increasing degree of volume is far longer than the characteristic of unbranched polyester macromolecule chain, and the increase of free volume advantageously reduces melt
Viscosity improves its processing performance.
The raw material of the high mould lower shrinkage type polyester industrial fiber of high uniformity of gained of the invention is modified poly ester, two containing branch
The not big destruction of structural regularity for the modified poly ester of first alcohol segment introduced pair, maintains the excellent performance of polyester fiber.
The arrangement mode of spinneret orifice is ellipse on the high mould lower shrinkage type polyester industrial fiber spinneret of high uniformity of the present invention
Shape arranges, and when the effective area of spinneret is identical, the number of plies of spinneret orifice oval shaped arrangements is less than the number of plies of circular arrangement, ring blowing
It is easier to blow through dynamic analysis of spinning, the cooling effect of dynamic analysis of spinning is more preferable, and the fibre property of preparation is also more excellent.
The arrangement mode of spinneret orifice is ellipse on the high mould lower shrinkage type polyester industrial fiber spinneret of high uniformity of the present invention
Shape arranges, and when the effective area of spinneret is identical, the hole count of spinneret orifice oval shaped arrangements is more than the hole count of circular arrangement, ellipse
Arrangement can realize a greater degree of cooling, significantly improve cooling efficiency.
Description of the drawings
Fig. 1 is the oval shaped arrangements figure of 374 spinneret orifices, and the aperture of spinneret orifice is 2.0mm, the length of transverse and short axle
It is 1.3 to spend ratio；
Fig. 2 is the circular arrangement figure of 370 spinneret orifices, and the aperture of spinneret orifice is 2.0mm；
Fig. 3 is the oval shaped arrangements figure of 382 spinneret orifices, and the aperture of spinneret orifice is 2.0mm, the length of transverse and short axle
It is 1.6 to spend ratio.
Specific implementation mode
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Embodiment 1
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.3 terephthalic acid (TPA) is made into slurry with 2- amyl -1,3 propylene glycol and is added in reactor,
A concentration of 50wt%, addition are to carry out esterification under the catalytic action of 0.3% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure are normal pressure, and temperature is 180 DEG C, when the water in esterification distillates
Amount is esterification terminal when reaching the 90% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.2 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, carry out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure are normal pressure, and temperature is 250 DEG C, when the water in esterification distillates
Amount is esterification terminal when reaching the 90% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 2%, is stirred 15 minutes, is being added
Amount is 0.01% the catalytic antimony trioxide of terephthalic acid (TPA) total weight and addition is terephthalic acid (TPA) total weight
Under the action of 0.01% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure
It is 500Pa that section pressure, which is steadily evacuated to absolute pressure by normal pressure, and at 260 DEG C, the reaction time is 30 minutes for temperature control；It then proceedes to
It vacuumizes, carries out the polycondensation reaction of high vacuum stage of Fig, it is 100Pa so that reaction pressure is down to absolute pressure, and reaction temperature control exists
275 DEG C, modified poly ester was made in 50 minutes reaction time.
The number-average molecular weight of modified poly ester is 15000, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- penta
Base -1,3 propylene glycol segment forms, and the Mole percent ratio of the dihydric alcohol segment containing branch and ethylene glycol segment is 2%.
Table 1：Embodiment 2-12 important technological parameters
Embodiment 2
The preparation method of the modified poly ester of embodiment 2, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly
Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 16 minutes, is in addition
0.011% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are the 0.02% of terephthalic acid (TPA) total weight
Stabilizer triphenyl phosphate under the action of, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure
Absolute pressure 490Pa is steadily evacuated to by normal pressure, at 262 DEG C, the reaction time is 31 minutes for temperature control；It then proceedes to vacuumize,
The polycondensation reaction for carrying out high vacuum stage of Fig makes reaction pressure be down to absolute pressure 90Pa, and reaction temperature is controlled at 276 DEG C, reaction
Modified poly ester was made in 51 minutes time.
The number-average molecular weight of modified poly ester be 16000, modified poly ester by terephthalic acid (TPA) segment, ethylene glycol segment and 2- oneself
Base -1,3 propylene glycol segment forms, and the Mole percent ratio of 2- hexyl -1,3 propylene glycol segments and ethylene glycol segment is 2.1%.
Embodiment 3
The preparation method of the modified poly ester of embodiment 3, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly
Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 16 minutes, is in addition
0.03% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are the 0.02% of terephthalic acid (TPA) total weight
Stabilizer triphenyl phosphate under the action of, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure
Absolute pressure 498Pa is steadily evacuated to by normal pressure, at 263 DEG C, the reaction time is 32 minutes for temperature control；It then proceedes to vacuumize,
The polycondensation reaction for carrying out high vacuum stage of Fig makes reaction pressure be down to absolute pressure 90Pa, and reaction temperature is controlled at 277 DEG C, reaction
Modified poly ester was made in 57 minutes time.
The number-average molecular weight of modified poly ester is 15900, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- heptan
Base -1,3 propylene glycol segment forms, and the Mole percent ratio of 2- heptyl -1,3 propylene glycol segments and ethylene glycol segment is 2.2%.
Embodiment 4
The preparation method of the modified poly ester of embodiment 4, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly
Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 17 minutes, is in addition
0.033% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are terephthalic acid (TPA) total weight
Under the action of 0.023% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure
It is 497Pa that section pressure, which is steadily evacuated to absolute pressure by normal pressure, and at 264 DEG C, the reaction time is 33 minutes for temperature control；It then proceedes to
It vacuumizes, carries out the polycondensation reaction of high vacuum stage of Fig, it is 80Pa so that reaction pressure is down to absolute pressure, and reaction temperature control exists
278 DEG C, modified poly ester was made in 58 minutes reaction time.
The number-average molecular weight of modified poly ester is 15800, and modified poly ester is pungent by terephthalic acid (TPA) segment, ethylene glycol segment and 2-
Base -1,3 propylene glycol segment forms, and the Mole percent ratio of 2- octyl -1,3 propylene glycol segments and ethylene glycol segment is 2.3%.
Embodiment 5
The preparation method of the modified poly ester of embodiment 5, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly
Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 17 minutes, is in addition
0.034% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are terephthalic acid (TPA) total weight
Under the action of 0.024% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure
Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and at 265 DEG C, the reaction time is 34 minutes for temperature control；It then proceedes to take out
Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and it is 80Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled 277
DEG C, modified poly ester was made in 59 minutes reaction time.
The number-average molecular weight of modified poly ester is 15900, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- nonyls
Base -1,3 propylene glycol segment forms, and the Mole percent ratio of 2- nonyl -1,3 propylene glycol segments and ethylene glycol segment is 2.4%.
Embodiment 6
The preparation method of the modified poly ester of embodiment 6, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly
Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 18 minutes, is in addition
0.035% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are terephthalic acid (TPA) total weight
Under the action of 0.025% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure
Section pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 266 DEG C, the reaction time is 35 minutes for temperature control；It then proceedes to take out
Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and it is 70Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled 278
DEG C, modified poly ester was made in 60 minutes reaction time.
The number-average molecular weight of modified poly ester is 16000, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and the 2- last of the ten Heavenly stems
Base -1,3 propylene glycol segment forms, and the Mole percent ratio of 2- decyl -1,3 propylene glycol segments and ethylene glycol segment is 2.5%.
Embodiment 7
The preparation method of the modified poly ester of embodiment 7, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly
Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 19 minutes, is in addition
0.036% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are terephthalic acid (TPA) total weight
Under the action of 0.025% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure
Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and at 267 DEG C, the reaction time is 36 minutes for temperature control；It then proceedes to take out
Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and it is 70Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled 278
DEG C, modified poly ester was made in 61 minutes reaction time.
The number-average molecular weight of modified poly ester is 16000, and the number-average molecular weight of modified poly ester is 16000, and modified poly ester is by right
Phthalic acid segment, ethylene glycol segment and 2- amyls-Isosorbide-5-Nitrae butanediol segment composition, 2- amyls-Isosorbide-5-Nitrae butanediol segment and second two
The Mole percent ratio of alcohol segment is 2.6%.
Embodiment 8
The preparation method of the modified poly ester of embodiment 8, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly
Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 19 minutes, is in addition
0.036% the catalytic antimony trioxide and addition of terephthalic acid (TPA) total weight are terephthalic acid (TPA) total weight
Under the action of 0.025% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure
Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and at 267 DEG C, the reaction time is 36 minutes for temperature control；It then proceedes to take out
Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and it is 70Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled 278
DEG C, modified poly ester was made in 61 minutes reaction time.
The number-average molecular weight of modified poly ester be 17000, modified poly ester by terephthalic acid (TPA) segment, ethylene glycol segment and 2- oneself
The Mole percent ratio of base-Isosorbide-5-Nitrae butanediol segment composition, 2- hexyls-Isosorbide-5-Nitrae butanediol segment and ethylene glycol segment is 2.7%.
Embodiment 9
The preparation method of the modified poly ester of embodiment 9, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly
Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 16 minutes, is in addition
0.04% catalyst glycol antimony and addition of terephthalic acid (TPA) total weight are the 0.026% of terephthalic acid (TPA) total weight
Under the action of stabilizer trimethyl phosphate, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure by
Normal pressure is steadily evacuated to absolute pressure 497Pa, and at 268 DEG C, the reaction time is 38 minutes for temperature control；It then proceedes to vacuumize, into
The polycondensation reaction of row high vacuum stage of Fig, it is 60Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled at 279 DEG C, reaction
Modified poly ester was made in 62 minutes time.
The number-average molecular weight of modified poly ester is 17000, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- heptan
The Mole percent ratio of base-Isosorbide-5-Nitrae butanediol segment composition, 2- heptyl-Isosorbide-5-Nitrae butanediol segment and ethylene glycol segment is 2.8%.
Embodiment 10
The preparation method of the modified poly ester of embodiment 10, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly
Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 17 minutes, is in addition
0.03% catalyst glycol antimony and addition of terephthalic acid (TPA) total weight are the 0.027% of terephthalic acid (TPA) total weight
Under the action of stabilizer trimethyl phosphate, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure by
Normal pressure is steadily evacuated to absolute pressure 498Pa, and at 269 DEG C, the reaction time is 39 minutes for temperature control；It then proceedes to vacuumize, into
The polycondensation reaction of row high vacuum stage of Fig, it is 60Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled at 278 DEG C, reaction
Modified poly ester was made in 64 minutes time.
The number-average molecular weight of modified poly ester is 17000, and modified poly ester is pungent by terephthalic acid (TPA) segment, ethylene glycol segment and 2-
The Mole percent ratio of base-Isosorbide-5-Nitrae butanediol segment composition, 2- octyls-Isosorbide-5-Nitrae butanediol segment and ethylene glycol segment is 3%.
Embodiment 11
The preparation method of the modified poly ester of embodiment 11, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly
Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 18 minutes, is in addition
0.04% catalyst glycol antimony and addition of terephthalic acid (TPA) total weight are the 0.03% of terephthalic acid (TPA) total weight
Under the action of stabilizer trimethyl phosphate, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure by
Normal pressure is steadily evacuated to absolute pressure 497Pa, and at 260 DEG C, the reaction time is 40 minutes for temperature control；It then proceedes to vacuumize, into
The polycondensation reaction of row high vacuum stage of Fig, it is 60Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled at 277 DEG C, reaction
Modified poly ester was made in 63 minutes time.
The number-average molecular weight of modified poly ester is 18000, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- nonyls
The Mole percent ratio of base-Isosorbide-5-Nitrae butanediol segment composition, 2- nonyls-Isosorbide-5-Nitrae butanediol segment and ethylene glycol segment is 4%.
Embodiment 12
The preparation method of the modified poly ester of embodiment 12, the wherein preparation process of modified poly ester are with embodiment 1, wherein mainly
Technical parameter referring to table 1；After terephthalic acid (TPA) binary alcohol esters are added in step (3), it is stirred 18 minutes, is in addition
The catalyst acetic acid antimony and addition of the 0.038% of terephthalic acid (TPA) weight are 0.03% stabilizer of terephthalic acid (TPA) weight
Under the action of Trimethyl phosphite, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, the staged pressure is by normal pressure
Steady to be evacuated to absolute pressure 497Pa, at 265 DEG C, the reaction time is 42 minutes for temperature control；It then proceedes to vacuumize, carry out high
The polycondensation reaction of vacuum stages, it is 40Pa so that reaction pressure is down to absolute pressure, and reaction temperature control is at 277 DEG C, the reaction time
70 minutes, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained is 26000, by terephthalic acid (TPA) segment, ethylene glycol segment and the 2- last of the ten Heavenly stems
The Mole percent ratio of base-Isosorbide-5-Nitrae butanediol segment composition, 2- decyls-Isosorbide-5-Nitrae butanediol segment and ethylene glycol segment is 4%.
Embodiment 13
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.5 terephthalic acid (TPA) is made into slurry with 2- decyl -1,6 hexylene glycols and is added in reactor,
A concentration of 60wt%, addition are to carry out esterification under the catalytic action of 0.5% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.3MPa, temperature is 240 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:2.0 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, carry out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.3MPa, temperature is 260 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 5%, is stirred 20 minutes, is being added
Amount be 0.05% catalyst acetic acid antimony of terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight 0.05% it is steady
Under the action of determining agent Trimethyl phosphite, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure by
It is 450Pa that normal pressure, which is steadily evacuated to absolute pressure, and at 270 DEG C, the reaction time is 50 minutes for temperature control；It then proceedes to vacuumize,
The polycondensation reaction for carrying out high vacuum stage of Fig, it is 30Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled at 280 DEG C, instead
90 minutes between seasonable, modified poly ester is made.
The number-average molecular weight of modified poly ester obtained is 30000, by terephthalic acid (TPA) segment, ethylene glycol segment and the 2- last of the ten Heavenly stems
Base -1,6 hexylene glycol segment forms, and the Mole percent ratio of 2- decyl -1,6 hexylene glycol segments and ethylene glycol segment is 5%.
Embodiment 14
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.47 terephthalic acid (TPA) is made into slurry with 2- nonyl -1,6 hexylene glycols and is added in reactor,
A concentration of 60wt%, addition are to carry out esterification under the catalytic action of 0.47% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 220 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.8 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, carry out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.27MPa, temperature is 258 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4%, is stirred 18 minutes, is being added
Amount is 0.04% catalyst glycol antimony of terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight 0.04%
Under the action of stabilizer trimethyl phosphate, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure by
Normal pressure is steadily evacuated to absolute pressure 460Pa, and at 263 DEG C, the reaction time is 47 minutes for temperature control；It then proceedes to vacuumize, into
The polycondensation reaction of row high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature is controlled at 278 DEG C, reaction
Between 85 minutes, be made modified poly ester.
The number-average molecular weight of modified poly ester obtained is 28000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- nonyls
Base -1,6 hexylene glycol segment forms, and the Mole percent ratio of 2- nonyl -1,6 hexylene glycol segments and ethylene glycol segment is 4%.
Embodiment 15
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.46 terephthalic acid (TPA) is made into slurry with 2- octyl -1,6 hexylene glycols and is added in reactor,
A concentration of 60wt%, addition are to carry out esterification under the catalytic action of 0.49% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 233 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.8 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, carry out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 259 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.5%, is stirred 19 minutes, is adding
It is terephthalic acid (TPA) weight to enter 0.044% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition
Under the action of 0.046% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure
Section pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 269 DEG C, the reaction time is 48 minutes for temperature control；It then proceedes to take out
Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be down to absolute pressure 40Pa, and reaction temperature is controlled at 279 DEG C,
Modified poly ester was made in 87 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 29000, pungent by terephthalic acid (TPA) segment, ethylene glycol segment and 2-
Base -1,6 hexylene glycol segment forms, and the Mole percent ratio of 2- octyl -1,6 hexylene glycol segments and ethylene glycol segment is 4.5%.
Embodiment 16
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.49 terephthalic acid (TPA) is made into slurry with 2- heptyl -1,6 hexylene glycols and is added in reactor,
A concentration of 60wt%, addition are to carry out esterification under the catalytic action of 0.48% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 230 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.8 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, carry out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 258 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.7%, is stirred 19 minutes, is adding
It is terephthalic acid (TPA) weight to enter 0.048% catalyst glycol antimony that amount is terephthalic acid (TPA) weight and addition
Under the action of 0.047% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure
Section pressure is steadily evacuated to absolute pressure 460Pa by normal pressure, and at 267 DEG C, the reaction time is 48 minutes for temperature control；It then proceedes to take out
Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be down to absolute pressure 40Pa, and reaction temperature is controlled at 279 DEG C,
Modified poly ester was made in 83 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 27000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- heptan
Base -1,6 hexylene glycol segment forms, and the Mole percent ratio of 2- heptyl -1,6 hexylene glycol segments and ethylene glycol segment is 4.7%.
Embodiment 17
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.467 terephthalic acid (TPA) is made into slurry with 2- hexyl -1,6 hexylene glycols and is added in reactor,
In a concentration of 60wt%, addition is be esterified anti-under the catalytic action of 0.47% concentrated sulfuric acid of terephthalic acid (TPA) weight
It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.27MPa, temperature is 236 DEG C, when in esterification
Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.89 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, be esterified anti-
It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 258 DEG C, when in esterification
Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.3%, is stirred 18 minutes, is adding
It is terephthalic acid (TPA) weight to enter 0.04% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition
Under the action of 0.041% stabilizer Trimethyl phosphite, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, it should
Staged pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 268 DEG C, the reaction time is 48 minutes for temperature control；It then proceedes to
It vacuumizes, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be down to absolute pressure 40Pa, reaction temperature is controlled 278
DEG C, modified poly ester was made in 85 minutes reaction time.
The number-average molecular weight of modified poly ester obtained be 29000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- oneself
Base -1,6 hexylene glycol segment forms, and the Mole percent ratio of 2- hexyl -1,6 hexylene glycol segments and ethylene glycol segment is 4.3%.
Embodiment 18
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.48 terephthalic acid (TPA) is made into slurry with 2- amyl -1,6 hexylene glycols and is added in reactor,
A concentration of 55wt%, addition are to carry out esterification under the catalytic action of 0.46% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 230 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.88 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, be esterified anti-
It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 256 DEG C, when in esterification
Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.7%, is stirred 18 minutes, is adding
It is terephthalic acid (TPA) weight to enter 0.047% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition
Under the action of 0.047% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure
Section pressure is steadily evacuated to absolute pressure 480Pa by normal pressure, and at 265 DEG C, the reaction time is 47 minutes for temperature control；It then proceedes to take out
Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be down to absolute pressure 40Pa, and reaction temperature is controlled at 279 DEG C,
Modified poly ester was made in 85 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 28000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- penta
Base -1,6 hexylene glycol segment forms, and the Mole percent ratio of 2- amyl -1,6 hexylene glycol segments and ethylene glycol segment is 4.7%.
Embodiment 19
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.46 terephthalic acid (TPA) is made into slurry with 2- decyl -1,5 pentanediols and is added in reactor,
A concentration of 55wt%, addition are to carry out esterification under the catalytic action of 0.47% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 238 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.9 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, carry out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 259 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching 92% of theoretical value or more, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.7%, is stirred 19 minutes, is adding
Enter the 0.046% catalyst acetic acid antimony that amount is terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight 0.048%
Stabilizer Trimethyl phosphite under the action of, under conditions of negative pressure start low vacuum stage polycondensation reaction, the stage pressure
It is 446Pa that power, which is steadily evacuated to absolute pressure by normal pressure, and at 267 DEG C, the reaction time is 49 minutes for temperature control；It then proceedes to take out true
Sky carries out the polycondensation reaction of high vacuum stage of Fig, and it is 40Pa so that reaction pressure is down to absolute pressure, and reaction temperature is controlled at 278 DEG C,
Modified poly ester was made in 87 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment and the 2- last of the ten Heavenly stems
Base -1,5 pentanediol segment forms, and the Mole percent ratio of 2- decyl -1,5 pentanediol segments and ethylene glycol segment is 4.7%.
Embodiment 20
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.46 terephthalic acid (TPA) is made into slurry with 2- nonyl -1,5 pentanediols and is added in reactor,
A concentration of 60wt%, addition are to carry out esterification under the catalytic action of 0.46% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.26MPa, temperature is 221 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.89 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, be esterified anti-
It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.25MPa, temperature is 259 DEG C, when in esterification
Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.1%, is stirred 18 minutes, is adding
It is terephthalic acid (TPA) weight to enter 0.041% catalyst glycol antimony that amount is terephthalic acid (TPA) weight and addition
Under the action of 0.042% stabilizer trimethyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure
Section pressure is steadily evacuated to absolute pressure 460Pa by normal pressure, and at 265 DEG C, the reaction time is 47 minutes for temperature control；It then proceedes to take out
Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be down to absolute pressure 40Pa, and reaction temperature is controlled at 278 DEG C,
Modified poly ester was made in 85 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 28000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- nonyls
Base -1,5 pentanediol segment forms, and the Mole percent ratio of 2- nonyl -1,5 pentanediol segments and ethylene glycol segment is 4.1%.
Embodiment 21
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.43 terephthalic acid (TPA) is made into slurry with 2- octyl -1,5 pentanediols and is added in reactor,
A concentration of 60wt%, addition are to carry out esterification under the catalytic action of 0.47% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.27MPa, temperature is 235 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.78 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, be esterified anti-
It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.26MPa, temperature is 255 DEG C, when in esterification
Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.3%, is stirred 17 minutes, is adding
It is terephthalic acid (TPA) weight to enter 0.043% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition
Under the action of 0.049% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure
Section pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 268 DEG C, the reaction time is 46 minutes for temperature control；It then proceedes to take out
Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be down to absolute pressure 40Pa, and reaction temperature is controlled at 275 DEG C,
Modified poly ester was made in 85 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 28000, pungent by terephthalic acid (TPA) segment, ethylene glycol segment and 2-
Base -1,5 pentanediol segment forms, and the Mole percent ratio of 2- octyl -1,5 pentanediol segments and ethylene glycol segment is 4.3%.
Embodiment 22
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.43 terephthalic acid (TPA) is made into slurry with 2- heptyl -1,5 pentanediols and is added in reactor,
A concentration of 55wt%, addition are to carry out esterification under the catalytic action of 0.45% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.29MPa, temperature is 235 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.87 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, be esterified anti-
It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.27MPa, temperature is 255 DEG C, when in esterification
Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.6%, is stirred 18 minutes, is adding
Enter 0.047% catalyst glycol antimony that amount is terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight 0.04%
Stabilizer triphenyl phosphate under the action of, under conditions of negative pressure start low vacuum stage polycondensation reaction, the staged pressure
Absolute pressure 470Pa is steadily evacuated to by normal pressure, at 268 DEG C, the reaction time is 45 minutes for temperature control；It then proceedes to vacuumize,
The polycondensation reaction for carrying out high vacuum stage of Fig makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature is controlled at 279 DEG C, reaction
Modified poly ester was made in 83 minutes time.
The number-average molecular weight of modified poly ester obtained is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- heptan
Base -1,5 pentanediol segment forms, and the Mole percent ratio of 2- heptyl -1,5 pentanediol segments and ethylene glycol segment is 4.6%.
Embodiment 23
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.457 terephthalic acid (TPA) is made into slurry with 2- hexyl -1,5 pentanediols and is added in reactor,
A concentration of 55%, addition is to carry out esterification under the catalytic action of 0.46% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 239 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.81 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, be esterified anti-
It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.27MPa, temperature is 255 DEG C, when in esterification
Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.41%, is stirred 19 minutes,
Addition is 0.042% the catalytic antimony trioxide of terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under the action of 0.048% stabilizer Trimethyl phosphite, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, it should
Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the reaction time is 45 minutes for temperature control；It then proceedes to
It vacuumizes, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be down to absolute pressure 50Pa, reaction temperature is controlled 275
DEG C, modified poly ester was made in 85 minutes reaction time.
The number-average molecular weight of modified poly ester obtained be 28000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- oneself
Base -1,5 pentanediol segment forms, and the Mole percent ratio of 2- hexyl -1,5 pentanediol segments and ethylene glycol segment is 4.41%.
Embodiment 24
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.47 terephthalic acid (TPA) is made into slurry with 2- amyl -1,5 pentanediols and is added in reactor,
A concentration of 55wt%, addition are to carry out esterification under the catalytic action of 0.48% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.27MPa, temperature is 245 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.81 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, be esterified anti-
It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.27MPa, temperature is 259 DEG C, when in esterification
Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.67%, is stirred 19 minutes,
Addition is 0.041% the catalytic antimony trioxide of terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under the action of 0.042% stabilizer triphenyl phosphate, start the polycondensation reaction of low vacuum stage, the rank under conditions of negative pressure
Section pressure is steadily evacuated to absolute pressure 485Pa by normal pressure, and at 268 DEG C, the reaction time is 46 minutes for temperature control；It then proceedes to take out
Vacuum carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be down to absolute pressure 50Pa, and reaction temperature is controlled at 275 DEG C,
Modified poly ester was made in 89 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- penta
Base -1,5 pentanediol segment forms, and the Mole percent ratio of 2- amyl -1,5 pentanediol segments and ethylene glycol segment is 4.67%.
Embodiment 25
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.45 terephthalic acid (TPA) is mixed with -1,4 butanediol of -1,5 pentanediol of 2- hexyls and 2- amyls
It closes object to be made into slurry addition reactor, wherein the molar ratio of 2- hexyls -1,5 pentanediol and 2- amyls-Isosorbide-5-Nitrae butanediol is 3:1,
A concentration of 55%, addition is to carry out esterification under the catalytic action of 0.49% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.26MPa, temperature is 236 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.8 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, carry out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 258 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.4%, is stirred 18 minutes, is adding
It is terephthalic acid (TPA) weight to enter 0.042% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition
Under the action of 0.047% stabilizer Trimethyl phosphite, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, it should
Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the reaction time is 49 minutes for temperature control；It then proceedes to
It vacuumizes, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be down to absolute pressure 50Pa, reaction temperature is controlled 278
DEG C, modified poly ester was made in 88 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment, 2- hexyls-
1,5 pentanediol segment and 2- amyls-Isosorbide-5-Nitrae butanediol segment composition, 2- hexyl -1,5 pentanediol segments and 2- amyls-Isosorbide-5-Nitrae fourth two
The summation of alcohol segment is 4.4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 26
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.45 terephthalic acid (TPA) and -1,6 hexylene glycol of 2- octyls and -1,5 pentanediol of 2- amyls
Mixture is made into slurry and is added in reactor, and the molar ratio of wherein 2- octyls -1,6 hexylene glycol and 2- amyl -1,5 pentanediols is 3:
2, a concentration of 60%, addition is be esterified anti-under the catalytic action of 0.45% concentrated sulfuric acid of terephthalic acid (TPA) weight
It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 239 DEG C, when in esterification
Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.84 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, be esterified anti-
It answers, esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.29MPa, temperature is 255 DEG C, when in esterification
Water quantity of distillate is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.6%, is stirred 18 minutes, is adding
It is terephthalic acid (TPA) weight to enter 0.0423% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition
Under the action of 0.045% stabilizer Trimethyl phosphite, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, it should
Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the reaction time is 45 minutes for temperature control；It then proceedes to
It vacuumizes, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be down to absolute pressure 50Pa, reaction temperature is controlled 278
DEG C, modified poly ester was made in 85 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 28000, by terephthalic acid (TPA) segment, ethylene glycol segment, 2- octyls-
1,6 hexylene glycol segment and 2- amyl -1,5 pentanediol segments composition, 2- octyl -1,6 hexylene glycol segments and 2- amyls -1,5 penta 2
The Mole percent ratio of alcohol segment and ethylene glycol segment is 4.6%.
Embodiment 27
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.45 terephthalic acid (TPA) is mixed with -1,4 butanediol of -1,5 pentanediol of 2- hexyls and 2- amyls
It closes object to be made into slurry addition reactor, wherein the molar ratio of 2- hexyls -1,5 pentanediol and 2- amyls-Isosorbide-5-Nitrae butanediol is 3:1,
A concentration of 55%, addition is to carry out esterification under the catalytic action of 0.49% concentrated sulfuric acid of terephthalic acid (TPA) weight,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.26MPa, temperature is 236 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 96% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.8 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, carry out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.28MPa, temperature is 258 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.4%, is stirred 18 minutes, is adding
It is terephthalic acid (TPA) weight to enter 0.042% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition
Under the action of 0.047% stabilizer Trimethyl phosphite, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, it should
Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the reaction time is 49 minutes for temperature control；It then proceedes to
It vacuumizes, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be down to absolute pressure 50Pa, reaction temperature is controlled 278
DEG C, modified poly ester was made in 88 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment, 2- hexyls-
1,5 pentanediol segment and 2- amyls-Isosorbide-5-Nitrae butanediol segment composition, 2- hexyl -1,5 pentanediol segments and 2- amyls-Isosorbide-5-Nitrae fourth two
The summation of alcohol segment is 4.4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 28
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
It is 1 by molar ratio:1.45 terephthalic acid (TPA) and -1,3 propylene glycol of 2- octyls, -1,4 butanediol of 2- amyls and 2- oneself
The mixture of base -1,6 hexylene glycol is made into slurry and is added in reactor, wherein 2- octyls -1,3 propylene glycol, 2- amyls-Isosorbide-5-Nitrae fourth two
The molar ratio of -1,6 hexylene glycol of alcohol and 2- hexyls is 3:2:1, a concentration of 60%, addition is terephthalic acid (TPA) weight
Under the catalytic action of 0.47% concentrated sulfuric acid, esterification, esterification compressive reaction in nitrogen atmosphere, moulding pressure are carried out
For 0.29MPa, temperature is 235 DEG C, is esterification terminal when the water quantity of distillate in esterification reaches the 92% of theoretical value,
Obtain terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is 1 by molar ratio:1.8 terephthalic acid (TPA)s and ethylene glycol are added after being made into slurry in reactor, carry out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure 0.27MPa, temperature is 258 DEG C, when the water in esterification evaporates
Output is esterification terminal when reaching the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, it is right
The Mole percent ratio of phthalic acid binary alcohol esters and ethylene glycol terephthalate is 4.71%, is stirred 18 minutes,
Addition is 0.04% the catalytic antimony trioxide of terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under the action of 0.041% stabilizer Trimethyl phosphite, start the polycondensation reaction of low vacuum stage under conditions of negative pressure, it should
Staged pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 268 DEG C, the reaction time is 49 minutes for temperature control；It then proceedes to
It vacuumizes, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be down to absolute pressure 50Pa, reaction temperature is controlled 277
DEG C, modified poly ester was made in 84 minutes reaction time.
The number-average molecular weight of modified poly ester obtained is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment, band branch
Glycol segment composition, wherein branched glycol segment be 2- octyl -1,3 propylene glycol segment, 2- amyls-Isosorbide-5-Nitrae butanediol chain
Section and 2- hexyl -1,6 hexylene glycol segments composition, the Mole percent ratio of branched glycol segment and ethylene glycol segment are
4.71%.
Embodiment 29
A kind of preparation method of the high-strength ultralow miniature polyester industrial fiber of high uniformity, the high-strength ultralow miniature polyester of high uniformity
Industrial yarn is made using porous spinneret, and the arrangement mode of spinneret orifice is oval shaped arrangements on spinneret, and oval shaped arrangements refer to
The hole center of spinneret orifice is located on concentration ellipse, and concentration ellipse is that series is oval, and all elliptical long axis are conllinear, and short axle is total
Line.
As shown in Figure 1, elliptical long axis and the ratio of minor axis length are 1.3, the spacing of adjacent spinneret orifice is equal to spinneret orifice
Guide hole diameter add 1.5mm, spinneret is round spinneret, diameter and the oval maximum long axial length of series of round spinneret
The difference of degree is 11mm, and the spinneret hole count of a diameter of 2.0mm of guide hole of spinneret orifice, spinneret are 374, the spinneret orifice of spinneret
Cross-sectional shape be circle.
Modified poly ester made from embodiment 1 is viscosified through solid phase polycondensation, is measured, porous spinneret squeezes out, is cooled down, is oiled, drawing
It stretches, thermal finalization and winding, the high-strength ultralow miniature polyester industrial fiber of obtained high uniformity cool down wherein the temperature squeezed out is 290 DEG C
Wind-warm syndrome be 20 DEG C, GR-1 speed 3000m/min；75 DEG C of temperature；GR-2 speed 3800m/min；85 DEG C of temperature；GR-3 speed
5000m/min；250 DEG C of temperature；GR-4 speed 5500m/min；250 DEG C of temperature；GR-5 speed 5630m/min；250 DEG C of temperature；
GR-6 speed 5500m/min；250 DEG C of temperature；The speed of winding is 5450m/min.
The fracture strength of the high-strength ultralow miniature polyester industrial fiber of high uniformity obtained is 7.2cN/dtex；Line density deviation
Rate is 0.6%, and fracture strength CV values are 1.8%, and extension at break CV values are 4.5%, extension at break 19.0, at 260 DEG C, is melted
Body viscosity declines 11%, and in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, dry-hot shrinkage is
1.8%, fiber modulus 110cN/dtex.
Fiber modulus >=100cN/dtex；Dry-hot shrinkage is 2.0 ± 0.25% (1.72-2.25), and extension at break is
20.0 ± 1.5% (18.5-21.5), fracture strength >=7.0cN/dtex；
Embodiment 30
A kind of preparation method of the high-strength ultralow miniature polyester industrial fiber of high uniformity, the high-strength ultralow miniature polyester of high uniformity
Industrial yarn is made using porous spinneret, and the arrangement mode of spinneret orifice is oval shaped arrangements on spinneret, and oval shaped arrangements refer to
The hole center of spinneret orifice is located on concentration ellipse, and concentration ellipse is that series is oval, and all elliptical long axis are conllinear, and short axle is total
Line.
As shown in figure 3, elliptical long axis and the ratio of minor axis length are 1.6, the spacing of adjacent spinneret orifice is equal to spinneret orifice
Guide hole diameter add 1.5mm, spinneret is round spinneret, diameter and the oval maximum long axial length of series of round spinneret
The difference of degree is 11mm, and the spinneret hole count of a diameter of 2.0mm of guide hole of spinneret orifice, spinneret are 382, the spinneret orifice of spinneret
Cross-sectional shape be circle.
Modified poly ester made from embodiment 1 is viscosified through solid phase polycondensation, is measured, porous spinneret squeezes out, is cooled down, is oiled, drawing
It stretches, thermal finalization and winding, the high-strength ultralow miniature polyester industrial fiber of obtained high uniformity cool down wherein the temperature squeezed out is 290 DEG C
Wind-warm syndrome be 20 DEG C, GR-1 speed 3000m/min；75 DEG C of temperature；GR-2 speed 3800m/min；85 DEG C of temperature；GR-3 speed
5000m/min；250 DEG C of temperature；GR-4 speed 5500m/min；250 DEG C of temperature；GR-5 speed 5630m/min；250 DEG C of temperature；
GR-6 speed 5500m/min；250 DEG C of temperature；The speed of winding is 5450m/min.
The fracture strength of the high-strength ultralow miniature polyester industrial fiber of high uniformity obtained is 7.3cN/dtex；Line density deviation
Rate is 0.7%, and fracture strength CV values are 1.7%, and extension at break CV values are 4.8%, extension at break 19.0, at 260 DEG C, is melted
Body viscosity declines 11%, and in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, dry-hot shrinkage is
1.9%, fiber modulus 110cN/dtex.
Comparative example 1
A kind of preparation method of the high-strength ultralow miniature polyester industrial fiber of high uniformity, the high-strength ultralow miniature polyester of high uniformity
Industrial yarn is made using porous spinneret, and the arrangement mode of spinneret orifice is circular arrangement on spinneret, and circular arrangement refers to spinneret
The hole center in hole is located on concentric circles, and concentric circles is that series is round.As shown in Fig. 2, the spacing of adjacent spinneret orifice is equal to spinneret orifice
Guide hole diameter add 1.5mm, spinneret is round spinneret, diameter and the round maximum diameter of series of round spinneret
Difference is 11mm, and the spinneret hole count of a diameter of 2.0mm of guide hole of spinneret orifice, spinneret are 370, the cross of the spinneret orifice of spinneret
Cross sectional shape is circle.
Modified poly ester made from embodiment 1 is viscosified through solid phase polycondensation, is measured, porous spinneret squeezes out, is cooled down, is oiled, drawing
It stretches, thermal finalization and winding, the high-strength ultralow miniature polyester industrial fiber of obtained high uniformity cool down wherein the temperature squeezed out is 290 DEG C
Wind-warm syndrome be 20 DEG C, GR-1 speed 3000m/min；75 DEG C of temperature；GR-2 speed 3800m/min；85 DEG C of temperature；GR-3 speed
5000m/min；250 DEG C of temperature；GR-4 speed 5500m/min；250 DEG C of temperature；GR-5 speed 5630m/min；250 DEG C of temperature；
GR-6 speed 5500m/min；250 DEG C of temperature；The speed of winding is 5450m/min.
The fracture strength of the high-strength ultralow miniature polyester industrial fiber of high uniformity obtained is 7.4cN/dtex；Line density deviation
Rate is 1%, and fracture strength CV values are 1.9%, and extension at break CV values are 5.3%, extension at break 20.1, at 260 DEG C, melt
Viscosity declines 11%, and in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, dry-hot shrinkage is
1.75%, fiber modulus 114cN/dtex.
With embodiment 29 comparison as can be seen that the effective area of spinneret it is identical when, (circular arrangement when spinneret hole count is close
Spinneret hole count is 370, and oval shaped arrangements spinneret hole count is that 374), the spinneret orifice number of plies of oval shaped arrangements is 6, is less than circular arrangement
The spinneret orifice number of plies 8, cooling effect is more preferable；It is oval with the comparison of embodiment 30 as can be seen that when the identical effective area of spinneret
The spinneret orifice number of plies of shape arrangement is 5, is less than the spinneret orifice number of plies 8 of circular arrangement, cooling effect is more preferable, the spinneret of oval shaped arrangements
The hole count 382 in hole is more than the hole count 370 of the spinneret orifice of circular arrangement, cooling efficiency higher.The comparing result of fibre property shows
Fiber linear density deviation ratio made from embodiment 29 and embodiment 30, fracture strength CV values, extension at break CV values are less than comparative example
1, under the conditions of illustrating same process, fibre property made from the spinneret using spinneret orifice oval shaped arrangements is better than using spinneret
The spinneret of circular arrangement.
Embodiment 31~33
A kind of preparation method of the high-strength ultralow miniature polyester industrial fiber of high uniformity, spinneret orifice are arranged as long axial symmetry,
Elliptical long axis and the ratio of minor axis length are 1.4, and the spacing of adjacent spinneret orifice is added equal to the guide hole diameter of spinneret orifice
1.6mm, spinneret are round spinneret, and the diameter of round spinneret and the difference of serial oval maximum long axis length are
12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 384 of spinneret, the cross section shape of the spinneret orifice of spinneret
Shape is square.
The high-strength ultralow miniature polyester industrial fiber of high uniformity is squeezed out through metering, porous spinneret, is cooled down, oiling, stretching, is hot
Sizing and winding, are made the high-strength ultralow miniature polyester industrial fiber of high uniformity, wherein the temperature squeezed out is 300 DEG C, cooling wind
Temperature is 25 DEG C；It stretches, heat setting process parameter is：GR-1 speed 600m/min；Temperature is room temperature；GR-2 speed 1000m/min；
100 DEG C of temperature；GR-3 speed 2500m/min；150 DEG C of temperature；GR-4 speed 3500m/min；250 DEG C of temperature；GR-5 speed
3500m/min；250 DEG C of temperature；GR-6 speed 3400m/min；220 DEG C of temperature；The speed of winding is 3400m/min.
For the high-strength ultralow miniature polyester industrial fiber of high uniformity obtained at 280 DEG C, melt viscosity declines percentage, room temperature
The mechanical performance data of lower industrial yarn, and in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, industry
The dry-hot shrinkage such as following table of silk.
Embodiment 34~36
A kind of preparation method of the high-strength ultralow miniature polyester industrial fiber of high uniformity is made, spinneret using porous spinneret
The arrangement mode of spinneret orifice is oval shaped arrangements on plate, and oval shaped arrangements refer to that the hole center of spinneret orifice is located on concentration ellipse,
Concentration ellipse is that series is oval, and all elliptical long axis are conllinear, and short axle is conllinear.
Spinneret orifice is arranged as long axial symmetry, and the ratio of elliptical long axis and minor axis length is 1.4, between adjacent spinneret orifice
1.6mm is added away from the guide hole diameter equal to spinneret orifice, spinneret is round spinneret, and the diameter and series of round spinneret are oval
The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 192 of spinneret, spinneret
The cross-sectional shape of the spinneret orifice of plate is square.
The high-strength ultralow miniature polyester industrial fiber of high uniformity is squeezed out through metering, porous spinneret, is cooled down, oiling, stretching, is hot
Sizing and winding, are made the high-strength ultralow miniature polyester industrial fiber of high uniformity, wherein the temperature squeezed out is 310 DEG C, cooling wind
Temperature is 30 DEG C；It stretches, heat setting process parameter is：GR-1 speed 3600m/min；75 DEG C of temperature；GR-2 speed 4500m/min；
95 DEG C of temperature；GR-3 speed 5600m/min；255 DEG C of temperature；GR-4 speed 5600m/min；255 DEG C of temperature；GR-5 speed
5650m/min；255 DEG C of temperature；GR-6 speed 5600m/min；255 DEG C of temperature；The speed of winding is 5500m/min.
The high-strength ultralow miniature polyester industrial fiber of high uniformity obtained melt viscosity at 290 DEG C declines percentage, room temperature
The mechanical performance data of lower industrial yarn, and in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, industry
The dry-hot shrinkage such as following table of silk.
Embodiment 37~39
A kind of preparation method of the high-strength ultralow miniature polyester industrial fiber of high uniformity, spinneret orifice are arranged as long axial symmetry,
Elliptical long axis and the ratio of minor axis length are 1.4, and the spacing of adjacent spinneret orifice is added equal to the guide hole diameter of spinneret orifice
1.6mm, spinneret are round spinneret, and the diameter of round spinneret and the difference of serial oval maximum long axis length are
12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 192 of spinneret, the cross section shape of the spinneret orifice of spinneret
Shape is square.
The high-strength ultralow miniature polyester industrial fiber of high uniformity is squeezed out through metering, porous spinneret, is cooled down, oiling, stretching, is hot
Sizing and winding, are made the high-strength ultralow miniature polyester industrial fiber of high uniformity, wherein the temperature squeezed out is 290 DEG C, cooling wind
Temperature is 20 DEG C；It stretches, heat setting process parameter is：GR-1 speed 3400m/min；78 DEG C of temperature；GR-2 speed 4300m/min；
90 DEG C of temperature；GR-3 speed 5200m/min；251 DEG C of temperature；GR-4 speed 5550m/min；250 DEG C of temperature；GR-5 speed
5630m/min；255 DEG C of temperature；GR-6 speed 5600m/min；255 DEG C of temperature；The speed of winding is 5460m/min.
The high-strength ultralow miniature polyester industrial fiber of high uniformity obtained melt viscosity at 270 DEG C declines percentage, room temperature
The mechanical performance data of lower industrial yarn, and in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, industry
The dry-hot shrinkage such as following table of silk.
Embodiment 40~42
A kind of preparation method of the high-strength ultralow miniature polyester industrial fiber of high uniformity, spinneret orifice are arranged as long axial symmetry,
Elliptical long axis and the ratio of minor axis length are 1.4, and the spacing of adjacent spinneret orifice is added equal to the guide hole diameter of spinneret orifice
1.6mm, spinneret are round spinneret, and the diameter of round spinneret and the difference of serial oval maximum long axis length are
12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 384 of spinneret, the cross section shape of the spinneret orifice of spinneret
Shape is square.
The high-strength ultralow miniature polyester industrial fiber of high uniformity is squeezed out through metering, porous spinneret, is cooled down, oiling, stretching, is hot
Sizing and winding, are made the high-strength ultralow miniature polyester industrial fiber of high uniformity, wherein the temperature squeezed out is 300 DEG C, cooling wind
Temperature is 25 DEG C；It stretches, heat setting process parameter is：GR-1 speed 3300m/min；80 DEG C of temperature；GR-2 speed 3900m/min；
88 DEG C of temperature；GR-3 speed 5300m/min；253 DEG C of temperature；GR-4 speed 5560m/min；254 DEG C of temperature；GR-5 speed
5640m/min；254 DEG C of temperature；GR-6 speed 5570m/min；253 DEG C of temperature；The speed of winding is 5450m/min.
The high-strength ultralow miniature polyester industrial fiber of high uniformity obtained melt viscosity at 260 DEG C declines percentage, room temperature
The mechanical performance data of lower industrial yarn, and in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, industry
The dry-hot shrinkage such as following table of silk.
Embodiment 43~45
A kind of preparation method of the high-strength ultralow miniature polyester industrial fiber of high uniformity, spinneret orifice are arranged as long axial symmetry,
Elliptical long axis and the ratio of minor axis length are 1.4, and the spacing of adjacent spinneret orifice is added equal to the guide hole diameter of spinneret orifice
1.6mm, spinneret are round spinneret, and the diameter of round spinneret and the difference of serial oval maximum long axis length are
12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 288 of spinneret, the cross section shape of the spinneret orifice of spinneret
Shape is square.
The high-strength ultralow miniature polyester industrial fiber of high uniformity is squeezed out through metering, porous spinneret, is cooled down, oiling, stretching, is hot
Sizing and winding, are made the high-strength ultralow miniature polyester industrial fiber of high uniformity, wherein the temperature squeezed out is 290 DEG C, cooling wind
Temperature is 30 DEG C；It stretches, heat setting process parameter is：GR-1 speed 3600m/min；75 DEG C of temperature；GR-2 speed 4500m/min；
85 DEG C of temperature；GR-3 speed 5000m/min；255 DEG C of temperature；GR-4 speed 5600m/min；250 DEG C of temperature；GR-5 speed
5630m/min；250 DEG C of temperature；GR-6 speed 5600m/min；250 DEG C of temperature；The speed of winding is 5450m/min.
The high-strength ultralow miniature polyester industrial fiber of high uniformity obtained is at 280 DEG C, melt viscosity, industrial yarn under room temperature
Mechanical performance data, and in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, the xeothermic receipts of industrial yarn
Shrinkage such as following table.
Embodiment 46~48
A kind of preparation method of the high-strength ultralow miniature polyester industrial fiber of high uniformity is made, spinneret using porous spinneret
The arrangement mode of spinneret orifice is oval shaped arrangements on plate, and oval shaped arrangements refer to that the hole center of spinneret orifice is located on concentration ellipse,
Concentration ellipse is that series is oval, and all elliptical long axis are conllinear, and short axle is conllinear.
Spinneret orifice is arranged as long axial symmetry, and the ratio of elliptical long axis and minor axis length is 1.4, between adjacent spinneret orifice
1.6mm is added away from the guide hole diameter equal to spinneret orifice, spinneret is round spinneret, and the diameter and series of round spinneret are oval
The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 244 of spinneret, spinneret
The cross-sectional shape of the spinneret orifice of plate is square.
The high-strength ultralow miniature polyester industrial fiber of high uniformity is squeezed out through metering, porous spinneret, is cooled down, oiling, stretching, is hot
Sizing and winding, are made the high-strength ultralow miniature polyester industrial fiber of high uniformity, wherein GR-1 speed 3500m/min；76 DEG C of temperature；
GR-2 speed 4000m/min；95 DEG C of temperature；GR-3 speed 5600m/min；251 DEG C of temperature；GR-4 speed 5600m/min；Temperature
250℃；GR-5 speed 5645m/min；255 DEG C of temperature；GR-6 speed 5600m/min；251 DEG C of temperature；The speed of winding is
5457m/min。
The high-strength ultralow miniature polyester industrial fiber of high uniformity obtained melt viscosity at 280 DEG C declines percentage, room temperature
The mechanical performance data of lower industrial yarn, and in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, industry
The dry-hot shrinkage such as following table of silk.
Embodiment 49~51
A kind of preparation method of the high-strength ultralow miniature polyester industrial fiber of high uniformity is made, spinneret using porous spinneret
The arrangement mode of spinneret orifice is oval shaped arrangements on plate, and oval shaped arrangements refer to that the hole center of spinneret orifice is located on concentration ellipse,
Concentration ellipse is that series is oval, and all elliptical long axis are conllinear, and short axle is conllinear.
Spinneret orifice is arranged as long axial symmetry, and the ratio of elliptical long axis and minor axis length is 1.4, between adjacent spinneret orifice
1.6mm is added away from the guide hole diameter equal to spinneret orifice, spinneret is round spinneret, and the diameter and series of round spinneret are oval
The difference of maximum long axis length is 12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 192 of spinneret, spinneret
The cross-sectional shape of the spinneret orifice of plate is square.
The high-strength ultralow miniature polyester industrial fiber of high uniformity is squeezed out through metering, porous spinneret, is cooled down, oiling, stretching, is hot
Sizing and winding, are made the high-strength ultralow miniature polyester industrial fiber of high uniformity, wherein the temperature squeezed out is 310 DEG C, cooling wind
Temperature is 30 DEG C；It stretches, heat setting process parameter is：GR-1 speed 3200m/min；79 DEG C of temperature；GR-2 speed 4100m/min；
8 DEG C of temperature；GR-3 speed 5200m/min；255 DEG C of temperature；GR-4 speed 5600m/min；255 DEG C of temperature；GR-5 speed
5650m/min；255 DEG C of temperature；GR-6 speed 5600m/min；255 DEG C of temperature；The speed of winding is 5500m/min.
The high-strength ultralow miniature polyester industrial fiber melt viscosity at 280 DEG C of high uniformity obtained, industrial yarn under room temperature
Mechanical performance data, and in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, the xeothermic receipts of industrial yarn
Shrinkage such as following table.
Embodiment 52~57
A kind of preparation method of the high-strength ultralow miniature polyester industrial fiber of high uniformity, spinneret orifice are arranged as long axial symmetry,
Elliptical long axis and the ratio of minor axis length are 1.4, and the spacing of adjacent spinneret orifice is added equal to the guide hole diameter of spinneret orifice
1.6mm, spinneret are round spinneret, and the diameter of round spinneret and the difference of serial oval maximum long axis length are
12mm, a diameter of 1.5mm of guide hole of spinneret orifice, the spinneret orifice numerical digit 192 of spinneret, the cross section shape of the spinneret orifice of spinneret
Shape is square.
The high-strength ultralow miniature polyester industrial fiber of high uniformity is squeezed out through metering, porous spinneret, is cooled down, oiling, stretching, is hot
Sizing and winding, are made the high-strength ultralow miniature polyester industrial fiber of high uniformity, wherein the temperature squeezed out is 310 DEG C, cooling wind
Temperature is 20 DEG C；It stretches, heat setting process parameter is：GR-1 speed 3500m/min；79 DEG C of temperature；GR-2 speed 4400m/min；
91 DEG C of temperature；GR-3 speed 5300m/min；251 DEG C of temperature；GR-4 speed 5200m/min；251 DEG C of temperature；GR-5 speed
5630m/min；255 DEG C of temperature；GR-6 speed 5600m/min；255 DEG C of temperature；The speed of winding is 5500m/min.
The high-strength ultralow miniature polyester industrial fiber of high uniformity obtained melt viscosity at 280 DEG C declines percentage, room temperature
The mechanical performance data of lower industrial yarn, and in the case where temperature is the test condition of 177 DEG C × 10min × 0.05cN/dtex, industry
The dry-hot shrinkage such as following table of silk.
Claims (10)
1. a kind of high mould lower shrinkage type polyester industrial fiber of high uniformity, it is characterized in that：The high mould lower shrinkage type of high uniformity is poly-
By modified poly ester, the spinning after solid-phase tack producing obtains ester industrial yarn；The material of the high mould lower shrinkage type polyester industrial fiber of high uniformity
For modified poly ester, the modified poly ester is made of terephthalic acid (TPA) segment, ethylene glycol segment and dihydric alcohol segment containing branch, institute
State that the dihydric alcohol segment containing branch refers on a non-end group carbon that branch is located in dihydric alcohol segment and branch is to contain 5-10
The dihydric alcohol segment of the linear carbon chain of a carbon atom, the molar percentage of the dihydric alcohol segment and ethylene glycol segment containing branch
Value is 2~5%；High mould lower shrinkage type polyester industrial linear density deviation ratio≤1.0% of high uniformity, fracture strength CV values
≤ 2.0%, extension at break CV value≤5.5%；Fiber modulus >=100cN/dtex；At 260~290 DEG C, melt viscosity declines
10-20%, temperature be 177 DEG C × 10min × 0.05cN/dtex test condition under, dry-hot shrinkage be 2.0 ±
0.25%, the melt viscosity declines refer to modified poly ester with normal polyester mutually synthermal melt viscosity comparison.
2. the high mould lower shrinkage type polyester industrial fiber of a kind of high uniformity according to claim 1, which is characterized in that the height
The extension at break of high uniformity mould lower shrinkage type polyester industrial fiber is 20.0 ± 1.5%, fracture strength >=7.0cN/dtex；It is described
The number-average molecular weight of modified poly ester is 15000-30000.
3. the high mould lower shrinkage type polyester industrial fiber of a kind of high uniformity according to claim 1, which is characterized in that described to contain
The dihydric alcohol segment of branch is -1,3 propylene glycol segment of 2- amyls, -1,3 propylene glycol segment of 2- hexyls, -1,3 propylene glycol of 2- heptyl
Segment, -1,3 propylene glycol segment of 2- octyls, -1,3 propylene glycol segment of 2- nonyls, -1,3 propylene glycol segment of 2- decyls, amyl -1 2-,
4 butanediol segments, -1,4 butanediol segment of 2- hexyls, -1,4 butanediol segment of 2- heptyl, -1,4 butanediol segment of 2- octyls, 2-
- 1,4 butanediol segment of nonyl, -1,4 butanediol segment of 2- decyls, -1,5 pentanediol segment of 2- amyls, -1,5 pentanediol of 2- hexyls
Segment, -1,5 pentanediol segment of 2- heptyl, -1,5 pentanediol segment of 2- octyls, -1,5 pentanediol segment of 2- nonyls, decyl -1 2-,
5 pentanediol segments, -1,6 hexylene glycol segment of 2- amyls, -1,6 hexylene glycol segment of 2- hexyls, -1,6 hexylene glycol segment of 2- heptyl, 2-
One or more of -1,6 hexylene glycol segment of -1,6 hexylene glycol segment of octyl, -1,6 hexylene glycol segment of 2- nonyls or 2- decyls.
4. a kind of preparation side of the high mould lower shrinkage type polyester industrial fiber of high uniformity as claimed in any one of claims 1-3
Method, it is characterized in that：Modified poly ester is squeezed out through solid phase polycondensation thickening, metering, porous spinneret, cools down, oil, stretching, heat is determined
The high mould lower shrinkage type polyester industrial fiber of high uniformity is made in type and winding；
The arrangement mode of spinneret orifice is oval shaped arrangements on the porous spinneret, and the oval shaped arrangements refer to the hole of spinneret orifice
Center is located on concentration ellipse, and the concentration ellipse is that series is oval, and all elliptical long axis are conllinear, and short axle is conllinear；
The preparation process of modified poly ester includes the following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
After terephthalic acid (TPA) and the dihydric alcohol containing branch are made into slurry, under the catalytic action of the concentrated sulfuric acid, esterification is carried out,
Obtain terephthalic acid (TPA) binary alcohol esters；The dihydric alcohol containing branch is the non-end group carbon that branch is located in dihydric alcohol segment
Upper and branch is the dihydric alcohol of the linear carbon chain containing 5-10 carbon atom；
(2) preparation of ethylene glycol terephthalate：
After terephthalic acid (TPA) and ethylene glycol are made into slurry, esterification is carried out, ethylene glycol terephthalate is obtained；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, stirring is mixed
It closes, under the action of catalyst and stabilizer, under conditions of negative pressure, carries out polycondensation reaction and the Gao Zhen of low vacuum stage successively
Modified poly ester is made in the polycondensation reaction in empty stage.
5. the preparation method of the high mould lower shrinkage type polyester industrial fiber of high uniformity according to claim 4, which is characterized in that
The modified poly ester prepare the specific steps are：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Terephthalic acid (TPA) and the dihydric alcohol containing branch are made into slurry to be added in reactor, under the catalytic action of the concentrated sulfuric acid, into
Row esterification, esterification compressive reaction in nitrogen atmosphere, moulding pressure are normal pressure~0.3MPa, and temperature is 180~240
DEG C, it is esterification terminal when the water quantity of distillate in esterification reaches 90% or more of theoretical value；Obtain terephthalic acid (TPA)
Binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
It is added in reactor after terephthalic acid (TPA) and ethylene glycol are made into slurry, carries out esterification, esterification is in nitrogen atmosphere
Middle compressive reaction is enclosed, moulding pressure is normal pressure~0.3MPa, and temperature is 250~260 DEG C, when the water quantity of distillate in esterification reaches
To theoretical value 90% or more when be esterification terminal, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After esterification in step (2), the terephthalic acid (TPA) binary alcohol esters prepared in step (1) are added, stirring is mixed
It closes 15-20 minutes, under the action of catalyst and stabilizer, starts the polycondensation reaction of low vacuum stage under conditions of negative pressure,
The staged pressure by normal pressure is steadily evacuated to absolute pressure 500Pa hereinafter, temperature control is at 260~270 DEG C, and the reaction time is 30~
50 minutes；It then proceedes to vacuumize, carries out the polycondensation reaction of high vacuum stage of Fig, so that reaction pressure is down to absolute pressure and be less than
Modified poly ester is made in 275~280 DEG C, 50~90 minutes reaction time in 100Pa, reaction temperature control；
Modified poly ester is obtained into Modified polyester chips through pelletizing again, acquired polyester slice is viscosified by solid phase polycondensation, makes polyester
The inherent viscosity of slice is increased to 1.0~1.2dL/g, as high viscous slice；Squeezed out again through metering, porous spinneret, be cooling, on
Oil, stretching, thermal finalization and winding, are made the high mould lower shrinkage type polyester industrial fiber of high uniformity；
Spinning main technologic parameters are：
The temperature of the extrusion is 290~310 DEG C；
The wind-warm syndrome of the cooling is 20~30 DEG C；
The stretching, heat setting process parameter are：
3000~3600m/min of GR-1 speed；75~80 DEG C of temperature；
3800~4500m/min of GR-2 speed；85~95 DEG C of temperature；
5000~5600m/min of GR-3 speed；250~255 DEG C of temperature；
5500~5600m/min of GR-4 speed；250~255 DEG C of temperature；
5630~5650m/min of GR-5 speed；250~255 DEG C of temperature；
5500~5600m/min of GR-6 speed；250~255 DEG C of temperature；
The speed of the winding is 5450~5500m/min.
6. a kind of preparation method of the high mould lower shrinkage type polyester industrial fiber of high uniformity according to claim 5, feature
It is, in the step (1), the molar ratio of terephthalic acid (TPA) and the dihydric alcohol containing branch is 1:1.3-1.5；Concentrated sulfuric acid addition
For the 0.3-0.5% of terephthalic acid (TPA) weight；A concentration of 50-60wt% of the concentrated sulfuric acid；In the step (2), to benzene two
The molar ratio of formic acid and ethylene glycol is 1:1.2~2.0；In the step (3), the terephthalic acid (TPA) binary alcohol esters with to benzene two
The Mole percent ratio of formic acid glycol ester is 2~5%；The catalyst is antimony oxide, antimony glycol or antimony acetate, is urged
Agent addition is the 0.01%~0.05% of terephthalic acid (TPA) total weight；The stabilizer is triphenyl phosphate, tripotassium phosphate
Ester or Trimethyl phosphite, stabilizer addition are the 0.01%~0.05% of the terephthalic acid (TPA) total weight.
7. a kind of preparation method of the high mould lower shrinkage type polyester industrial fiber of high uniformity according to claim 5, feature
Be, the dihydric alcohol containing branch be 2- amyls -1,3 propylene glycol, 2- hexyls -1,3 propylene glycol, 2- heptyl -1,3 propylene glycol,
- 1,3 propylene glycol of 2- octyls, -1,3 propylene glycol of 2- nonyls, -1,3 propylene glycol of 2- decyls, -1,4 butanediol of 2- amyls, hexyl -1 2-,
4 butanediols, -1,4 butanediol of 2- heptyl, -1,4 butanediol of 2- octyls, -1,4 butanediol of 2- nonyls, -1,4 butanediol of 2- decyls,
- 1,5 pentanediol of 2- amyls, -1,5 pentanediol of 2- hexyls, -1,5 pentanediol of 2- heptyl, -1,5 pentanediol of 2- octyls, nonyl -1 2-,
5 pentanediols, 2- decyls -1,5 pentanediol, 2- amyls -1,6 hexylene glycol, 2- hexyl -1,6 hexylene glycols, 2- heptyl -1,6 hexylene glycol,
One or more of -1,6 hexylene glycol of -1,6 hexylene glycol of 2- octyls, -1,6 hexylene glycol of 2- nonyls or 2- decyls.
8. a kind of preparation method of the high mould lower shrinkage type polyester industrial fiber of high uniformity according to claim 4, feature
It is, the porous spinneret is round spinneret or elliptical spinneret plate；The diameter and series of the circle spinneret are oval
The difference of maximum long axis length is more than 10mm, and the elliptical spinneret plate and the difference of serial oval maximum long axis length are big
In 10mm.
9. a kind of preparation method of the high mould lower shrinkage type polyester industrial fiber of high uniformity according to claim 4, feature
Be, on the porous spinneret spinneret orifice be arranged as long axis and/or short axle is symmetrical, the spacing of adjacent spinneret orifice is more than or equal to
The guide hole diameter of spinneret orifice adds 1.5mm；Elliptical long axis and the ratio of minor axis length are 1.3~1.8.
10. a kind of preparation method of the high mould lower shrinkage type polyester industrial fiber of high uniformity according to claim 4, feature
It is, a diameter of 1.5~2.5mm of guide hole of the spinneret orifice；The spinneret hole count of the spinneret is more than or equal to 192, the spray
The cross-sectional shape of the spinneret orifice of filament plate is circle, square, diamond shape, "-" type, triangular form, trilobal cross, hollow type or flat
Flat pattern.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610781240.9A CN107059152B (en) | 2016-08-31 | 2016-08-31 | A kind of high mould lower shrinkage type polyester industrial fiber of high uniformity and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610781240.9A CN107059152B (en) | 2016-08-31 | 2016-08-31 | A kind of high mould lower shrinkage type polyester industrial fiber of high uniformity and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107059152A CN107059152A (en) | 2017-08-18 |
| CN107059152B true CN107059152B (en) | 2018-09-14 |
Family
ID=59617036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610781240.9A Active CN107059152B (en) | 2016-08-31 | 2016-08-31 | A kind of high mould lower shrinkage type polyester industrial fiber of high uniformity and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107059152B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108130615B (en) * | 2017-12-14 | 2020-02-21 | 江苏恒力化纤股份有限公司 | Method for reducing oligomer content in polyester fiber |
| CN108385189B (en) * | 2017-12-14 | 2020-05-05 | 江苏恒力化纤股份有限公司 | Low-shrinkage high-strength polyester industrial yarn and preparation method thereof |
| CN108385418B (en) * | 2017-12-14 | 2020-02-21 | 江苏恒力化纤股份有限公司 | High-modulus low-shrinkage hard cord and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3769354B2 (en) * | 1997-06-05 | 2006-04-26 | 帝人ファイバー株式会社 | Method for producing modified polyester and method for producing the fiber |
| CN102030893A (en) * | 2009-09-29 | 2011-04-27 | 东丽纤维研究所（中国）有限公司 | Copolyester as well as preparation method and application 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 |
| CN104499080B (en) * | 2014-12-31 | 2016-06-15 | 江苏恒力化纤股份有限公司 | A kind of high-strength activated polyester industrial yarn and preparation method thereof |
-
2016
- 2016-08-31 CN CN201610781240.9A patent/CN107059152B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107059152A (en) | 2017-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106381557B (en) | A kind of high uniformity safety belt polyester industrial fiber and preparation method thereof | |
| CN106400162B (en) | A kind of high uniformity high intensity low shrinkage type polyester industrial fiber and preparation method thereof | |
| CN106245149B (en) | A kind of high uniformity vehicle mould polyester industrial fiber and preparation method thereof | |
| CN106283250B (en) | A kind of high-strength ultralow miniature polyester industrial fiber of high uniformity and preparation method thereof | |
| CN106245150B (en) | A kind of high uniformity coloured polyester industrial yarn and preparation method thereof | |
| CN106381558B (en) | A kind of abnormal contraction composite filament and preparation method thereof | |
| CN106400166B (en) | A kind of three leaf special-shaped polyester fiber of porous superbright light and preparation method thereof | |
| CN106381547B (en) | A kind of porous flexible polyester fiber FDY and preparation method thereof | |
| CN106350886B (en) | A kind of high uniformity high-strength polyester industrial fiber and preparation method thereof | |
| CN106283260B (en) | Porous super flexible polyester fiber FDY of one kind and preparation method thereof | |
| CN107059152B (en) | A kind of high mould lower shrinkage type polyester industrial fiber of high uniformity and preparation method thereof | |
| CN106400169B (en) | A kind of porous polyester fiber POY and preparation method thereof | |
| CN106400165B (en) | A kind of military soft type polyester industrial fiber of high uniformity and preparation method thereof | |
| CN106381546B (en) | A kind of high uniformity air bag polyester industrial fiber and preparation method thereof | |
| CN106319678B (en) | Porous super soft imitative hair polyester fiber of one kind and preparation method thereof | |
| CN106283261B (en) | Porous super soft super fine denier polyester fiber of one kind and preparation method thereof | |
| CN106149396B (en) | A kind of high uniformity Coated Fabrics 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 | |
| CN106319676B (en) | A kind of high uniformity activated polyester industrial filament and preparation method thereof | |
| CN106400167B (en) | Porous ultra-fine denier flat filament of one kind and preparation method thereof | |
| CN106400170B (en) | Porous super soft imitative numb polyester fiber of one kind and preparation method thereof | |
| CN106381549B (en) | A kind of porous super fine denier polyester fiber and preparation method thereof | |
| CN106350888B (en) | A kind of high uniformity platypelloid type polyester industrial fiber and preparation method thereof | |
| CN106397745B (en) | A kind of high uniformity polyester heavy caliber conveyer belt and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |