CN106381557A - High-uniformity polyester industrial yarn used for safety belt and production method thereof - Google Patents
High-uniformity polyester industrial yarn used for safety belt and production method thereof Download PDFInfo
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- CN106381557A CN106381557A CN201610777370.5A CN201610777370A CN106381557A CN 106381557 A CN106381557 A CN 106381557A CN 201610777370 A CN201610777370 A CN 201610777370A CN 106381557 A CN106381557 A CN 106381557A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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- 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
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- 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
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D4/00—Spinnerette packs; Cleaning thereof
- D01D4/02—Spinnerettes
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
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- 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
- D01D5/12—Stretch-spinning methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a high-uniformity polyester industrial yarn used for a safety belt and a production method thereof. The raw material of the high-uniformity polyester industrial yarn is modified polyester composed of a terephthalic acid chain segment, a glycol chain segment and a branched chain-containing dihydric alcohol chain segment. The production method is characterized in that terephthalic acid and branched chain-containing dihydric alcohol are subjected to an esterification reaction under catalysis of concentrated sulfuric acid to obtain dihydricalcohol terephthalate; then terephthalic acid and glycol are prepared for the esterification reaction to obtain ethylene terephthalate; finally ethylene terephthalate and dihydricalcohol terephthalate are stirred and mixed, under a catalyst and a stabilizing agent, the condensation polymerization reactions under a low vacuum phase and a high vacuum phase are carried out to prepare the modified polyester, and the modified polyester is subjected to metering, extrusion by a porous spinneret, cooling, oiling, stretching, thermoforming and reeling to prepare the high-uniformity polyester industrial yarn.
Description
Technical field
The invention belongs to polyester fiber technical field, it is related to a kind of high uniformity safety belt polyester industrial fiber and its preparation side
Method.
Background technology
Polyethylene terephthalate (PET or polyester fiber) fiber since the advent of the world, have fracture strength and
Elastic modelling quantity is high, and resilience is moderate, and thermal finalization is excellent, and heat-resisting light resistance is good and acid-fast alkali-proof corrosion resistance etc. is a series of excellent
Performance, and fabric have crease-resistant exempt to provide, the advantages of stiffness is good, be widely used in the fields such as clothes, home textile.
Pet Industrial Fiber is primarily referred to as mostly being applied to industry, national defence, medical treatment, environmental protection and most advanced branches of science each side
Face, is to have relatively special physicalchemical structure, performance and purposes, or has the chemical fibre of specific function, major embodiment
Being able to bear strong corrosion, low abrasion, high temperature resistant, radiation hardness, fire-retardant, fire-resistant, high voltage withstanding, high strength and modulus and plurality of medical work(
Energy.The PVC shelter cloth being produced as raw material using high-strength low-shrinkage polyester industrial filament yarn, has higher peel strength and tear is strong
Degree, makes shelter cloth be applied to various uses, flexible body advertising lamp box material, inflatable structure material, fluffy lid architectural fabrics sunshade account
Paulin etc..Based on high-strength low-shrinkage industrial yarn, textile material obtains in terms of the military supplies such as special protective garment, camouflage, covering, knapsack
To application.The application of Pet Industrial Fiber expands the whole competitiveness lifting driving application, no matter is mitigating again
The weight of condensation material, the durability of use and minimizing are keeped in repair, are raised all many-sides such as cost, and polyesters high-performance fiber is increasingly
Give play to its synthetic competitive advantages.Following many decades, the development of high-performance poly ester fiber not only has considerable in quantity
Progress, more obtains substantial effect in the expansion of application and the lifting of industrial chain whole competitiveness.
High intensity,The Main way that Pet Industrial Fiber is developed by dimensional stability, and affect fiber quality is poly-
Ester high molecular collection state structure, is mainly concerned with the active force between polyester molecule, the form of crystallization and structure, orientation structure
Deng, and the form crystallizing and structure are emphasis therein.Low-shrinkage high-strength PET industrial yarn, is the big class in polyester, due to
Its intensity is high, and percent thermal shrinkage is low, and impact resistance is excellent, and its fabric or the rubber made have good dimensional stability
And heat-resistant stability, impact load can be absorbed, and have the characteristics that polyamide fibre is soft, be therefore widely used field.
Low-shrinkage high-strength PET industrial yarn is mainly used in coated fabric and (lamp house cloth, tent, shelter cloth, billboard, puggaree, waterproof cloth, fills
Gas type swimming pool, roof drape, for building, agriculture use, aircushion vehicle, pneumatic boat etc.), canvas, soft water pipe, fire hose
Band, pitch tube, sewing thread, Industry thread, geotextile, filter cloth etc..
Have many parameters during melt spinning, these parameters determine fiberizing course and spin fiber structure and
Performance, production is exactly the fiber of desired properties is obtained by controlling these parameters.Experimental branch line all adopts side for a long time
As the type of cooling, energy resource consumption accounts for the significant portion of long filament production cost, with people to chemical fibre performance and quality for blowing
Require increasingly to improve, the exploitation of chemical-fibres filaments new product develops it is desirable to higher is cold to the fibre in differentiation direction of high added value
But blowing condition, then proposes ring blowing device.Ring blowing device not only possesses the uniform advantage of every synnema wind-engaging, Er Qieneng
Consumption is compared relatively low, effectively solves the wind energy loss problem that cross air blasting causes because blowing area is big.
In spinning process, although ring blowing has obvious advantage, but still the cooling of porous yarn cannot be solved well
Uneven problem：Because spun silk is after circular spinneret is extruded, by ring wind quenching, due to the circular spinneret number of turns relatively
Many lead to that the silk of innermost layer may be also uncolled after cooling in outermost silk so that ring blowing hardly enters innermost layer,
Thus the problems such as fiber number is irregular, and intensity is irregular in the silk of gained, cause follow-up to silk be processed further difficulty occurs.
Content of the invention
The technical problem to be solved in the present invention is for the deficiencies in the prior art, provides a kind of high uniformity safety belt with gathering
Ester industrial yarn and preparation method thereof, the raw material of high uniformity safety belt polyester industrial fiber of the present invention is modified poly ester, modified poly-
The dihydroxylic alcohols segment containing side chain, the modified high uniformity safety belt polyester work of modified polyester preparation is introduced in the strand of ester
Industry silk, under the conditions of uniform temperature, the increase width of the spatial joint clearance with polyester industrial fiber interior molecules interchain for the high uniformity safety belt
Degree is far longer than unbranched industrial yarn at equal temperature, and the melt viscosity of high uniformity safety belt polyester industrial fiber reduces,
Reduce processing temperature, reduce degradation rate, be conducive to processing.The high uniformity safety belt polyester industrial fiber of the other present invention
On porous spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and oval shaped arrangements refer to that the hole of spinneret orifice is centrally located at one heart
On ellipse, concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear；Higher cooling effect can be reached
Rate and preferable cooling effect.
A kind of high uniformity safety belt polyester industrial fiber, described high uniformity safety belt polyester industrial fiber is by modified poly-
Ester spinning after solid-phase tack producing obtains；The material of described high uniformity safety belt polyester industrial fiber is modified poly ester, described modification
Polyester is made up of terephthalic acid (TPA) segment, ethylene glycol segment and the dihydroxylic alcohols segment containing side chain, the described dihydroxylic alcohols chain containing side chain
Section refers to that side chain is located on one of dihydroxylic alcohols segment non-end group carbon and side chain is the linear carbon chain containing 5-10 carbon atom
Dihydroxylic alcohols segment；Fracture strength >=the 8.1cN/dtex of described high uniformity safety belt polyester industrial fiber, extension at break is
The percentage elongation 5.5 ± 0.5% of 14.0 ± 1.5%, 4.0cN/dtex load；Described high uniformity safety belt polyester industrial fiber exists
At 260～290 DEG C, melt viscosity declines 10-20%, line density deviation ratio≤1.0%, fracture strength CV value≤2.0%, fracture
Elongation CV value≤5.5%, described melt viscosity decline refers to modified poly ester and normal polyester in mutually synthermal melt viscosity
Contrast.
A kind of high uniformity safety belt polyester industrial fiber is modified poly ester, introduces and contain on modified poly ester macromolecular long-chain
The dihydroxylic alcohols segment of side chain, and the length of side chain and quantity are larger to the crystal property of modified poly ester and the impact of flow behavior,
The too short purpose not reaching polyester modification of branch lengths, length is oversize to cause new entanglement, affect its flow behavior, work as side chain
On one of dihydroxylic alcohols segment non-end group carbon and when side chain is the linear carbon chain containing 5-10 carbon atom, modified poly-
A kind of high uniformity safety belt polyester industrial fiber of ester preparation, under the conditions of uniform temperature, industrial yarn interior molecules interchain
The increasing degree of spatial joint clearance is far longer than unbranched industrial yarn at equal temperature, is conducive to industrial yarn melt viscosity to reduce,
It is easy to further process.
As preferred technical scheme：
A kind of high uniformity safety belt polyester industrial fiber as above, described high uniformity safety belt polyester industrial
Under the test condition for 177 DEG C × 10min × 0.05cN/dtex for the temperature, dry-hot shrinkage is 8.0 ± 1.5% to silk, network 6
±2；The number-average molecular weight of described modified poly ester is 15000-30000.
A kind of high uniformity safety belt polyester industrial fiber as above, the described dihydroxylic alcohols segment containing side chain is 2- penta
Base -1,3 propane diols segment, 2- hexyl -1,3 propane diols segment, 2- heptyl -1,3 propane diols segment, 2- octyl group -1,3 propane diols chain
Section, 2- nonyl -1,3 propane diols segment, 2- decyl -1,3 propane diols segment, 2- amyl group -1,4 butanediol segment, 2- hexyl -1,4
Butanediol segment, 2- heptyl -1,4 butanediol segment, 2- octyl group -1,4 butanediol segment, 2- nonyl -1,4 butanediol segment, 2-
Decyl -1,4 butanediol segment, 2- amyl group -1,5 pentanediol segment, 2- hexyl -1,5 pentanediol segment, 2- heptyl -1,5 pentanediol
Segment, 2- octyl group -1,5 pentanediol segment, 2- nonyl -1,5 pentanediol segment, 2- decyl -1,5 pentanediol segment, 2- amyl group -1,
6 hexylene glycol segments, 2- hexyl -1,6 hexylene glycol segment, 2- heptyl -1,6 hexylene glycol segment, 2- octyl group -1,6 hexylene glycol segment, 2-
One or more of nonyl -1,6 hexylene glycol segment or 2- decyl -1,6 hexylene glycol segment；The described dihydroxylic alcohols segment containing side chain with
The Mole percent ratio of ethylene glycol segment is 2～5%.
A kind of preparation method of high uniformity safety belt polyester industrial fiber of the present invention, by modified poly ester through solid phase polycondensation
Thickening, metering, porous spinneret are extruded, cool down, oiling, stretching, thermal finalization and winding, prepared high uniformity safety belt polyester
Industrial yarn；
On described porous spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and described oval shaped arrangements refer to spinneret orifice
Hole be centrally located on concentration ellipse, described concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear；
The preparation process of modified poly ester comprises the following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Terephthalic acid (TPA) is made into after slurry with the dihydroxylic alcohols containing side chain, under the catalytic action of the concentrated sulfuric acid, is esterified
Reaction, obtains terephthalic acid (TPA) binary alcohol esters；It is non-that the described dihydroxylic alcohols containing side chain is that side chain is located at one of dihydroxylic alcohols segment
On end group carbon and side chain is the dihydroxylic alcohols of the linear carbon chain containing 5-10 carbon atom；
For the dihydroxylic alcohols containing side chain, its side chain is alkyl, is electron withdraw group, in the presence of side chain, makes strand
Spatial volume increases, and solvation diminishes, and in dihydroxylic alcohols, proton is difficult to dissociate so that containing dihydroxylic alcohols and the terephthaldehyde of side chain
The reactivity of acid is less than ethylene glycol, according to the mixing of same ethylene glycol and terephthaldehyde's acid reaction, can cause the binary containing side chain
Alcohol reaction is imperfect, thus ratio in polyester macromolecule for the dihydroxylic alcohols containing side chain for the impact, and then affect the performance of polyester.This
Using first the dihydroxylic alcohols containing side chain being carried out esterification with terephthalic acid (TPA) under the catalytic action of sulfuric acid, its product exists for invention
Ethylene glycol and p phthalic acid esterification add it is ensured that containing the stability of the dihydroxylic alcohols proportioning of side chain after terminating.
(2) preparation of ethylene glycol terephthalate：
Terephthalic acid (TPA) and ethylene glycol are made into after slurry, carry out esterification, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), stir
Mix mixing, in the presence of catalyst and stabilizer, under conditions of negative pressure, carry out successively the low vacuum stage polycondensation reaction and
The polycondensation reaction of high vacuum stage of Fig, prepared modified poly ester.
A kind of preparation method of high uniformity safety belt polyester industrial fiber as above, described modified poly ester preparation
Concretely comprise the following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Terephthalic acid (TPA) and the dihydroxylic alcohols containing side chain are made into slurry and add in reactor, in the catalytic action of the concentrated sulfuric acid
Under, carry out esterification, esterification compressive reaction in nitrogen atmosphere, moulding pressure is normal pressure～0.3MPa, temperature is 180
～240 DEG C, be esterification terminal when the water quantity of distillate in esterification reaches more than the 90% of theoretical value；Obtain to benzene two
Formic acid binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Terephthalic acid (TPA) and ethylene glycol are made into after slurry and add in reactor, carry out esterification, esterification is in nitrogen
Atmosphere encloses middle compressive reaction, and moulding pressure is normal pressure～0.3MPa, and temperature is 250～260 DEG C, when the water in esterification distillates
It is esterification terminal that amount reaches during more than the 90% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), stir
Mix mixing 15-20 minute, in the presence of catalyst and stabilizer, the polycondensation starting the low vacuum stage under conditions of negative pressure is anti-
Should, this staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, and at 260～270 DEG C, the reaction time is temperature control
30～50 minutes；Then proceed to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure and be less than
100Pa, reaction temperature controls at 275～280 DEG C, 50～90 minutes reaction time, prepared modified poly ester；
Again modified poly ester is obtained Modified polyester chips through pelletizing, obtained polyester slice is viscosified by solid phase polycondensation, makes
The inherent viscosity of polyester slice brings up to 1.0～1.2dL/g, as high viscous section；Again through metering, porous spinneret extrusion, cold
But, oil, stretch, thermal finalization and winding, prepared high uniformity safety belt polyester industrial fiber；
Spinning main technologic parameters are：The temperature of described extrusion is 290～310 DEG C；The wind-warm syndrome of described cooling is 20～30
℃；
Described stretching, heat setting process parameter are：GR-1 speed 440～650m/min；75～85 DEG C of temperature；GR-2 speed
460～680m/min；90～100 DEG C of temperature；GR-3 speed 1900～2400m/min；125～140 DEG C of temperature；GR-4 speed
2700～3600m/min；220～250 DEG C of temperature；GR-5 speed 2500～3600m/min；150～170 DEG C of temperature；Described volume
Around speed be 2500～3600m/min.
A kind of preparation method of high uniformity safety belt polyester industrial fiber as above, in described step (1), to benzene
Dioctyl phthalate is 1 with the mol ratio of the dihydroxylic alcohols containing side chain:1.3-1.5；Concentrated sulfuric acid addition is the 0.3- of terephthalic acid (TPA) weight
0.5%；The concentration of the described concentrated sulfuric acid is 50-60wt%；In described step (2), terephthalic acid (TPA) with the mol ratio of ethylene glycol is
1:1.2～2.0；In described step (3), the Mole percent of described terephthalic acid (TPA) binary alcohol esters and ethylene glycol terephthalate
Ratio is 2～5%；Described catalyst is antimony oxide, antimony glycol or antimony acetate, and catalyst charge is terephthalic acid (TPA)
The 0.01%～0.05% of gross weight；Described stabilizer is triphenyl phosphate, trimethyl phosphate or Trimethyl phosphite, stabilizer
Addition is the 0.01%～0.05% of described terephthalic acid (TPA) gross weight.
A kind of preparation method of high uniformity safety belt polyester industrial fiber as above, the described dihydroxylic alcohols containing side chain
For 2- amyl group -1,3 propane diols, 2- hexyl -1,3 propane diols, 2- heptyl -1,3 propane diols, 2- octyl group -1,3 propane diols, 2- nonyl -
1,3 propane diols, 2- decyl -1,3 propane diols, 2- amyl group -1,4 butanediol, 2- hexyl -1,4 butanediol, 2- heptyl -1,4 fourth two
Alcohol, 2- octyl group -1,4 butanediol, 2- nonyl -1,4 butanediol, 2- decyl -1,4 butanediol, 2- amyl group -1,5 pentanediol, 2- are own
Base -1,5 pentanediol, 2- heptyl -1,5 pentanediol, 2- octyl group -1,5 pentanediol, 2- nonyl -1,5 pentanediol, 2- decyl -1,5 penta
Glycol, 2- amyl group -1,6 hexylene glycols, 2- hexyl -1,6 hexylene glycols, 2- heptyl -1,6 hexylene glycols, 2- octyl group -1,6 hexylene glycols, 2- nonyl
One or more of base -1,6 hexylene glycol or 2- decyl -1,6 hexylene glycol.
A kind of preparation method of high uniformity safety belt polyester industrial fiber as above, described porous spinneret is circle
Shape spinneret or elliptical spinneret plate；The diameter of described circle spinneret is more than with the difference of the oval maximum long axis length of series
10mm, described elliptical spinneret plate is more than 10mm with the difference of the oval maximum long axis length of series.
A kind of preparation method of high uniformity safety belt polyester industrial fiber as above, described porous spinneret sprays
Silk hole be arranged as that major axis and/or short axle are symmetrical, the guide hole diameter that the spacing of adjacent spinneret orifice is more than or equal to spinneret orifice adds
1.5mm；Oval major axis is 1.3～1.8 with the ratio of minor axis length.
When the effective area phase of spinneret is simultaneously as the girth of ellipse is more than circular girth, spinneret orifice is oval
The number of plies of arrangement is less than the number of plies of circular arrangement, and the hole count of spinneret orifice oval shaped arrangements is more than the hole count of circular arrangement, therefore, spray
Silk hole oval shaped arrangements are conducive to the cooling of ring blowing, improve the cooling effectiveness of ring blowing, the fibre property of preparation is also more excellent
Good.Major axis is closer to 1 with the ratio of minor axis length, and ellipse is more similar to justify, and the difference of cooling effectiveness and cooling effect is little；
When the ratio of major axis and minor axis length is 1.3, cooling effect significantly improves, and individual pen hole count is corresponding to increase by 16%；Major axis and short axle
When the ratio of length is 1.8, cooling effect improves larger, the corresponding increase by 33% of individual pen hole count, in the case of identical hole count, the present invention
Oval shaped arrangements reduce than the number of turns of conventional concentric circle best-fit it is easy to cooling wind thoroughly, makes the fiber cooling condition of Internal and external cycle
Evenly；When the ratio of major axis and minor axis length is more than 1.8, ellipse is partial to form flat shape, is difficult to punch, simultaneously cold
But effect no longer raises.Therefore, the oval major axis of series and the ratio of minor axis length are 1.3～1.8, can reach higher cold
But efficiency and preferable cooling effect.
A kind of preparation method of high uniformity safety belt polyester industrial fiber as above, the guide hole of described spinneret orifice is straight
Footpath is 1.5～2.5mm；The spinneret hole count of described spinneret is more than or equal to 192, the cross section shape of the spinneret orifice of described spinneret
Shape is circle, square, rhombus, yi word pattern, triangular form, trilobal cross, hollow type or platypelloid type
The principle of the present invention is：
The raw material of the high uniformity safety belt polyester industrial fiber of the present invention is modified poly ester, contains in modified poly ester macromolecular
The dihydroxylic alcohols segment containing side chain having, when temperature is higher than vitrification point, side chain, prior to backbone motion, makes the increasing of free volume
Plus amplitude is far longer than the characteristic of unbranched polyester macromolecule chain, the increase of free volume improves molecule and enters polyester
Internal degree.The free volume of the industrial yarn of modified polyester preparation is far longer than unbranched industrial yarn at equal temperature,
Advantageously reduce its melt viscosity.
On the spinneret of the present invention, the arrangement mode of spinneret orifice is oval shaped arrangements, when the effective area of spinneret is identical,
The number of plies of spinneret orifice oval shaped arrangements is less than the number of plies of circular arrangement, and ring blowing is easier to blow through dynamic analysis of spinning, dynamic analysis of spinning
More preferably, the industrial yarn of preparation is also more excellent for cooling effect.When the effective area of spinneret is identical, spinneret orifice oval shaped arrangements
Hole count is more than the hole count of circular arrangement, and oval shaped arrangements are capable of greatly cooling down, and significantly improve cooling effectiveness.
Beneficial effect：
The raw material of the high uniformity safety belt polyester industrial fiber of gained of the present invention is modified poly ester, modified poly ester macromolecular
In the dihydroxylic alcohols segment containing side chain that contains, when temperature is higher than vitrification point, side chain, prior to backbone motion, makes free volume
Increasing degree be far longer than the characteristic of unbranched polyester macromolecule chain, the increase of free volume advantageously reduces melt and glues
Degree, improves its processing characteristics.
The raw material of the high uniformity safety belt polyester industrial fiber of gained of the present invention is modified poly ester, the dihydroxylic alcohols containing side chain
The introducing of segment to the structural regularity of modified poly ester there is no big destruction, maintain the premium properties of polyester fiber.
On the high uniformity safety belt polyester industrial fiber spinneret of the present invention, the arrangement mode of spinneret orifice is oval row
Row, 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 more held
Easily blow through dynamic analysis of spinning, more preferably, the fibre property of preparation is also more excellent for the cooling effect of dynamic analysis of spinning.
On the high uniformity safety belt polyester industrial fiber spinneret of the present invention, the arrangement mode of spinneret orifice is oval row
Row, when the effective area of spinneret is identical, the hole count of spinneret orifice oval shaped arrangements is more than the hole count of circular arrangement, oval shaped arrangements
It is capable of greatly cooling down, significantly improve cooling effectiveness.
Brief description
Fig. 1 is the oval shaped arrangements figure of 374 spinneret orifices, and the aperture of spinneret orifice is 2.0mm, the length of transverse and short axle
Degree ratio is 1.3；
Fig. 2 is the circular arrangement figure of 370 spinneret orifices, and the aperture of spinneret orifice is 2.0mm；
Fig. 3 is the oval shaped arrangements figure of 382 spinneret orifices, and the aperture of spinneret orifice is 2.0mm, the length of transverse and short axle
Degree ratio is 1.6.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate this
Bright rather than limit the scope of the present invention.In addition, it is to be understood that after having read the content of present invention instruction, art technology
Personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Fixed scope.
Embodiment 1
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.3 terephthalic acid (TPA) and 2- amyl group -1,3 propane diols are made into slurry and add in reactor,
Concentration is 50wt%, and addition is under the catalytic action of 0.3% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure is normal pressure, and temperature is 180 DEG C, when the water in esterification distillates
It is esterification terminal that amount reaches during the 90% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.2 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure is normal pressure, and temperature is 250 DEG C, when the water in esterification distillates
It is esterification terminal that amount reaches during the 90% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right
Phthalic acid binary alcohol esters are 2% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 15 minutes is adding
Measure for terephthalic acid (TPA) gross weight 0.01% the catalytic antimony trioxide and addition be terephthalic acid (TPA) gross weight
Under conditions of negative pressure, in the presence of 0.01% stabilizer triphenyl phosphate, start the polycondensation reaction in low vacuum stage, this rank
It is 500Pa that section pressure is steadily evacuated to absolute pressure by normal pressure, and at 260 DEG C, the reaction time is 30 minutes to temperature control；Then proceed to
Vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 100Pa, and reaction temperature controls
275 DEG C, 50 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of modified poly ester is 15000, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- penta
Base -1,3 propane diols segment compositions, the dihydroxylic alcohols segment containing side chain is 2% with the Mole percent ratio of ethylene glycol segment.
Table 1：Embodiment 2-12 important technological parameters
Embodiment 2
, with embodiment 1, wherein main technical parameter is referring to table 1 for the preparation process of modified poly ester；It is right to add in step (3)
After phthalic acid binary alcohol esters, stirring mixing 16 minutes, addition for terephthalic acid (TPA) gross weight 0.011% catalyst
In the presence of antimony oxide and addition are 0.02% stabilizer triphenyl phosphate of terephthalic acid (TPA) gross weight, in negative pressure
Under conditions of start the polycondensation reaction in low vacuum stage, this staged pressure is steadily evacuated to absolute pressure 490Pa, temperature control by normal pressure
At 262 DEG C, the reaction time is 31 minutes to system；Then proceed to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure
It is down to absolute pressure 90Pa, reaction temperature controls at 276 DEG C, 51 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of modified poly ester is 16000, and modified poly ester is own by terephthalic acid (TPA) segment, ethylene glycol segment and 2-
Base -1,3 propane diols segment compositions, 2- hexyl -1,3 propane diols segments are 2.1% with the Mole percent ratio of ethylene glycol segment.
Embodiment 3
, with embodiment 1, wherein main technical parameter is referring to table 1 for the preparation process of modified poly ester；It is right to add in step (3)
After phthalic acid binary alcohol esters, stirring mixing 16 minutes, addition for terephthalic acid (TPA) gross weight 0.03% catalyst
In the presence of antimony oxide and addition are 0.02% stabilizer triphenyl phosphate of terephthalic acid (TPA) gross weight, in negative pressure
Under conditions of start the polycondensation reaction in low vacuum stage, this staged pressure is steadily evacuated to absolute pressure 498Pa, temperature control by normal pressure
At 263 DEG C, the reaction time is 32 minutes to system；Then proceed to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure
It is down to absolute pressure 90Pa, reaction temperature controls at 277 DEG C, 57 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of modified poly ester is 15900, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- heptan
Base -1,3 propane diols segment compositions, 2- heptyl -1,3 propane diols segments are 2.2% with the Mole percent ratio of ethylene glycol segment.
Embodiment 4
, with embodiment 1, wherein main technical parameter is referring to table 1 for the preparation process of wherein modified poly ester；Add in step (3)
After entering terephthalic acid (TPA) binary alcohol esters, stirring mixing 17 minutes, addition for terephthalic acid (TPA) gross weight 0.033% urge
In the presence of agent antimony oxide and addition are 0.023% stabilizer triphenyl phosphate of terephthalic acid (TPA) gross weight,
Start the polycondensation reaction in low vacuum stage under conditions of negative pressure, this staged pressure is steadily evacuated to absolute pressure by normal pressure and is
497Pa, at 264 DEG C, the reaction time is 33 minutes to temperature control；Then proceed to vacuumize, the polycondensation carrying out high vacuum stage of Fig is anti-
Should, making reaction pressure be down to absolute pressure is 80Pa, and reaction temperature controls at 278 DEG C, 58 minutes reaction time, is obtained modified poly-
Ester.
The number-average molecular weight of modified poly ester is 15800, and modified poly ester is pungent by terephthalic acid (TPA) segment, ethylene glycol segment and 2-
Base -1,3 propane diols segment compositions, 2- octyl group -1,3 propane diols segments are 2.3% with the Mole percent ratio of ethylene glycol segment.
Embodiment 5
The preparation process of the preparation method of the modified poly ester of embodiment 5, wherein modified poly ester with embodiment 1, wherein mainly
Technical parameter referring to table 1；After step (3) adds terephthalic acid (TPA) binary alcohol esters, stirring mixing 17 minutes, in addition be
The catalytic antimony trioxide of the 0.034% of terephthalic acid (TPA) gross weight and addition are terephthalic acid (TPA) gross weight
Under conditions of negative pressure, in the presence of 0.024% stabilizer triphenyl phosphate, start the polycondensation reaction in low vacuum stage, this rank
Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and at 265 DEG C, the reaction time is 34 minutes to temperature control；Then proceed to take out
Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 80Pa, and reaction temperature controls 277
DEG C, 59 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of modified poly ester is 15900, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- nonyl
Base -1,3 propane diols segment compositions, 2- nonyl -1,3 propane diols segments are 2.4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 6
The preparation process of the preparation method of the modified poly ester of embodiment 6, wherein modified poly ester with embodiment 1, wherein mainly
Technical parameter referring to table 1；After step (3) adds terephthalic acid (TPA) binary alcohol esters, stirring mixing 18 minutes, in addition be
The catalytic antimony trioxide of the 0.035% of terephthalic acid (TPA) gross weight and addition are terephthalic acid (TPA) gross weight
Under conditions of negative pressure, in the presence of 0.025% stabilizer triphenyl phosphate, start the polycondensation reaction in low vacuum stage, this rank
Section pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 266 DEG C, the reaction time is 35 minutes to temperature control；Then proceed to take out
Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 70Pa, and reaction temperature controls 278
DEG C, 60 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of modified poly ester is 16000, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and the 2- last of the ten Heavenly stems
Base -1,3 propane diols segment compositions, 2- decyl -1,3 propane diols segments are 2.5% with the Mole percent ratio of ethylene glycol segment.
Embodiment 7
The preparation process of the preparation method of the modified poly ester of embodiment 7, wherein modified poly ester with embodiment 1, wherein mainly
Technical parameter referring to table 1；After step (3) adds terephthalic acid (TPA) binary alcohol esters, stirring mixing 19 minutes, in addition be
The catalytic antimony trioxide of the 0.036% of terephthalic acid (TPA) gross weight and addition are terephthalic acid (TPA) gross weight
Under conditions of negative pressure, in the presence of 0.025% stabilizer triphenyl phosphate, start the polycondensation reaction in low vacuum stage, this rank
Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and at 267 DEG C, the reaction time is 36 minutes to temperature control；Then proceed to take out
Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 70Pa, and reaction temperature controls 278
DEG C, 61 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of modified poly ester is 16000, and the number-average molecular weight of modified poly ester is 16000, and modified poly ester is by right
Phthalic acid segment, ethylene glycol segment and 2- amyl group-Isosorbide-5-Nitrae butanediol segment composition, 2- amyl group-Isosorbide-5-Nitrae butanediol segment and second two
The Mole percent ratio of alcohol segment is 2.6%.
Embodiment 8
The preparation process of the preparation method of the modified poly ester of embodiment 8, wherein modified poly ester with embodiment 1, wherein mainly
Technical parameter referring to table 1；After step (3) adds terephthalic acid (TPA) binary alcohol esters, stirring mixing 19 minutes, in addition be
The catalytic antimony trioxide of the 0.036% of terephthalic acid (TPA) gross weight and addition are terephthalic acid (TPA) gross weight
Under conditions of negative pressure, in the presence of 0.025% stabilizer triphenyl phosphate, start the polycondensation reaction in low vacuum stage, this rank
Section pressure is steadily evacuated to absolute pressure 496Pa by normal pressure, and at 267 DEG C, the reaction time is 36 minutes to temperature control；Then proceed to take out
Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 70Pa, and reaction temperature controls 278
DEG C, 61 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of modified poly ester is 17000, and modified poly ester is own by terephthalic acid (TPA) segment, ethylene glycol segment and 2-
Base-Isosorbide-5-Nitrae butanediol segment composition, 2- hexyl-Isosorbide-5-Nitrae butanediol segment is 2.7% with the Mole percent ratio of ethylene glycol segment.
Embodiment 9
The preparation process of the preparation method of the modified poly ester of embodiment 9, wherein modified poly ester with embodiment 1, wherein mainly
Technical parameter referring to table 1；After step (3) adds terephthalic acid (TPA) binary alcohol esters, stirring mixing 16 minutes, in addition be
The catalyst glycol antimony of the 0.04% of terephthalic acid (TPA) gross weight and addition are the 0.026% of terephthalic acid (TPA) gross weight
In the presence of stabilizer trimethyl phosphate, under conditions of negative pressure start the low vacuum stage polycondensation reaction, this staged pressure by
Normal pressure is steadily evacuated to absolute pressure 497Pa, and at 268 DEG C, the reaction time is 38 minutes to temperature control；Then proceed to vacuumize, enter
The polycondensation reaction of row high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 60Pa, and reaction temperature controls at 279 DEG C, reaction
62 minutes time, prepared modified poly ester.
The number-average molecular weight of modified poly ester is 17000, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- heptan
Base-Isosorbide-5-Nitrae butanediol segment composition, 2- heptyl-Isosorbide-5-Nitrae butanediol segment is 2.8% with the Mole percent ratio of ethylene glycol segment.
Embodiment 10
The preparation process of the preparation method of the modified poly ester of embodiment 10, wherein modified poly ester with embodiment 1, wherein mainly
Technical parameter referring to table 1；After step (3) adds terephthalic acid (TPA) binary alcohol esters, stirring mixing 17 minutes, in addition be
The catalyst glycol antimony of the 0.03% of terephthalic acid (TPA) gross weight and addition are the 0.027% of terephthalic acid (TPA) gross weight
In the presence of stabilizer trimethyl phosphate, under conditions of negative pressure start the low vacuum stage polycondensation reaction, this staged pressure by
Normal pressure is steadily evacuated to absolute pressure 498Pa, and at 269 DEG C, the reaction time is 39 minutes to temperature control；Then proceed to vacuumize, enter
The polycondensation reaction of row high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 60Pa, and reaction temperature controls at 278 DEG C, reaction
64 minutes time, prepared modified poly ester.
The number-average molecular weight of modified poly ester is 17000, and modified poly ester is pungent by terephthalic acid (TPA) segment, ethylene glycol segment and 2-
Base-Isosorbide-5-Nitrae butanediol segment composition, 2- octyl group-Isosorbide-5-Nitrae butanediol segment is 3% with the Mole percent ratio of ethylene glycol segment.
Embodiment 11
The preparation process of the preparation method of the modified poly ester of embodiment 11, wherein modified poly ester with embodiment 1, wherein mainly
Technical parameter referring to table 1；After step (3) adds terephthalic acid (TPA) binary alcohol esters, stirring mixing 18 minutes, in addition be
The catalyst glycol antimony of the 0.04% of terephthalic acid (TPA) gross weight and addition are the 0.03% of terephthalic acid (TPA) gross weight
In the presence of stabilizer trimethyl phosphate, under conditions of negative pressure start the low vacuum stage polycondensation reaction, this staged pressure by
Normal pressure is steadily evacuated to absolute pressure 497Pa, and at 260 DEG C, the reaction time is 40 minutes to temperature control；Then proceed to vacuumize, enter
The polycondensation reaction of row high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 60Pa, and reaction temperature controls at 277 DEG C, reaction
63 minutes time, prepared modified poly ester.
The number-average molecular weight of modified poly ester is 18000, and modified poly ester is by terephthalic acid (TPA) segment, ethylene glycol segment and 2- nonyl
Base-Isosorbide-5-Nitrae butanediol segment composition, 2- nonyl-Isosorbide-5-Nitrae butanediol segment is 4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 12
The preparation process of the preparation method of the modified poly ester of embodiment 12, wherein modified poly ester with embodiment 1, wherein mainly
Technical parameter referring to table 1；After step (3) adds terephthalic acid (TPA) binary alcohol esters, stirring mixing 18 minutes, in addition be
The catalyst acetic acid antimony of the 0.038% of terephthalic acid (TPA) weight and addition are the stabilizer of the 0.03% of terephthalic acid (TPA) weight
Under conditions of negative pressure, in the presence of Trimethyl phosphite, start the polycondensation reaction in low vacuum stage, this staged pressure is by normal pressure
Steadily it is evacuated to absolute pressure 497Pa, at 265 DEG C, the reaction time is 42 minutes to temperature control；Then proceed to vacuumize, carry out height
The polycondensation reaction of vacuum stages, making reaction pressure be down to absolute pressure is 40Pa, and reaction temperature controls at 277 DEG C, the reaction time
70 minutes, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 26000, by terephthalic acid (TPA) segment, ethylene glycol segment and the 2- last of the ten Heavenly stems
Base-Isosorbide-5-Nitrae butanediol segment composition, 2- decyl-Isosorbide-5-Nitrae butanediol segment is 4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 13
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.5 terephthalic acid (TPA) and 2- decyl -1,6 hexylene glycols are made into slurry and add in reactor,
Concentration is 60wt%, and addition is under the catalytic action of 0.5% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.3MPa, and temperature is 240 DEG C, when the water in esterification evaporates
It is esterification terminal that output reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:2.0 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.3MPa, and temperature is 260 DEG C, when the water in esterification evaporates
It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right
Phthalic acid binary alcohol esters are 5% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 20 minutes is adding
Measure for terephthalic acid (TPA) weight 0.05% catalyst acetic acid antimony and addition be terephthalic acid (TPA) weight 0.05% steady
In the presence of determining agent Trimethyl phosphite, under conditions of negative pressure start the low vacuum stage polycondensation reaction, this staged pressure by
It is 450Pa that normal pressure is steadily evacuated to absolute pressure, and at 270 DEG C, the reaction time is 50 minutes to temperature control；Then proceed to vacuumize,
Carry out the polycondensation reaction of high vacuum stage of Fig, making reaction pressure be down to absolute pressure is 30Pa, and reaction temperature controls at 280 DEG C, instead
90 minutes between seasonable, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 30000, by terephthalic acid (TPA) segment, ethylene glycol segment and the 2- last of the ten Heavenly stems
Base -1,6 hexylene glycol segment compositions, 2- decyl -1,6 hexylene glycol segments are 5% with the Mole percent ratio of ethylene glycol segment.
Embodiment 14
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.47 terephthalic acid (TPA) and 2- nonyl -1,6 hexylene glycols are made into slurry and add in reactor,
Concentration is 60wt%, and addition is under the catalytic action of 0.47% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 220 DEG C, when the water in esterification evaporates
It is esterification terminal that output reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.8 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27MPa, and temperature is 258 DEG C, when the water in esterification evaporates
It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right
Phthalic acid binary alcohol esters are 4% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding
Measure for terephthalic acid (TPA) weight 0.04% catalyst glycol antimony and addition be the 0.04% of terephthalic acid (TPA) weight
In the presence of stabilizer trimethyl phosphate, under conditions of negative pressure start the low vacuum stage polycondensation reaction, this staged pressure by
Normal pressure is steadily evacuated to absolute pressure 460Pa, and at 263 DEG C, the reaction time is 47 minutes to temperature control；Then proceed to vacuumize, enter
The polycondensation reaction of row high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 278 DEG C, during reaction
Between 85 minutes, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 28000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- nonyl
Base -1,6 hexylene glycol segment compositions, 2- nonyl -1,6 hexylene glycol segments are 4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 15
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.46 terephthalic acid (TPA) and 2- octyl group -1,6 hexylene glycols are made into slurry and add in reactor,
Concentration is 60wt%, and addition is under the catalytic action of 0.49% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 233 DEG C, when the water in esterification evaporates
It is esterification terminal that output reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.8 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 259 DEG C, when the water in esterification evaporates
It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right
Phthalic acid binary alcohol esters are 4.5% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 19 minutes is adding
Entering 0.044% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under conditions of negative pressure, in the presence of 0.046% stabilizer triphenyl phosphate, start the polycondensation reaction in low vacuum stage, this rank
Section pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 269 DEG C, the reaction time is 48 minutes to temperature control；Then proceed to take out
Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 279 DEG C,
87 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 29000, pungent by terephthalic acid (TPA) segment, ethylene glycol segment and 2-
Base -1,6 hexylene glycol segment compositions, 2- octyl group -1,6 hexylene glycol segments are 4.5% with the Mole percent ratio of ethylene glycol segment.
Embodiment 16
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.49 terephthalic acid (TPA) and 2- heptyl -1,6 hexylene glycols are made into slurry and add in reactor,
Concentration is 60wt%, and addition is under the catalytic action of 0.48% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 230 DEG C, when the water in esterification evaporates
It is esterification terminal that output reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.8 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 258 DEG C, when the water in esterification evaporates
It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right
Phthalic acid binary alcohol esters are 4.7% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 19 minutes is adding
Entering 0.048% catalyst glycol antimony that amount is terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under conditions of negative pressure, in the presence of 0.047% stabilizer triphenyl phosphate, start the polycondensation reaction in low vacuum stage, this rank
Section pressure is steadily evacuated to absolute pressure 460Pa by normal pressure, and at 267 DEG C, the reaction time is 48 minutes to temperature control；Then proceed to take out
Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 279 DEG C,
83 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 27000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- heptan
Base -1,6 hexylene glycol segment compositions, 2- heptyl -1,6 hexylene glycol segments are 4.7% with the Mole percent ratio of ethylene glycol segment.
Embodiment 17
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.467 terephthalic acid (TPA) and 2- hexyl -1,6 hexylene glycols are made into slurry and add in reactor,
It is 60wt% in concentration, addition is under the catalytic action of 0.47% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification anti-
Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27MPa, and temperature is 236 DEG C, when in esterification
It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.89 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification anti-
Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 258 DEG C, when in esterification
It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right
Phthalic acid binary alcohol esters are 4.3% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding
Entering 0.04% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under conditions of negative pressure, in the presence of 0.041% stabilizer Trimethyl phosphite, start the polycondensation reaction in low vacuum stage, should
Staged pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 268 DEG C, the reaction time is 48 minutes to temperature control；Then proceed to
Vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 40Pa, reaction temperature controls 278
DEG C, 85 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 29000, own by terephthalic acid (TPA) segment, ethylene glycol segment and 2-
Base -1,6 hexylene glycol segment compositions, 2- hexyl -1,6 hexylene glycol segments are 4.3% with the Mole percent ratio of ethylene glycol segment.
Embodiment 18
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.48 terephthalic acid (TPA) and 2- amyl group -1,6 hexylene glycols are made into slurry and add in reactor,
Concentration is 55wt%, and addition is under the catalytic action of 0.46% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 230 DEG C, when the water in esterification evaporates
It is esterification terminal that output reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.88 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification anti-
Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 256 DEG C, when in esterification
It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right
Phthalic acid binary alcohol esters are 4.7% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding
Entering 0.047% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under conditions of negative pressure, in the presence of 0.047% stabilizer triphenyl phosphate, start the polycondensation reaction in low vacuum stage, this rank
Section pressure is steadily evacuated to absolute pressure 480Pa by normal pressure, and at 265 DEG C, the reaction time is 47 minutes to temperature control；Then proceed to take out
Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 279 DEG C,
85 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 28000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- penta
Base -1,6 hexylene glycol segment compositions, 2- amyl group -1,6 hexylene glycol segments are 4.7% with the Mole percent ratio of ethylene glycol segment.
Embodiment 19
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.46 terephthalic acid (TPA) and 2- decyl -1,5 pentanediols are made into slurry and add in reactor,
Concentration is 55wt%, and addition is under the catalytic action of 0.47% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 238 DEG C, when the water in esterification evaporates
It is esterification terminal that output reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.9 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 259 DEG C, when the water in esterification evaporates
It is esterification terminal that output reaches during more than the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right
Phthalic acid binary alcohol esters are 4.7% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 19 minutes is adding
Entering the 0.046% catalyst acetic acid antimony that amount is terephthalic acid (TPA) weight and addition is the 0.048% of terephthalic acid (TPA) weight
Stabilizer Trimethyl phosphite in the presence of, under conditions of negative pressure start the low vacuum stage polycondensation reaction, this stage press
It is 446Pa that power is steadily evacuated to absolute pressure by normal pressure, and at 267 DEG C, the reaction time is 49 minutes to temperature control；Then proceed to take out very
Sky, carries out the polycondensation reaction of high vacuum stage of Fig, and making reaction pressure be down to absolute pressure is 40Pa, and reaction temperature controls at 278 DEG C,
87 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment and the 2- last of the ten Heavenly stems
Base -1,5 pentanediol segment compositions, 2- decyl -1,5 pentanediol segments are 4.7% with the Mole percent ratio of ethylene glycol segment.
Embodiment 20
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.46 terephthalic acid (TPA) and 2- nonyl -1,5 pentanediols are made into slurry and add in reactor,
Concentration is 60wt%, and addition is under the catalytic action of 0.46% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.26MPa, and temperature is 221 DEG C, when the water in esterification evaporates
It is esterification terminal that output reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.89 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification anti-
Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.25MPa, and temperature is 259 DEG C, when in esterification
It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right
Phthalic acid binary alcohol esters are 4.1% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding
Entering 0.041% catalyst glycol antimony that amount is terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under conditions of negative pressure, in the presence of 0.042% stabilizer trimethyl phosphate, start the polycondensation reaction in low vacuum stage, this rank
Section pressure is steadily evacuated to absolute pressure 460Pa by normal pressure, and at 265 DEG C, the reaction time is 47 minutes to temperature control；Then proceed to take out
Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 278 DEG C,
85 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 28000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- nonyl
Base -1,5 pentanediol segment compositions, 2- nonyl -1,5 pentanediol segments are 4.1% with the Mole percent ratio of ethylene glycol segment.
Embodiment 21
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.43 terephthalic acid (TPA) and 2- octyl group -1,5 pentanediols are made into slurry and add in reactor,
Concentration is 60wt%, and addition is under the catalytic action of 0.47% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27MPa, and temperature is 235 DEG C, when the water in esterification evaporates
It is esterification terminal that output reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.78 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification anti-
Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.26MPa, and temperature is 255 DEG C, when in esterification
It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right
Phthalic acid binary alcohol esters are 4.3% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 17 minutes is adding
Entering 0.043% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under conditions of negative pressure, in the presence of 0.049% stabilizer triphenyl phosphate, start the polycondensation reaction in low vacuum stage, this rank
Section pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 268 DEG C, the reaction time is 46 minutes to temperature control；Then proceed to take out
Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 40Pa, and reaction temperature controls at 275 DEG C,
85 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 28000, pungent by terephthalic acid (TPA) segment, ethylene glycol segment and 2-
Base -1,5 pentanediol segment compositions, 2- octyl group -1,5 pentanediol segments are 4.3% with the Mole percent ratio of ethylene glycol segment.
Embodiment 22
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.43 terephthalic acid (TPA) and 2- heptyl -1,5 pentanediols are made into slurry and add in reactor,
Concentration is 55wt%, and addition is under the catalytic action of 0.45% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.29MPa, and temperature is 235 DEG C, when the water in esterification evaporates
It is esterification terminal that output reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.87 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification anti-
Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27MPa, and temperature is 255 DEG C, when in esterification
It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right
Phthalic acid binary alcohol esters are 4.6% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding
Entering 0.047% catalyst glycol antimony that amount is terephthalic acid (TPA) weight and addition is the 0.04% of terephthalic acid (TPA) weight
Stabilizer triphenyl phosphate in the presence of, under conditions of negative pressure start the low vacuum stage polycondensation reaction, this staged pressure
Absolute pressure 470Pa is steadily evacuated to by normal pressure, at 268 DEG C, the reaction time is 45 minutes to temperature control；Then proceed to vacuumize,
Carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 40Pa, reaction temperature controls at 279 DEG C, reaction
83 minutes time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- heptan
Base -1,5 pentanediol segment compositions, 2- heptyl -1,5 pentanediol segments are 4.6% with the Mole percent ratio of ethylene glycol segment.
Embodiment 23
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.457 terephthalic acid (TPA) and 2- hexyl -1,5 pentanediols are made into slurry and add in reactor,
It is 55% in concentration, addition is under the catalytic action of 0.46% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 239 DEG C, when the water in esterification evaporates
It is esterification terminal that output reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.81 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification anti-
Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27MPa, and temperature is 255 DEG C, when in esterification
It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right
Phthalic acid binary alcohol esters are 4.41% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 19 minutes,
Addition is 0.042% the catalytic antimony trioxide of terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under conditions of negative pressure, in the presence of 0.048% stabilizer Trimethyl phosphite, start the polycondensation reaction in low vacuum stage, should
Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the reaction time is 45 minutes to temperature control；Then proceed to
Vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 50Pa, reaction temperature controls 275
DEG C, 85 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 28000, own by terephthalic acid (TPA) segment, ethylene glycol segment and 2-
Base -1,5 pentanediol segment compositions, 2- hexyl -1,5 pentanediol segments are 4.41% with the Mole percent ratio of ethylene glycol segment.
Embodiment 24
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.47 terephthalic acid (TPA) and 2- amyl group -1,5 pentanediols are made into slurry and add in reactor,
Concentration is 55wt%, and addition is under the catalytic action of 0.48% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27MPa, and temperature is 245 DEG C, when the water in esterification evaporates
It is esterification terminal that output reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.81 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification anti-
Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27MPa, and temperature is 259 DEG C, when in esterification
It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right
Phthalic acid binary alcohol esters are 4.67% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 19 minutes,
Addition is 0.041% the catalytic antimony trioxide of terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under conditions of negative pressure, in the presence of 0.042% stabilizer triphenyl phosphate, start the polycondensation reaction in low vacuum stage, this rank
Section pressure is steadily evacuated to absolute pressure 485Pa by normal pressure, and at 268 DEG C, the reaction time is 46 minutes to temperature control；Then proceed to take out
Vacuum, carries out the polycondensation reaction of high vacuum stage of Fig, makes reaction pressure be down to absolute pressure 50Pa, and reaction temperature controls at 275 DEG C,
89 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment and 2- penta
Base -1,5 pentanediol segment compositions, 2- amyl group -1,5 pentanediol segments are 4.67% with the Mole percent ratio of ethylene glycol segment.
Embodiment 25
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.45 terephthalic acid (TPA) and 2- hexyl -1,5 pentanediol and 2- amyl group -1,4 butanediol mixed
Compound is made into slurry and adds in reactor, wherein 2- hexyl -1, and the mol ratio of 5 pentanediols and 2- amyl group-Isosorbide-5-Nitrae butanediol is 3:1,
It is 55% in concentration, addition is under the catalytic action of 0.49% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.26MPa, and temperature is 236 DEG C, when the water in esterification evaporates
It is esterification terminal that output reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.8 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 258 DEG C, when the water in esterification evaporates
It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right
Phthalic acid binary alcohol esters are 4.4% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding
Entering 0.042% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under conditions of negative pressure, in the presence of 0.047% stabilizer Trimethyl phosphite, start the polycondensation reaction in low vacuum stage, should
Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the reaction time is 49 minutes to temperature control；Then proceed to
Vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 50Pa, reaction temperature controls 278
DEG C, 88 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester be 29000, by terephthalic acid (TPA) segment, ethylene glycol segment, 2- hexyl-
1,5 pentanediol segment and 2- amyl group-Isosorbide-5-Nitrae butanediol segment composition, 2- hexyl -1,5 pentanediol segments and 2- amyl group-Isosorbide-5-Nitrae fourth two
The summation of alcohol segment is 4.4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 26
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:2- octyl group -1,6 hexylene glycol of 1.45 terephthalic acid (TPA) sum and 2- amyl group -1,5 pentanediol
Mixture is made into slurry and adds in reactor, wherein 2- octyl group -1,6 hexylene glycols and 2- amyl group -1, and the mol ratio of 5 pentanediols is 3:
2, it is 60% in concentration, addition is under the catalytic action of 0.45% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification anti-
Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 239 DEG C, when in esterification
It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.84 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification anti-
Should, esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.29MPa, and temperature is 255 DEG C, when in esterification
It is esterification terminal that water quantity of distillate reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right
Phthalic acid binary alcohol esters are 4.6% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding
Entering 0.0423% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under conditions of negative pressure, in the presence of 0.045% stabilizer Trimethyl phosphite, start the polycondensation reaction in low vacuum stage, should
Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the reaction time is 45 minutes to temperature control；Then proceed to
Vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 50Pa, reaction temperature controls 278
DEG C, 85 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester be 28000, by terephthalic acid (TPA) segment, ethylene glycol segment, 2- octyl group-
1,6 hexylene glycol segment and 2- amyl group -1,5 pentanediol segment compositions, 2- octyl group -1,6 hexylene glycol segments and 2- amyl group -1,5 penta 2
Alcohol segment is 4.6% with the Mole percent ratio of ethylene glycol segment.
Embodiment 27
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.45 terephthalic acid (TPA) and 2- hexyl -1,5 pentanediol and 2- amyl group -1,4 butanediol mixed
Compound is made into slurry and adds in reactor, wherein 2- hexyl -1, and the mol ratio of 5 pentanediols and 2- amyl group-Isosorbide-5-Nitrae butanediol is 3:1,
It is 55% in concentration, addition is under the catalytic action of 0.49% concentrated sulfuric acid of terephthalic acid (TPA) weight, carries out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.26MPa, and temperature is 236 DEG C, when the water in esterification evaporates
It is esterification terminal that output reaches during the 96% of theoretical value, obtains terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.8 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.28MPa, and temperature is 258 DEG C, when the water in esterification evaporates
It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right
Phthalic acid binary alcohol esters are 4.4% with the Mole percent ratio of ethylene glycol terephthalate, and stirring mixing 18 minutes is adding
Entering 0.042% the catalytic antimony trioxide that amount is terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under conditions of negative pressure, in the presence of 0.047% stabilizer Trimethyl phosphite, start the polycondensation reaction in low vacuum stage, should
Staged pressure is steadily evacuated to absolute pressure 495Pa by normal pressure, and at 265 DEG C, the reaction time is 49 minutes to temperature control；Then proceed to
Vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 50Pa, reaction temperature controls 278
DEG C, 88 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester be 29000, by terephthalic acid (TPA) segment, ethylene glycol segment, 2- hexyl-
1,5 pentanediol segment and 2- amyl group-Isosorbide-5-Nitrae butanediol segment composition, 2- hexyl -1,5 pentanediol segments and 2- amyl group-Isosorbide-5-Nitrae fourth two
The summation of alcohol segment is 4.4% with the Mole percent ratio of ethylene glycol segment.
Embodiment 28
A kind of preparation method of modified poly ester, specifically includes following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Mol ratio is 1:1.45 terephthalic acid (TPA) is own with 2- octyl group -1,3 propane diols, 2- amyl group -1,4 butanediol and 2-
Base -1, the mixture of 6 hexylene glycols is made into slurry and adds in reactor, wherein 2- octyl group -1,3 propane diols, 2- amyl group-Isosorbide-5-Nitrae fourth two
The mol ratio of alcohol and 2- hexyl -1,6 hexylene glycol is 3:2:1, it is 60% in concentration, addition is terephthalic acid (TPA) weight
Under the catalytic action of 0.47% concentrated sulfuric acid, carry out esterification, esterification compressive reaction in nitrogen atmosphere, moulding pressure
For 0.29MPa, temperature is 235 DEG C, is esterification terminal when the water quantity of distillate in esterification reaches the 92% of theoretical value,
Obtain terephthalic acid (TPA) binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Mol ratio is 1:1.8 terephthalic acid (TPA)s and ethylene glycol add in reactor after being made into slurry, carry out esterification,
Esterification compressive reaction in nitrogen atmosphere, moulding pressure is 0.27MPa, and temperature is 258 DEG C, when the water in esterification evaporates
It is esterification terminal that output reaches during the 92% of theoretical value, obtains ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), right
Phthalic acid binary alcohol esters are 4.71% with the Mole percent ratio of ethylene glycol terephthalate, stirring mixing 18 minutes,
Addition is 0.04% the catalytic antimony trioxide of terephthalic acid (TPA) weight and addition is terephthalic acid (TPA) weight
Under conditions of negative pressure, in the presence of 0.041% stabilizer Trimethyl phosphite, start the polycondensation reaction in low vacuum stage, should
Staged pressure is steadily evacuated to absolute pressure 490Pa by normal pressure, and at 268 DEG C, the reaction time is 49 minutes to temperature control；Then proceed to
Vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure 50Pa, reaction temperature controls 277
DEG C, 84 minutes reaction time, prepared modified poly ester.
The number-average molecular weight of prepared modified poly ester is 29000, by terephthalic acid (TPA) segment, ethylene glycol segment, band side chain
Glycol segment composition, wherein branched glycol segment be 2- octyl group -1,3 propane diols segments, 2- amyl group-Isosorbide-5-Nitrae butanediol chain
Section and 2- hexyl -1,6 hexylene glycol segments form, and branched glycol segment with the Mole percent ratio of ethylene glycol segment is
4.71%.
Embodiment 29
A kind of preparation method of high uniformity safety belt polyester industrial fiber, high uniformity safety belt polyester industrial fiber is adopted
It is obtained with porous spinneret, on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, oval shaped arrangements refer to spinneret orifice
Hole is centrally located on concentration ellipse, and concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear.
As shown in figure 1, the major axis of ellipse is 1.3 with the ratio of minor axis length, the spacing of adjacent spinneret orifice is equal to spinneret orifice
Guide hole diameter add 1.5mm, spinneret is circular spinneret, the diameter of circular spinneret oval maximum long axial length with series
The difference of degree is 11mm, a diameter of 2.0mm of guide hole of spinneret orifice, and the spinneret hole count of spinneret is 374, the spinneret orifice of spinneret
Shape of cross section be circle.
The modified poly ester that embodiment 1 is obtained is extruded, cools down, oils, is drawn through solid phase polycondensation thickening, metering, porous spinneret
Stretch, thermal finalization and winding, prepared high uniformity safety belt polyester industrial fiber, the wherein temperature of extrusion be 280 DEG C, the wind of cooling
Temperature is 20 DEG C, GR-1 speed 440m/min；80 DEG C of temperature；GR-2 speed 680m/min；100 DEG C of temperature；GR-3 speed 2000m/
min；130 DEG C of temperature；GR-4 speed 2700m/min；230 DEG C of temperature；GR-5 speed 3000m/min；150 DEG C of temperature；Winding
Speed is 3000m/min.
The fracture strength of prepared high uniformity safety belt polyester industrial fiber is 8.4cN/dtex；Line density deviation ratio is
0.6%, fracture strength CV value is 1.8%, and extension at break CV value is 4.5%, and extension at break is 14.0, network 6,4.0cN/dtex
The percentage elongation 5.5% of load；At 260 DEG C, melt viscosity declines 11%, is 177 DEG C × 10min × 0.05cN/ in temperature
Under the test condition of dtex, dry-hot shrinkage is 8.8%.
Embodiment 30
A kind of preparation method of high uniformity safety belt polyester industrial fiber, high uniformity safety belt polyester industrial fiber is adopted
It is obtained with porous spinneret, on spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, oval shaped arrangements refer to spinneret orifice
Hole is centrally located on concentration ellipse, and concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear.
As shown in figure 3, the major axis of ellipse is 1.6 with the ratio of minor axis length, the spacing of adjacent spinneret orifice is equal to spinneret orifice
Guide hole diameter add 1.5mm, spinneret is circular spinneret, the diameter of circular spinneret oval maximum long axial length with series
The difference of degree is 11mm, a diameter of 2.0mm of guide hole of spinneret orifice, and the spinneret hole count of spinneret is 382, the spinneret orifice of spinneret
Shape of cross section be circle.
The modified poly ester that embodiment 1 is obtained is extruded, cools down, oils, is drawn through solid phase polycondensation thickening, metering, porous spinneret
Stretch, thermal finalization and winding, prepared high uniformity safety belt polyester industrial fiber, the wherein temperature of extrusion be 280 DEG C, the wind of cooling
Temperature is 20 DEG C, GR-1 speed 440m/min；80 DEG C of temperature；GR-2 speed 680m/min；100 DEG C of temperature；GR-3 speed 2000m/
min；130 DEG C of temperature；GR-4 speed 2700m/min；230 DEG C of temperature；GR-5 speed 3000m/min；150 DEG C of temperature；Winding
Speed is 3000m/min.
The fracture strength of prepared high uniformity safety belt polyester industrial fiber is 8.8cN/dtex；Line density deviation ratio is
0.7%, fracture strength CV value is 1.7%, and extension at break CV value is 4.8%, and extension at break is 13.5,4.0cN/dtex load
Percentage elongation 5.5%, network 6, at 260 DEG C, melt viscosity declines 11%, is 177 DEG C × 10min × 0.05cN/ in temperature
Under the test condition of dtex, dry-hot shrinkage is 9.2%.
Comparative example 1
A kind of preparation method of high uniformity safety belt polyester industrial fiber, high uniformity safety belt polyester industrial fiber is adopted
It is obtained with porous spinneret, on spinneret, the arrangement mode of spinneret orifice is circular arrangement, circular arrangement refers in the hole of spinneret orifice
The heart is located on concentric circles, and concentric circles is that series is circular.As shown in Fig. 2 the guide hole that the spacing of adjacent spinneret orifice is equal to spinneret orifice is straight
Footpath adds 1.5mm, and spinneret is circular spinneret, and the diameter of circular spinneret with the difference of the circular maximum diameter of series is
11mm, a diameter of 2.0mm of guide hole of spinneret orifice, the spinneret hole count of spinneret is 370, the cross section shape of the spinneret orifice of spinneret
Shape is circle.
The modified poly ester that embodiment 1 is obtained is extruded, cools down, oils, is drawn through solid phase polycondensation thickening, metering, porous spinneret
Stretch, thermal finalization and winding, prepared high uniformity safety belt polyester industrial fiber, the wherein temperature of extrusion be 280 DEG C, the wind of cooling
Temperature is 20 DEG C, GR-1 speed 440m/min；80 DEG C of temperature；GR-2 speed 680m/min；100 DEG C of temperature；GR-3 speed 2000m/
min；130 DEG C of temperature；GR-4 speed 2700m/min；230 DEG C of temperature；GR-5 speed 3000m/min；150 DEG C of temperature；Winding
Speed is 3000m/min.
The fracture strength of prepared high uniformity safety belt polyester industrial fiber is 8.6cN/dtex；Line density deviation ratio is
1%, fracture strength CV value is 1.9%, and extension at break CV value is 5.3%, and extension at break is stretching of 14.1,4.0cN/dtex load
Long rate 5.7%, network 7, at 260 DEG C, melt viscosity declines 11%, is 177 DEG C × 10min × 0.05cN/dtex in temperature
Test condition under, dry-hot shrinkage be 8.5%.
When identical with the effective area that embodiment 29 contrast can be seen that spinneret, (circular arrangement when spinneret hole count is close
Spinneret hole count is 370, and oval shaped arrangements spinneret hole count is 374), the spinneret orifice number of plies of oval shaped arrangements is 6, less than circular arrangement
The spinneret orifice number of plies 8, cooling effect is more preferable；When identical with the effective area that embodiment 30 contrast can be seen that spinneret, oval
The spinneret orifice number of plies of shape arrangement is 5, and less than the spinneret orifice number of plies 8 of circular arrangement, cooling effect is more preferable, the spinneret of oval shaped arrangements
The hole count 382 in hole is more than the hole count 370 of the spinneret orifice of circular arrangement, and cooling effectiveness is higher.The comparing result of fibre property shows,
Fiber linear density deviation ratio that embodiment 29 and embodiment 30 are obtained, fracture strength CV value, extension at break CV value are less than comparative example
1, under the conditions of same process is described, it is better than adopting spinneret using the fibre property that the spinneret of spinneret orifice oval shaped arrangements is obtained
The spinneret of circular arrangement.
Embodiment 31～33
A kind of preparation method of high uniformity safety belt polyester industrial fiber, spinneret orifice be arranged as long axial symmetry, oval
The ratio of major axis and minor axis length be 1.4, the guide hole diameter that the spacing of adjacent spinneret orifice is equal to spinneret orifice adds 1.6mm, spray
Filament plate is circular spinneret, and the diameter of circular spinneret is 12mm with the difference of the oval maximum long axis length of series, spinneret orifice
The a diameter of 1.5mm of guide hole, the spinneret orifice numerical digit 192 of spinneret, the shape of cross section of the spinneret orifice of spinneret is square.
High uniformity safety belt polyester industrial fiber is extruded, cools down, oiling, stretching through metering, porous spinneret, thermal finalization
And winding, prepared high uniformity safety belt polyester industrial fiber, the wherein temperature of extrusion be 300 DEG C, and the wind-warm syndrome of cooling is 25 DEG C；
Stretching, heat setting process parameter are：GR-1 speed 650m/min；85 DEG C of temperature；GR-2 speed 680m/min；100 DEG C of temperature；
GR-3 speed 2400m/min；140 DEG C of temperature；GR-4 speed 3600m/min；220 DEG C of temperature；GR-5 speed 3600m/min；Temperature
150 DEG C of degree；The speed of winding is 2500m/min.
At 280 DEG C, melt viscosity declines percentage, work under normal temperature to prepared high uniformity safety belt polyester industrial fiber
The mechanical performance data of industry silk, and under the test condition for 177 DEG C × 10min × 0.05cN/dtex for the temperature, industrial yarn
Dry-hot shrinkage such as following table.
Embodiment 34～36
A kind of preparation method of high uniformity safety belt polyester industrial fiber, spinneret orifice be arranged as long axial symmetry, oval
The ratio of major axis and minor axis length be 1.4, the guide hole diameter that the spacing of adjacent spinneret orifice is equal to spinneret orifice adds 1.6mm, spray
Filament plate is circular spinneret, and the diameter of circular spinneret is 12mm with the difference of the oval maximum long axis length of series, spinneret orifice
The a diameter of 1.5mm of guide hole, the spinneret orifice numerical digit 384 of spinneret, the shape of cross section of the spinneret orifice of spinneret is square.
High uniformity safety belt polyester industrial fiber is extruded, cools down, oiling, stretching through metering, porous spinneret, thermal finalization
And winding, prepared high uniformity safety belt polyester industrial fiber, the wherein temperature of extrusion be 310 DEG C, and the wind-warm syndrome of cooling is 30 DEG C；
Stretching, heat setting process parameter are：GR-1 speed 650m/min；85 DEG C of temperature；GR-2 speed 680m/min；100 DEG C of temperature；
GR-3 speed 2400m/min；140 DEG C of temperature；GR-4 speed 3300m/min；220 DEG C of temperature；GR-5 speed 3400m/min；Temperature
160 DEG C of degree；The speed of winding is 3100m/min.
Prepared high uniformity safety belt polyester industrial fiber melt viscosity at 290 DEG C declines percentage, work under normal temperature
The mechanical performance data of industry silk, and under the test condition for 177 DEG C × 10min × 0.05cN/dtex for the temperature, industrial yarn
Dry-hot shrinkage such as following table.
Embodiment 37～39
A kind of preparation method of high uniformity safety belt polyester industrial fiber, spinneret orifice be arranged as long axial symmetry, oval
The ratio of major axis and minor axis length be 1.4, the guide hole diameter that the spacing of adjacent spinneret orifice is equal to spinneret orifice adds 1.6mm, spray
Filament plate is circular spinneret, and the diameter of circular spinneret is 12mm with the difference of the oval maximum long axis length of series, spinneret orifice
The a diameter of 1.5mm of guide hole, the spinneret orifice numerical digit 192 of spinneret, the shape of cross section of the spinneret orifice of spinneret is square.
High uniformity safety belt polyester industrial fiber is extruded, cools down, oiling, stretching through metering, porous spinneret, thermal finalization
And winding, prepared high uniformity safety belt polyester industrial fiber, the wherein temperature of extrusion be 290 DEG C, and the wind-warm syndrome of cooling is 20 DEG C；
Stretching, heat setting process parameter are：GR-1 speed 440m/min；75 DEG C of temperature；GR-2 speed 460m/min；90 DEG C of temperature；GR-
3 speed 1900m/min；125 DEG C of temperature；GR-4 speed 2800m/min；250 DEG C of temperature；GR-5 speed 2600m/min；Temperature
165℃；The speed of winding is 2900m/min.
Prepared high uniformity safety belt polyester industrial fiber melt viscosity at 270 DEG C declines percentage, work under normal temperature
The mechanical performance data of industry silk, and under the test condition for 177 DEG C × 10min × 0.05cN/dtex for the temperature, industrial yarn
Dry-hot shrinkage such as following table.
Embodiment 40～42
A kind of preparation method of high uniformity safety belt polyester industrial fiber, spinneret orifice be arranged as long axial symmetry, oval
The ratio of major axis and minor axis length be 1.4, the guide hole diameter that the spacing of adjacent spinneret orifice is equal to spinneret orifice adds 1.6mm, spray
Filament plate is circular spinneret, and the diameter of circular spinneret is 12mm with the difference of the oval maximum long axis length of series, spinneret orifice
The a diameter of 1.5mm of guide hole, the spinneret orifice numerical digit 288 of spinneret, the shape of cross section of the spinneret orifice of spinneret is square.
High uniformity safety belt polyester industrial fiber is extruded, cools down, oiling, stretching through metering, porous spinneret, thermal finalization
And winding, prepared high uniformity safety belt polyester industrial fiber, the wherein temperature of extrusion be 300 DEG C, and the wind-warm syndrome of cooling is 25 DEG C；
Stretching, heat setting process parameter are：GR-1 speed 450m/min；80 DEG C of temperature；GR-2 speed 500m/min；95 DEG C of temperature；GR-
3 speed 2000m/min；130 DEG C of temperature；GR-4 speed 3000m/min；224 DEG C of temperature；GR-5 speed 3200m/min；Temperature
170℃；The speed of winding is 3600m/min.
Prepared high uniformity safety belt polyester industrial fiber melt viscosity at 260 DEG C declines percentage, work under normal temperature
The mechanical performance data of industry silk, and under the test condition for 177 DEG C × 10min × 0.05cN/dtex for the temperature, industrial yarn
Dry-hot shrinkage such as following table.
Embodiment 43～45
A kind of preparation method of high uniformity safety belt polyester industrial fiber, spinneret orifice be arranged as long axial symmetry, oval
The ratio of major axis and minor axis length be 1.4, the guide hole diameter that the spacing of adjacent spinneret orifice is equal to spinneret orifice adds 1.6mm, spray
Filament plate is circular spinneret, and the diameter of circular spinneret is 12mm with the difference of the oval maximum long axis length of series, spinneret orifice
The a diameter of 1.5mm of guide hole, the spinneret orifice numerical digit 192 of spinneret, the shape of cross section of the spinneret orifice of spinneret is square.
High uniformity safety belt polyester industrial fiber is extruded, cools down, oiling, stretching through metering, porous spinneret, thermal finalization
And winding, prepared high uniformity safety belt polyester industrial fiber, the wherein temperature of extrusion be 290 DEG C, and the wind-warm syndrome of cooling is 30 DEG C；
Stretching, heat setting process parameter are：GR-1 speed 460m/min；85 DEG C of temperature；GR-2 speed 600m/min；90 DEG C of temperature；GR-
3 speed 2000m/min；130 DEG C of temperature；GR-4 speed 3600m/min；230 DEG C of temperature；GR-5 speed 3500m/min；Temperature
168℃；The speed of winding is 3000m/min.
Prepared high uniformity safety belt polyester industrial fiber at 280 DEG C, melt viscosity, the mechanics of industrial yarn under normal temperature
Performance data, and under the test condition for 177 DEG C × 10min × 0.05cN/dtex for the temperature, the dry-hot shrinkage of industrial yarn
As following table.
Embodiment 46～48
A kind of preparation method of high uniformity safety belt polyester industrial fiber, spinneret orifice be arranged as long axial symmetry, oval
The ratio of major axis and minor axis length be 1.4, the guide hole diameter that the spacing of adjacent spinneret orifice is equal to spinneret orifice adds 1.6mm, spray
Filament plate is circular spinneret, and the diameter of circular spinneret is 12mm with the difference of the oval maximum long axis length of series, spinneret orifice
The a diameter of 1.5mm of guide hole, the spinneret orifice numerical digit 244 of spinneret, the shape of cross section of the spinneret orifice of spinneret is square.
High uniformity safety belt polyester industrial fiber is extruded, cools down, oiling, stretching through metering, porous spinneret, thermal finalization
And winding, prepared high uniformity safety belt polyester industrial fiber, the wherein temperature of extrusion be 310 DEG C, and the wind-warm syndrome of cooling is 25 DEG C；
Stretching, heat setting process parameter are：GR-1 speed 500m/min；80 DEG C of temperature；GR-2 speed 580m/min；100 DEG C of temperature；
GR-3 speed 2200m/min；135 DEG C of temperature；GR-4 speed 3100m/min；240 DEG C of temperature；GR-5 speed 2800m/min；Temperature
155 DEG C of degree；The speed of winding is 3000m/min.
Prepared high uniformity safety belt polyester industrial fiber melt viscosity at 280 DEG C declines percentage, work under normal temperature
The mechanical performance data of industry silk, and under the test condition for 177 DEG C × 10min × 0.05cN/dtex for the temperature, industrial yarn
Dry-hot shrinkage such as following table.
Embodiment 49～51
A kind of preparation method of high uniformity safety belt polyester industrial fiber, spinneret orifice be arranged as long axial symmetry, oval
The ratio of major axis and minor axis length be 1.4, the guide hole diameter that the spacing of adjacent spinneret orifice is equal to spinneret orifice adds 1.6mm, spray
Filament plate is circular spinneret, and the diameter of circular spinneret is 12mm with the difference of the oval maximum long axis length of series, spinneret orifice
The a diameter of 1.5mm of guide hole, the spinneret orifice numerical digit 192 of spinneret, the shape of cross section of the spinneret orifice of spinneret is square.
High uniformity safety belt polyester industrial fiber is extruded, cools down, oiling, stretching through metering, porous spinneret, thermal finalization
And winding, prepared high uniformity safety belt polyester industrial fiber, the wherein temperature of extrusion be 310 DEG C, and the wind-warm syndrome of cooling is 30 DEG C；
Stretching, heat setting process parameter are：GR-1 speed 480m/min；82 DEG C of temperature；GR-2 speed 580m/min；97 DEG C of temperature；GR-
3 speed 2200m/min；130 DEG C of temperature；GR-4 speed 3400m/min；230 DEG C of temperature；GR-5 speed 3100m/min；Temperature
165℃；The speed of winding is 3300m/min.
Prepared high uniformity safety belt polyester industrial fiber melt viscosity at 280 DEG C, the mechanics of industrial yarn under normal temperature
Performance data, and under the test condition for 177 DEG C × 10min × 0.05cN/dtex for the temperature, the dry-hot shrinkage of industrial yarn
As following table.
Embodiment 52～57
A kind of preparation method of high uniformity safety belt polyester industrial fiber, spinneret orifice be arranged as long axial symmetry, oval
The ratio of major axis and minor axis length be 1.4, the guide hole diameter that the spacing of adjacent spinneret orifice is equal to spinneret orifice adds 1.6mm, spray
Filament plate is circular spinneret, and the diameter of circular spinneret is 12mm with the difference of the oval maximum long axis length of series, spinneret orifice
The a diameter of 1.5mm of guide hole, the spinneret orifice numerical digit 384 of spinneret, the shape of cross section of the spinneret orifice of spinneret is square.
High uniformity safety belt polyester industrial fiber is extruded, cools down, oiling, stretching through metering, porous spinneret, thermal finalization
And winding, prepared high uniformity safety belt polyester industrial fiber, the wherein temperature of extrusion be 310 DEG C, and the wind-warm syndrome of cooling is 20 DEG C；
Stretching, heat setting process parameter are：GR-1 speed 440m/min；75～85 DEG C of temperature；GR-2 speed 680m/min；Temperature 90
℃；GR-3 speed 2400m/min；140 DEG C of temperature；GR-4 speed 2700m/min；250 DEG C of temperature；GR-5 speed 3600m/min；
170 DEG C of temperature；The speed of winding is 3000m/min.
Prepared high uniformity safety belt polyester industrial fiber melt viscosity at 280 DEG C declines percentage, work under normal temperature
The mechanical performance data of industry silk, and under the test condition for 177 DEG C × 10min × 0.05cN/dtex for the temperature, industrial yarn
Dry-hot shrinkage such as following table.
Claims (10)
1. a kind of high uniformity safety belt polyester industrial fiber, is characterized in that：Described high uniformity safety belt polyester industrial fiber
By modified poly ester, after solid-phase tack producing, spinning obtains；The material of described high uniformity safety belt polyester industrial fiber is modified poly ester,
Described modified poly ester form by terephthalic acid (TPA) segment, ethylene glycol segment and containing the dihydroxylic alcohols segment of side chain, described containing side chain
Dihydroxylic alcohols segment refers to that side chain is located on one of dihydroxylic alcohols segment non-end group carbon and side chain is containing 5-10 carbon atom
The dihydroxylic alcohols segment of linear carbon chain；Fracture strength >=the 8.1cN/dtex of described high uniformity safety belt polyester industrial fiber, breaks
Split the percentage elongation 5.5 ± 0.5% for 14.0 ± 1.5%, 4.0cN/dtex load for the elongation；Described high uniformity safety belt polyester
Industrial linear density deviation ratio≤1.0%, fracture strength CV value≤2.0%, extension at break CV value≤5.5%, 260～290
At DEG C, melt viscosity declines 10-20%, and described melt viscosity decline refers to modified poly ester and normal polyester mutually synthermal molten
The contrast of body viscosity.
2. a kind of high uniformity safety belt polyester industrial fiber according to claim 1 is it is characterised in that described height is uniform
Sexual safety belt polyester industrial fiber temperature be 177 DEG C × 10min × 0.05cN/dtex test condition under, dry-hot shrinkage
For 8.0 ± 1.5%, network 6 ± 2；The number-average molecular weight of described modified poly ester is 15000-30000.
3. a kind of high uniformity safety belt polyester industrial fiber according to claim 1 it is characterised in that described containing side chain
Dihydroxylic alcohols segment be 2- amyl group -1,3 propane diols segment, 2- hexyl -1,3 propane diols segment, 2- heptyl -1,3 propane diols segment,
2- octyl group -1,3 propane diols segment, 2- nonyl -1,3 propane diols segment, 2- decyl -1,3 propane diols segment, 2- amyl group -1,4 fourth two
Alcohol segment, 2- hexyl -1,4 butanediol segment, 2- heptyl -1,4 butanediol segment, 2- octyl group -1,4 butanediol segment, 2- nonyl -
1,4 butanediol segments, 2- decyl -1,4 butanediol segment, 2- amyl group -1,5 pentanediol segment, 2- hexyl -1,5 pentanediol segment,
2- heptyl -1,5 pentanediol segment, 2- octyl group -1,5 pentanediol segment, 2- nonyl -1,5 pentanediol segment, 2- decyl -1,5 penta 2
Alcohol segment, 2- amyl group -1,6 hexylene glycol segment, 2- hexyl -1,6 hexylene glycol segment, 2- heptyl -1,6 hexylene glycol segment, 2- octyl group -
One or more of 1,6 hexylene glycol segments, 2- nonyl -1,6 hexylene glycol segment or 2- decyl -1,6 hexylene glycol segment；Described containing
The dihydroxylic alcohols segment of chain and the Mole percent ratio of ethylene glycol segment are 2～5%.
4. the preparation method of a kind of high uniformity safety belt polyester industrial fiber as any one of claim 1-3, its
Feature is：Modified poly ester is extruded, cools down, oiling, stretching through solid phase polycondensation thickening, metering, porous spinneret, thermal finalization and volume
Around prepared high uniformity safety belt polyester industrial fiber；
On described porous spinneret, the arrangement mode of spinneret orifice is oval shaped arrangements, and described oval shaped arrangements refer to the hole of spinneret orifice
It is centrally located on concentration ellipse, described concentration ellipse is that series is oval, and all oval major axis are conllinear, and short axle is conllinear；
The preparation process of modified poly ester comprises the following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Terephthalic acid (TPA) is made into after slurry with the dihydroxylic alcohols containing side chain, under the catalytic action of the concentrated sulfuric acid, carries out esterification,
Obtain terephthalic acid (TPA) binary alcohol esters；The described dihydroxylic alcohols containing side chain is that side chain is located at one of dihydroxylic alcohols segment non-end group carbon
Upper and side chain is the dihydroxylic alcohols of the linear carbon chain containing 5-10 carbon atom；
(2) preparation of ethylene glycol terephthalate：
Terephthalic acid (TPA) and ethylene glycol are made into after slurry, carry out esterification, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), stirring is mixed
Close, in the presence of catalyst and stabilizer, under conditions of negative pressure, carry out polycondensation reaction and the Gao Zhen in low vacuum stage successively
The polycondensation reaction in empty stage, prepared modified poly ester.
5. the preparation method of high uniformity safety belt polyester industrial fiber according to claim 4 is it is characterised in that described
Prepared by modified poly ester concretely comprises the following steps：
(1) preparation of terephthalic acid (TPA) binary alcohol esters：
Terephthalic acid (TPA) and the dihydroxylic alcohols containing side chain are made into slurry add in reactor, under the catalytic action of the concentrated sulfuric acid, enter
Row esterification, esterification compressive reaction in nitrogen atmosphere, moulding pressure is normal pressure～0.3MPa, and temperature is 180～240
DEG C, it is esterification terminal when the water quantity of distillate in esterification reaches more than the 90% of theoretical value；Obtain terephthalic acid (TPA)
Binary alcohol esters；
(2) preparation of ethylene glycol terephthalate：
Terephthalic acid (TPA) and ethylene glycol are made into after slurry and add in reactor, carry out esterification, esterification is in blanket of nitrogen
Enclose middle compressive reaction, moulding pressure is normal pressure～0.3MPa, and temperature is 250～260 DEG C, when the water quantity of distillate in esterification reaches
To theoretical value more than 90% when be esterification terminal, obtain ethylene glycol terephthalate；
(3) preparation of modified poly ester：
After the esterification in step (2) terminates, add the terephthalic acid (TPA) binary alcohol esters of preparation in step (1), stirring is mixed
Close 15-20 minute, under conditions of negative pressure, in the presence of catalyst and stabilizer, start the polycondensation reaction in low vacuum stage,
This staged pressure is steadily evacuated to below absolute pressure 500Pa by normal pressure, temperature control at 260～270 DEG C, the reaction time be 30～
50 minutes；Then proceed to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be down to absolute pressure and be less than
100Pa, reaction temperature controls at 275～280 DEG C, 50～90 minutes reaction time, prepared modified poly ester；
Again modified poly ester is obtained Modified polyester chips through pelletizing, obtained polyester slice is viscosified by solid phase polycondensation, makes polyester
The inherent viscosity of section brings up to 1.0～1.2dL/g, as high viscous section；Again through metering, porous spinneret extrusion, cooling, on
Oil, stretching, thermal finalization and winding, prepared high uniformity safety belt polyester industrial fiber；
Spinning main technologic parameters are：
The temperature of described extrusion is 290～310 DEG C；
The wind-warm syndrome of described cooling is 20～30 DEG C；
Described stretching, heat setting process parameter are：
GR-1 speed 440～650m/min；75～85 DEG C of temperature；
GR-2 speed 460～680m/min；90～100 DEG C of temperature；
GR-3 speed 1900～2400m/min；125～140 DEG C of temperature；
GR-4 speed 2700～3600m/min；220～250 DEG C of temperature；
GR-5 speed 2500～3600m/min；150～170 DEG C of temperature；
The speed of described winding is 2500～3600m/min.
6. a kind of high uniformity safety belt polyester industrial fiber according to claim 5 preparation method it is characterised in that
In described step (1), terephthalic acid (TPA) is 1 with the mol ratio of the dihydroxylic alcohols containing side chain:1.3-1.5；Concentrated sulfuric acid addition is right
The 0.3-0.5% of phthalic acid weight；The concentration of the described concentrated sulfuric acid is 50-60wt%；In described step (2), terephthalic acid (TPA)
Mol ratio with ethylene glycol is 1:1.2～2.0；In described step (3), described terephthalic acid (TPA) binary alcohol esters and terephthalic acid (TPA)
The Mole percent ratio of glycol ester is 2～5%；Described catalyst is antimony oxide, antimony glycol or antimony acetate, catalyst
Addition is the 0.01%～0.05% of terephthalic acid (TPA) gross weight；Described stabilizer be triphenyl phosphate, trimethyl phosphate or
Trimethyl phosphite, stabilizer addition is the 0.01%～0.05% of described terephthalic acid (TPA) gross weight.
7. a kind of high uniformity safety belt polyester industrial fiber according to claim 5 preparation method it is characterised in that
The described dihydroxylic alcohols containing side chain is 2- amyl group -1,3 propane diols, 2- hexyl -1,3 propane diols, 2- heptyl -1,3 propane diols, 2- are pungent
Base -1,3 propane diols, 2- nonyl -1,3 propane diols, 2- decyl -1,3 propane diols, 2- amyl group -1,4 butanediol, 2- hexyl -1,4 fourth
Glycol, 2- heptyl -1,4 butanediol, 2- octyl group -1,4 butanediol, 2- nonyl -1,4 butanediol, 2- decyl -1,4 butanediol, 2- penta
Base -1,5 pentanediol, 2- hexyl -1,5 pentanediol, 2- heptyl -1,5 pentanediol, 2- octyl group -1,5 pentanediol, 2- nonyl -1,5 penta
Glycol, 2- decyl -1,5 pentanediols, 2- amyl group -1,6 hexylene glycols, 2- hexyl -1,6 hexylene glycols, 2- heptyl -1,6 hexylene glycols, 2- are pungent
One or more of base -1,6 hexylene glycol, 2- nonyl -1,6 hexylene glycol or 2- decyl -1,6 hexylene glycol.
8. a kind of high uniformity safety belt polyester industrial fiber according to claim 4 preparation method it is characterised in that
Described porous spinneret is circular spinneret or elliptical spinneret plate；The diameter of described circle spinneret and the oval maximum of series
The difference of long axis length is more than 10mm, and described elliptical spinneret plate is more than with the difference of the oval maximum long axis length of series
10mm.
9. a kind of high uniformity safety belt polyester industrial fiber according to claim 4 preparation method it is characterised in that
On described porous spinneret spinneret orifice be arranged as that major axis and/or short axle are symmetrical, the spacing of adjacent spinneret orifice is more than or equal to spinneret
The guide hole diameter in hole adds 1.5mm；Oval major axis is 1.3～1.8 with the ratio of minor axis length.
10. the preparation method of a kind of high uniformity safety belt polyester industrial fiber according to claim 4, its feature exists
In a diameter of 1.5～2.5mm of guide hole of described spinneret orifice；The spinneret hole count of described spinneret is more than or equal to 192, described spinneret
The shape of cross section of the spinneret orifice of plate is circle, square, rhombus, yi word pattern, triangular form, trilobal cross, hollow type or flat
Type.
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| JP2014189933A (en) * | 2013-03-28 | 2014-10-06 | Toray Ind Inc | Normal pressure dispersion-dyeable polyester ultra-fine fiber |
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