CN108130614A - A kind of polyester HOY fibers and preparation method thereof - Google Patents

A kind of polyester HOY fibers and preparation method thereof Download PDF

Info

Publication number
CN108130614A
CN108130614A CN201711341992.4A CN201711341992A CN108130614A CN 108130614 A CN108130614 A CN 108130614A CN 201711341992 A CN201711341992 A CN 201711341992A CN 108130614 A CN108130614 A CN 108130614A
Authority
CN
China
Prior art keywords
fibers
thermal insulation
modified poly
poly ester
pressure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201711341992.4A
Other languages
Chinese (zh)
Other versions
CN108130614B (en
Inventor
汤方明
王雪
邵义伟
王建根
晏金龙
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Hengli Chemical Fiber Co Ltd
Original Assignee
Jiangsu Hengli Chemical Fiber Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Hengli Chemical Fiber Co Ltd filed Critical Jiangsu Hengli Chemical Fiber Co Ltd
Priority to CN201711341992.4A priority Critical patent/CN108130614B/en
Publication of CN108130614A publication Critical patent/CN108130614A/en
Application granted granted Critical
Publication of CN108130614B publication Critical patent/CN108130614B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • 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

Landscapes

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

Abstract

The present invention relates to a kind of polyester HOY fibers and preparation method thereof, and preparation method is：By modified poly ester melt through measuring, squeezing out, cooling down, oiling and polyester HOY fibers are made in high speed high-speed winding, high-speed winding speed >=6000m/min of its high speed high-speed winding, during cooling, keep longitudinal direction height constant, increase the cross-sectional area of slow cooling chamber, while slow cooling chamber keeps the plate face temperature of spinneret by the way of heat preservation.Fiber Materials include the modified poly ester of terephthalic acid (TPA) segment, ethylene glycol segment and branched dihydric alcohol segment for strand, and the structural formula of branched dihydric alcohol is：In formula, R1And R2It is each independently selected from the straight-chain alkyl-sub that carbon atom number is 1~3, R3Selected from the alkyl that carbon atom number is 1~5, R4Selected from the alkyl that carbon atom number is 2~5, the aberration Δ E of fiber obtained is less than 0.200.The method of the present invention preparation flow advantages of simple, fibre property obtained are excellent.

Description

A kind of polyester HOY fibers and preparation method thereof
Technical field
The invention belongs to fiber preparation fields, are related to a kind of polyester HOY fibers and preparation method thereof.
Background technology
Polyethylene terephthalate (PET) is a kind of polymer of function admirable, and PET is high, strong with modulus because of it The advantages that degree is high, conformality is good and barrier property is good is widely used in the fields such as fiber, bottle packaging, film and sheet material, production Cumulative year after year is measured, position in industry is obviously improved.
But during the polycondensation reaction of synthesis ethylene terephthalate, particularly when generating linear polymer, Since high-temperature oxydation degradation also association linear and cyclic oligomer, cyclic oligomer are due to macromolecular chain in polycondensation phase Hold back sting cyclisation and formed, about more than 70% is cyclic trimer in cyclic oligomer, cyclic trimer have easily aggregation, The easily characteristics such as crystallization, chemistry and heat-resistant stability height, generation cyclic trimer can there are following influences on polyester processing：(1) meeting The blocking of filament spinning component is caused, influences the service life of fondant filter and component；(2) it can be precipitated in fiber heat-setting process, It is deposited on heating roller, frictional force is caused to increase and heat irregular；(3) dyeing course can be made centered on cyclic trimer Dye aggregation is simultaneously adhered to fiber surface, and phenomena such as dyestuff color dot, spot and dyeing defect occurs in fiber surface, influences to be weaved by it The feel and coloured light of the fabric formed, the normal flow velocity of melt can be limited by being simultaneously filled with the cyclic oligomer of pipeline and valve Degree, causes stock-dye irregular, poor reproducibility；(4) fiber surface is adhered to, leads to, around yarn difficulty, broken yarn and thickness occur Phenomena such as uneven, influences the mechanical properties such as fracture strength and the elongation at break of fiber, seriously affects product quality.
It is growing with polyester fiber yield, polyester quality requirement is also increasingly improved, therefore by cyclic oligomer The problem of caused polyester post-processing, gradually causes people to pay close attention to, in particular with the fast development of microdenier polyester fibers, market Higher requirement is proposed to the dyeing of polyester fiber.In order to reduce the production of the cyclic oligomer during polyester polycondensation reaction Raw, domestic and international researcher has carried out a large amount of research.The main method for reducing the cyclic oligomer in polyester at this stage has：(1) Pentavalent phosphorous compound or ether compound are added in, it is made to be combined or increase heat with the metallic catalyst in process of polyester synthesizing The amount of stabilizer so as to generate stabilization to polyester, thus can inhibit the generation of cyclic trimer under high-temperature fusion； (2) residence time of polyester fondant at high temperature is reduced.But the above method can cause molecular weight of polyesters reduction and distribution to widen, The quality of final fiber obtained is influenced, while the reduction effect of cyclic trimer oligomer is not obvious.
In PET fiber production technology, slow cooling area is usually both provided with, purpose has two：One is to ensure that strand will not one Just be rapidly cooled after going out spinneret, cause it is highly oriented due to chilling outside strand, inside because of high temperature, macromolecular is also in nothing Sequence state, fiber radial direction architectural difference is big, i.e., so-called " core-skin " effect；Second, maintain one higher temperature of spinning plate surface Degree, makes wire vent smooth, and aperture bulking effect is normal, is unlikely to " melt fracture " formation " weak silk " occur.Heating to slow cooling area Mode is actively to heat there are mainly two types of pattern, when as shown in Figure 1, the heating agent using babinet is heated, spinning temperature Degree once it is determined that, generally no longer adjust, it is relatively passive, it is difficult to adapt to different application conditions；It is another as shown in Fig. 2, using Electrically heated mode is heated, and set temperature can be higher than babinet heat medium temperature, can also be lower, relatively more flexible, can To be configured according to actual conditions, but high temperature can aggravate coking of the oligomer on spinneret, if reducing temperature such as It cuts off the power and does not heat, since the aluminum material that heater is usually the good quality weight of a heat-transfer effect is formed, can be inhaled from babinet Amount of heat is walked, component chambers outer surrounding heating agent is caused to condense rapidly, heat supplement is insufficient, so as to make filament spinning component temperature Degree declines, and melt flowability is remarkably decreased, and the problems such as a large amount of lousiness drops occurs in product, especially for profiled fibre Production, odd-shaped cross section cause aperture perimeter significantly to increase, and coking material is more in aperture accumulating amount, it is easy to scratch strand, and occur Elbow silk, the presence of this flaw generate single wire fracture in strand high-speed cruising, in cake surface in the form of lousiness drop etc. It shows, the presence of lousiness is brought a great deal of trouble, and tow strength and elongation is made to be affected to post-processing unwinding, this is To be avoided as possible in production other than the defects of mode of heating, slow cooling area of the prior art is also there are a critical defect, i.e., Slow cooling area is cylindrical chamber, oligomer cannot quickly, the loss of unobstructed ground, oligomer is gathered in high-temperature field, must spray A large amount of cokings, cause spinneret to block on filament plate, shorten the clear plate period, and otherwise coking material is attached to around spinneret orifice, production Raw elbow silk, product appearance quality deteriorate rapidly, and broken end dramatically increases, and production efficiency declines, and labor intensity is high, especially It is to show particularly evident on production superbright light profiled fibre, has seriously affected normal production run, caused production Cost greatly wastes.
Therefore, research is a kind of can significantly reduce the content of cyclic oligomer in polyester and can effectively promote polyester The preparation method of energy has a very important significance.
Invention content
The purpose of the invention is to overcome the above-mentioned prior art that cannot significantly reduce the content of cyclic oligomer in polyester And harmful effect can be led to the problem of to the performance of polyester in itself, cyclic oligomer in polyester can be significantly reduced by providing one kind Content and can effectively promote the preparation method of polyester fiber, mainly there is specific knot by increasing in polyester raw material What the branched dihydric alcohol of structure was realized.
In order to achieve the above object, the technical solution adopted by the present invention is：
A kind of polyester HOY fibers, the material of polyester HOY fibers is modified poly ester；
The strand of modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment and branched dihydric alcohol segment, band The structural formula of the dihydric alcohol of branch is as follows：
In formula, R1And R2It is each independently selected from the straight-chain alkyl-sub that carbon atom number is 1~3, R3It is 1 selected from carbon atom number ~5 alkyl, R4Selected from the alkyl that carbon atom number is 2~5, the purpose that carbon atom number limits：Due to introducing branch in dihydric alcohol Chain structure and backbone can weaken the electronegativity of alkoxy portion, and the carbon atom number of branched structure is too small, to alcoxyl The electronegativity influence of base section is small, has little significance to the generation for reducing cyclic oligomer；The carbon atom number mistake of branched structure Greatly, intermolecular entanglement can be generated, the distribution of molecular weight is had an impact；
The aberration Δ E of polyester HOY fibers is less than 0.200.
As preferred technical solution：
A kind of polyester HOY fibers as described above, the filament number of the polyester HOY fibers is 0.3~2.0dtex, just Beginning modulus≤70cN/dtex, line density deviation ratio≤0.2%, fracture strength >=3.0cN/dtex, fracture strength CV values≤ 2.5%, elongation at break is 50.0 ± 4.0%, extension at break CV value≤5.0%, and boiling water shrinkage is 5.5 ± 0.8%, one Lousiness≤2 of a spinning cake.
A kind of polyester HOY fibers as described above, content≤0.6wt% of cyclic oligomer, existing in the modified poly ester The amount for having cyclic oligomer in polyester made from technology is 1.5~2.1wt%, and the present invention is significantly reduced relative to the prior art The production quantity of cyclic oligomer；
The number-average molecular weight 20000~27000 of the modified poly ester, molecular weight distributing index are 1.8~2.2, molecular weight Profile exponent is 1.8~2.2, and the molecular weight of modified poly ester produced by the present invention is higher, and molecular weight distribution is relatively narrow, Neng Gouman The demand of sufficient spinning processing, and be conducive to the excellent fiber of processability；
The molar content of branched dihydric alcohol segment is terephthalic acid (TPA) segment molar content in the modified poly ester 3~5%, the molar content of branched dihydric alcohol segment is relatively low in modified poly ester of the invention, is conducive to keep polyester itself Excellent performance；
The branched dihydric alcohol for 2- Ethyl-2-Methyl -1,3- propylene glycol, 2,2- diethyl -1,3- propylene glycol, 2-butyl-2-ethyl-1,3-propanediol, 3,3- diethyl -1,5- pentanediols, 4,4- diethyl -1,7- heptandiols, 4,4- bis- (1,-Methylethyl) -1,7- heptandiols, 3,3- dipropyl -1,5- pentanediols, 4,4- dipropyl -1,7- heptandiols, 4- methyl - 4- (1,1- dimethyl ethyls) -1,7- heptandiols, 3- methyl -3- amyls -1,6-HD or 3,3- diamyl -1,5- penta 2 Alcohol.
A kind of polyester HOY fibers as described above, the preparation method of the modified poly ester are：By terephthalic acid (TPA), second two Successively progress esterification and polycondensation reaction obtain modified poly ester after mixing for alcohol and the branched dihydric alcohol；Specifically Step is as follows：
(1) esterification；
Terephthalic acid (TPA), ethylene glycol and the branched dihydric alcohol are made into slurry, add in catalyst, delustering agent and After mixing, the pressurization progress esterification in nitrogen atmosphere, moulding pressure is normal pressure~0.3MPa to stabilizer, and esterification is anti- The temperature answered is 250~260 DEG C, is esterification when the water quantity of distillate in esterification reaches more than 90% theoretical value Terminal；
(2) polycondensation reaction；
After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, the staged pressure 30~ Absolute pressure 500Pa is steadily evacuated to by normal pressure in 50min hereinafter, reaction temperature is 260~270 DEG C, the reaction time for 30~ 50min then proceedes to vacuumize, and carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be further reduced to absolute pressure For 100Pa hereinafter, reaction temperature is 275~285 DEG C, the reaction time is 50~90min, and modified poly ester is made.
A kind of polyester HOY fibers as described above, in step (1), terephthalic acid (TPA), ethylene glycol and described branched The molar ratio of dihydric alcohol is 1:1.2~2.0:0.03~0.06, the addition of the catalyst is terephthalic acid (TPA) weight 0.01~0.05%, the addition of the delustering agent is the 0.20~0.25% of terephthalic acid (TPA) weight, and the stabilizer adds Enter 0.01~0.05% that amount is terephthalic acid (TPA) weight；
The catalyst is antimony oxide, antimony glycol or antimony acetate, and the delustering agent is titanium dioxide, described steady Agent is determined for triphenyl phosphate, trimethyl phosphate or Trimethyl phosphite.
A kind of method of polyester HOY fibers as described above is prepared the present invention also provides a kind of, the modified poly ester is melted Body is through measuring, squeezing out, cooling down, oiling and polyester HOY fibers are made in high speed high-speed winding；
High-speed winding speed >=6000m/min of the high speed high-speed winding；
During the cooling, keep longitudinal direction height constant, increase the cross-sectional area of slow cooling chamber, make the oligomer in fiber It can further be diffused into air, reduce its amount being trapped in spinneret, on the one hand extend spinneret uses week Phase, the reduction of oligomer, has been obviously improved the performance of product in another aspect fiber；
Slow cooling chamber keeps the plate face temperature of spinneret by the way of heat preservation simultaneously, improves the quality of product, avoids The spinning uniformity caused by spinneret face temperature is too low declines and then influences the quality of product, and the prior art passes through heating Mode keep spinneret temperature, on the one hand cause the significant wastage of energy consumption, another aspect accuracy of temperature control is to product quality shadow Sound is larger, and stability is poor.
As preferred technical solution：
Method as described above, the cross-sectional area of the increase slow cooling chamber refer to keeping what is connect with slow cooling chamber Under the premise of spinneret is constant, the cross section of slow cooling chamber is changed to rectangle by circle, to increase the area of evaporation area, is had Conducive to the volatilization of linear oligomer, extend the clear plate period；
The slow cooling chamber is surrounded by thermal insulation board and partition, the embedded bottom for hanging on spinning manifold of thermal insulation board, heat preservation Hollow chamber I is opened up in plate, partition, which is assigned into hollow chamber I, is divided into multiple slow cooling chambers, in each slow cooling chamber There is one block of spinneret；
Stainless steel plate of the thermal insulation board for the thermal insulation material of internal 400 DEG C of heatproof of filling or more, the thickness of thermal insulation board are 30~50mm, the wall thickness of stainless steel plate is 0.9~1.5mm.Stainless steel plate wall thickness can reduce the face of evaporation area accordingly Product；Stainless steel wooden partition is thin, and heat insulation effect is bad, influences the quality of product.
Method as described above, the thermal insulation material are rock wool or ceramic fibre；Protection scope of the present invention simultaneously not only limits In this, as long as thermal insulation material high temperature resistant, do not burn and with preferably heat-insulating property and security performance；
The thickness of the partition is 1~3mm；
Polylith spinneret in the hollow chamber I is round spinneret, and the diameter of polylith spinneret is identical, center of circle position In on same straight line and close adjacent；
The cross section of the hollow chamber I is rectangle, and the side for being parallel to polylith spinneret circle center line connecting is long side, is hung down Directly in the side of long side be short side；
The length of the long side is 1.2 times of the sum of the polylith spinneret board diameter, and the length of the short side is the spray 1.7 times of filament plate diameter, by this set to expand the area of evaporation area as far as possible.
Method as described above is superimposed thermal insulation board under the thermal insulation board, and the material of thermal insulation board is identical with thermal insulation board, heat-insulated Hollow chamber II is opened up in plate, hollow chamber II is identical with the cross-sectional shape of hollow chamber I；
In the position that hollow chamber II connects with hollow chamber I, two sides of II cross section of hollow chamber respectively with it is hollow Two short sides of I cross section of chamber overlap, and the length on two sides is more than two short sides；
The thickness of the thermal insulation board is 25~45mm.
Method as described above, the main spinning technology parameter of the polyester HOY fibers are as follows：
The temperature of extrusion：290~300 DEG C；
The wind-warm syndrome of cooling：20~25 DEG C；
The speed of high-speed winding：6000~7000m/min；
The initial pressure of filament spinning component is 120bar, and pressure rises Δ P≤0.6bar/ days.
Invention mechanism：
The method comprises the steps of firstly, preparing include terephthalic acid (TPA) segment, ethylene glycol segment and branched dihydric alcohol segment Modified poly ester, then by modified poly ester melt through measuring, squeezing out, cooling down, oiling, stretching, thermal finalization and high-speed winding are made soft Soft-type polyester fiber during cooling, keeps longitudinal direction height constant, increases the cross-sectional area of slow cooling chamber, while slow cooling chamber uses The mode of heat preservation keeps the plate face temperature of spinneret, wherein modified poly ester, slow cooling chamber structure change and its between each other Synergistic effect the performance of final polyester fiber obtained is influenced it is specific as follows：
The addition of modified poly ester, reduces the generation of cyclic oligomer, on the one hand improves the service life of component, separately On the one hand the uniformity of fiber is improved；The change of slow cooling chamber structure accelerates the volatilization of oligomer, so as to further carry The quality of high microsteping.The two mutually cooperates with, and one contains the generation of cyclic oligomer from source, and one accelerates the volatilization of oligomer, To reduce the content of cyclic oligomer in fiber, fiber aberration is reduced, promotes the stock-dye uniformity.
In organic compound, the angle between two chemical bonds that the same atom of intramolecular is formed is known as bond angle, and bond angle leads to It commonly uses the number of degrees to represent, the electronegativity of central atom and coordination atom in organic compound molecule, the bond angle of molecule can be influenced.When During the electronegativity increase for the coordination atom being bonded with central atom, the enhancing of coordination atom electron-withdrawing ability, bond electron pair will be to Ligand direction is moved, from central atom farther out, make it is close to each other when repulsion reduces between key pair, so that bond angle also subtracts therewith It is small, on the contrary, when the electronegativity for the coordination atom being bonded with central atom reduces, the enhancing of coordination atom electron donation, bonding Electronics to will be moved to central atom direction, from central atom closer to, make to be located remotely from each other due to repulsion increases between key pair, so as to Bond angle also increases therewith.
According to Pauling Electronegativities, the electronegativity of C, H and O atom is respectively 2.55,2.20 and 3.44, and according to Valence electron balancing energy is theoretical, and the calculation formula of Group Electronegativity is shown below：
In formula, xiFor the electronegativity of i atoms neutral atom before bonding, NVe, iFor valence electron number in i atoms, niFor The number of i atoms in the molecule.Calculating step for more complicated Group Electronegativity is mainly：Simple radical is calculated first Then the electronegativity of group regards simple group as electronegativity that quasiatom calculates more complicated group again, such successive iteration, Finally obtain the electronegativity of Targeting groups.It should be noted that calculate quasiatom electronegativity when, base son (for example, Base of group-OH is O atoms) in the valence electron of non-bonding regard the valence electron of quasiatom as.
C atoms can be with the O atom of hydroxyl in dihydric alcohol after the C-O keys fracture of carboxyl in terephthalic acid (TPA) in the present invention With reference to the new C-O keys formed in ester group, the C atoms key C-C formed with C atoms on phenyl ring and the change newly formed in ester group The bond angle learned between key C-O is denoted as α, and the change of bond angle α can influence annulation, and when α is less than 109 °, molecule is easy to cyclization, And with the increase of α, the probability of molecule cyclization can decline.Present invention introduces branched dihydric alcohol, structural formula such as following formula institutes Show：
In formula, R1And R2It is each independently selected from the straight-chain alkyl-sub that carbon atom number is 1~3, R3It is 1 selected from carbon atom number ~5 alkyl, R4Selected from the alkyl that carbon atom number is 2~5.The diol structure due to introducing branched structure and backbone, Can weaken the electronegativity of its alkoxy portion, by the calculation formula of Group Electronegativity can also obtain in the diol structure with The electronegativity for the group that carbonyl is connected is between 2.59~2.79 in diacid, and the base being connected in ethylene glycol with carbonyl in diacid Group-OCH2CH2Electronegativity for 3.04, thus its alkoxy is than-the OCH in ethylene glycol2CH2There is stronger electron Property, so that the bond electron pair on the chemical bond C-O keys newly formed will be moved to center C atomic orientations, from central atom Closer to making to be located remotely from each other due to repulsion increases between key pair, so that bond angle α is more than 109 °, generate the probability of linear polymer Increase, elimination phenomena such as so as to reduce the generation of cyclic oligomer, be conducive to fracture of wire and uneven thickness is conducive to increase The fracture strength of fiber reduces irregularity, so as to improve product quality.
Advantageous effect：
(1) a kind of polyester HOY fibers of the invention, preparation flow advantages of simple, polyester HOY fibers obtained have good Good performance, aberration is relatively low, and dye uniformity is good, great popularization；
(2) preparation method of a kind of polyester HOY fibers of the invention, by introducing branched two in modified poly ester First alcohol changes the bond angle of polyester molecule, so as to significantly reduce the generation of cyclic oligomer in process of polyester synthesizing；
(3) preparation method of a kind of polyester HOY fibers of the invention when being cooled down in spinning process, keeps longitudinal direction high Constant, the cross-sectional area of increase slow cooling chamber is spent, while slow cooling chamber keeps the plate face temperature of spinneret by the way of heat preservation The characteristics of, accelerate the volatilization of oligomer, to reduce cyclic oligomer levels in fiber.
Description of the drawings
Fig. 1 is that the cylindrical slow cooling area of the prior art uses the schematic diagram of gas phase heating medium for heating；
Fig. 2 is that the cylindrical slow cooling area of the prior art uses electrically heated schematic diagram；
Fig. 3 is that the square frame-shaped slow cooling area of the present invention uses the schematic diagram of thermal insulation board heat preservation；
Wherein, 1- spinning manifolds, gas phase heating agent in 2- spinning manifolds, 3- hollow chamber I, 4- electric heater, 5- hollow cavities Room II, 6- thermal insulation boards, 7- thermal insulation boards.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this It invents rather than limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, this field Technical staff can make various changes or modifications the present invention, and such equivalent forms equally fall within the application appended claims Book limited range.
Embodiment 1
A kind of preparation method of polyester HOY fibers, is as follows：
(1) modified poly ester is prepared：
(a) esterification；It is 1 by molar ratio:1.2:0.03 terephthalic acid (TPA), ethylene glycol and 2- ethyl -2- methyl - 1,3-PD is made into slurry, antimony oxide, titanium dioxide and triphenyl phosphate is added in after mixing, in nitrogen atmosphere Middle pressurization carries out esterification, and moulding pressure is normal pressure, and the temperature of esterification is 250 DEG C, when the water in esterification distillates Amount is esterification terminal when reaching the 90% of theoretical value, and wherein the addition of antimony oxide is terephthalic acid (TPA) weight 0.01%, the addition of titanium dioxide is the 0.20% of terephthalic acid (TPA) weight, and the addition of triphenyl phosphate is terephthaldehyde The 0.05% of sour weight, the structural formula of wherein 2- Ethyl-2-Methyls -1,3- propylene glycol are as follows：
(b) polycondensation reaction；After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, Pressure is steadily evacuated to absolute pressure as 500Pa by normal pressure in 30min, reaction temperature is 260 DEG C, reaction time 40min, It then proceedes to vacuumize, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be further reduced to absolute pressure as 100Pa, Reaction temperature is 275 DEG C, reaction time 70min, and modified poly ester is made.Wherein the strand of modified poly ester is included to benzene two Formic acid segment, ethylene glycol segment and 2- ethyl -2- methyl-1s, 3-propanediol segment, the content of cyclic oligomer in modified poly ester For 0.6wt%, number-average molecular weight 20000, molecular weight distributing index 2.0,2- Ethyl-2-Methyls -1,3- third in modified poly ester The molar content of glycol segment is the 3% of terephthalic acid (TPA) segment molar content；
(2) by modified poly ester melt through measuring, squeezing out, cooling down, oil is made polyester HOY fibers with high-speed winding, wherein The winding speed of high-speed winding is 6100m/min.
While cooling, it keeps longitudinal direction height constant, increases the cross-sectional area of slow cooling chamber, while slow cooling chamber is used and protected The mode of temperature keeps the plate face temperature of spinneret, and slow cooling chamber structure schematic diagram is as shown in figure 3, by 6 embedded suspension of thermal insulation board In the bottom of spinning manifold 1, there is gas phase heating agent 2 in spinning manifold 1, " rectangular-ambulatory-plane " is hollow in thermal insulation board 6, inside opens up hollow cavity Room I 3, the cross section of the chamber are rectangle, to be parallel to the side of polylith spinneret circle center line connecting as long side direction, long side 1.2 times for the sum of polylith spinneret board diameter of length, using perpendicular to the direction of long side as short side direction, the length of short side It it is 1.7 times of spinneret board diameter, thickness assigns into hollow chamber I 3 for the partition of 1mm and is divided into multiple slow cooling chambers Room has one block of round spinneret in each slow cooling chamber.The diameter of each spinneret is identical and the center of circle is located along the same line and tightly It is close adjacent.Stainless steel plate of the thermal insulation board 6 for the rock wool of internal 400 DEG C of heatproof of filling, the thickness of thermal insulation board 6 is 30mm, stainless The wall thickness of steel plate is 0.9mm.The thermal insulation board 7 that 6 times superposition thickness of thermal insulation board are 25mm, material and 6 phase of thermal insulation board of thermal insulation board 7 Together, hollow chamber II 5 is opened up in thermal insulation board 7, hollow chamber II 5 is identical with the cross-sectional shape of hollow chamber I 3；Hollow cavity Room II 5 is identical with the long edge lengths of the cross section of hollow chamber I 3；It is connected in hollow chamber II 5 with hollow chamber I 3 Position, two sides of II 5 cross section of hollow chamber overlap respectively with two short sides of hollow chamber I 3 cross section, and this two The length on side is more than two short sides.The rectangular cylindrical slow cooling area for wherein corresponding to single round spinneret is kept the temperature using thermal insulation board, The embedded bottom for hanging on spinning manifold of thermal insulation board, thermal insulation board is interior to be equipped with hollow chamber I, and thermal insulation board is superimposed under thermal insulation board, every Hollow chamber II is offered in hot plate, wherein in the position that hollow chamber II connects with hollow chamber I, hollow chamber II is transversal Two sides in face overlap respectively with two short sides of hollow chamber I cross section, and the length on two sides is more than two short sides, Hollow chamber II and hollow chamber I form a step to accelerate oligomer diffusion after the superposition of two plates.
The main spinning technology parameter of polyester HOY fibers is as follows：The temperature of extrusion is 290 DEG C；The wind-warm syndrome of cooling is 20 ℃；The speed of winding is 6500m/min；The initial pressure of filament spinning component is 120bar, and it is 0.52bar/ days that pressure, which rises Δ P,.Most The aberration Δ E of polyester HOY fibers made from end is 0.159, filament number 2.0dtex, initial modulus 70cN/dtex, line Density variation rate is 0.15%, and fracture strength 3.0cN/dtex, fracture strength CV values are 2.5%, and elongation at break is 46.0%, extension at break CV value are 4.2%, boiling water shrinkage 5.5%, and the lousiness of a spinning cake is 2.
Embodiment 2
A kind of preparation method of polyester HOY fibers, is as follows：
(1) modified poly ester is prepared：
(a) esterification；It is 1 by molar ratio:1.3:0.04 terephthalic acid (TPA), ethylene glycol and 2,2- diethyl -1,3- Propylene glycol is made into slurry, adds in antimony glycol, titanium dioxide and trimethyl phosphate after mixing, pressurizes in nitrogen atmosphere Esterification is carried out, moulding pressure is normal pressure, and the temperature of esterification is 260 DEG C, when the water quantity of distillate in esterification reaches Theoretical value 91% when for esterification terminal, wherein the addition of antimony glycol is the 0.02% of terephthalic acid (TPA) weight, two The addition of titanium oxide is the 0.21% of terephthalic acid (TPA) weight, and the addition of trimethyl phosphate is terephthalic acid (TPA) weight 0.03%, wherein the structural formula of 2,2- diethyl -1,3- propylene glycol is as follows：
(b) polycondensation reaction；After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, Pressure is steadily evacuated to absolute pressure as 490Pa by normal pressure in 35min, reaction temperature is 261 DEG C, reaction time 30min, It then proceedes to vacuumize, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be further reduced to absolute pressure as 100Pa, Reaction temperature is 277 DEG C, reaction time 85min, and modified poly ester is made.Wherein the strand of modified poly ester is included to benzene two Formic acid segment, ethylene glycol segment and 2,2- diethyl -1,3-PD segment, the content of cyclic oligomer is in modified poly ester 0.6wt%, number-average molecular weight 27000, molecular weight distributing index 1.8,2,2- diethyl -1,3-PD in modified poly ester The molar content of segment is the 5% of terephthalic acid (TPA) segment molar content；
(2) by modified poly ester melt through measuring, squeezing out, cooling down, oil is made polyester HOY fibers with high-speed winding, wherein The winding speed of high-speed winding is 6000m/min.
While cooling, it keeps longitudinal direction height constant, increases the cross-sectional area of slow cooling chamber, while slow cooling chamber is used and protected The mode of temperature keeps the plate face temperature of spinneret, and slow cooling chamber configuration is substantially the same manner as Example 1, and difference is septa thickness For 2mm, the interior filling thermal insulation material of thermal insulation board is ceramic fibre, and heat resisting temperature is 405 DEG C, and heat preservation plate thickness is 40mm, stainless Steel plate wall thickness is 1.2mm, and heat-insulated plate thickness is 35mm.
The main spinning technology parameter of polyester HOY fibers is as follows：The temperature of extrusion is 296 DEG C；The wind-warm syndrome of cooling is 21 ℃；The speed of winding is 6600m/min；The initial pressure of filament spinning component is 120bar, and it is 0.55bar/ days that pressure, which rises Δ P,.Most The aberration Δ E of polyester HOY fibers made from end is 0.186, filament number 0.8dtex, initial modulus 66cN/dtex, line Density variation rate is 0.16%, and fracture strength 3.8cN/dtex, fracture strength CV values are 2.3%, and elongation at break is 50.0%, extension at break CV value are 4.8%, boiling water shrinkage 4.7%, and the lousiness of a spinning cake is 1.
Embodiment 3
A kind of preparation method of polyester HOY fibers, is as follows：
(1) modified poly ester is prepared：
(a) esterification；It is 1 by molar ratio:1.4:0.05 terephthalic acid (TPA), ethylene glycol and 2- butyl -2- ethyls - 1,3-PD is made into slurry, antimony acetate, titanium dioxide and Trimethyl phosphite is added in after mixing, in nitrogen atmosphere Pressurization carries out esterification, and moulding pressure 0.1MPa, the temperature of esterification is 252 DEG C, when the water in esterification distillates Amount is esterification terminal when reaching the 92% of theoretical value, and wherein the addition of antimony acetate is terephthalic acid (TPA) weight 0.03%, the addition of titanium dioxide is the 0.23% of terephthalic acid (TPA) weight, and the addition of Trimethyl phosphite is to benzene two The 0.01% of formic acid weight, the structural formula of wherein 2- butyl -2- ethyls -1,3-PD are as follows：
(b) polycondensation reaction；After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, Pressure is steadily evacuated to absolute pressure as 495Pa by normal pressure in 40min, reaction temperature is 263 DEG C, reaction time 45min, It then proceedes to vacuumize, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be further reduced to absolute pressure as 95Pa, Reaction temperature is 278 DEG C, reaction time 60min, and modified poly ester is made, and the wherein strand of modified poly ester is included to benzene two Formic acid segment, ethylene glycol segment and 2- butyl -2- ethyls -1,3-PD segment, the content of cyclic oligomer in modified poly ester For 0.5wt%, number-average molecular weight 21000, molecular weight distributing index 2.2,2- butyl -2- ethyls -1,3- third in modified poly ester The molar content of glycol segment is the 4% of terephthalic acid (TPA) segment molar content；
(2) by modified poly ester melt through measuring, squeezing out, cooling down, oil is made polyester HOY fibers with high-speed winding, wherein The winding speed of high-speed winding is 6000m/min.While cooling, it keeps longitudinal direction height constant, increases the cross section of slow cooling chamber Product, while slow cooling chamber keeps the plate face temperature of spinneret by the way of heat preservation, slow cooling chamber configuration is basic with embodiment 1 Identical, difference is septa thickness for 3mm, and filling thermal insulation material is rock wool in thermal insulation board, and heat resisting temperature is 410 DEG C, heat preservation Plate thickness is 50mm, and stainless steel plate wall thickness is 1.5mm, and heat-insulated plate thickness is 45mm.
The main spinning technology parameter of polyester HOY fibers is as follows：The temperature of extrusion is 299 DEG C；The wind-warm syndrome of cooling is 24 ℃；The speed of winding is 6800m/min；The initial pressure of filament spinning component is 120bar, and it is 0.6bar/ days that pressure, which rises Δ P,.Most The aberration Δ E of polyester HOY fibers made from end is 0.190, filament number 1.6dtex, initial modulus 63cN/dtex, line Density variation rate is 0.19%, and fracture strength 3.3cN/dtex, fracture strength CV values are 2.4%, and elongation at break is 51.0%, extension at break CV value are 4.3%, boiling water shrinkage 6.3%, and the lousiness of a spinning cake is 0.
Embodiment 4
A kind of preparation method of polyester HOY fibers, is as follows：
(1) modified poly ester is prepared：
(a) 3,3- diethyl -1,5- pentanediols are prepared；At 90 DEG C, under nitrogen atmosphere, by 3,3- diethyl-propionic aldehyde, acetaldehyde With triethylamine react 20min, then concentrate addition is had in the hydrogenation reactor of thunder girl's Raney nickel, in 2.914MPa hydrogen Pressure and 100 DEG C at react, reaction finish, cooling, catalyst is precipitated, solution spent ion exchange resin processing after, decompression steam water, Separation, purification, obtains 3,3- diethyl -1,5-PD, wherein the structural formula of 3,3- diethyl -1,5-PD is as follows：
(b) esterification；It is 1 by molar ratio:1.5:0.06 terephthalic acid (TPA), ethylene glycol and 3,3- diethyl -1,5- Pentanediol is made into slurry, adds in antimony oxide, titanium dioxide and triphenyl phosphate after mixing, adds in nitrogen atmosphere Pressure carries out esterification, and moulding pressure 0.3MPa, the temperature of esterification is 255 DEG C, when the water quantity of distillate in esterification It is esterification terminal when reaching the 95% of theoretical value, wherein the addition of antimony oxide is terephthalic acid (TPA) weight 0.04%, the addition of titanium dioxide is the 0.25% of terephthalic acid (TPA) weight, and the addition of triphenyl phosphate is terephthaldehyde The 0.01% of sour weight；
(c) polycondensation reaction；After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, Pressure is steadily evacuated to absolute pressure as 400Pa by normal pressure in 50min, reaction temperature is 265 DEG C, reaction time 33min, It then proceedes to vacuumize, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be further reduced to absolute pressure as 90Pa, Reaction temperature is 280 DEG C, reaction time 50min, and modified poly ester is made, and the wherein strand of modified poly ester is included to benzene two Formic acid segment, ethylene glycol segment and 3,3- diethyl -1,5-PD segment, the content of cyclic oligomer is in modified poly ester 0.2wt%, number-average molecular weight 23000, molecular weight distributing index 1.9,3,3- diethyl -1,5-PD in modified poly ester The molar content of segment is the 3.5% of terephthalic acid (TPA) segment molar content；
(2) by modified poly ester melt through measuring, squeezing out, cooling down, oil is made polyester HOY fibers with high-speed winding, wherein The winding speed of high-speed winding is 6200m/min.While cooling, it keeps longitudinal direction height constant, increases the cross section of slow cooling chamber Product, while slow cooling chamber keeps the plate face temperature of spinneret by the way of heat preservation, slow cooling chamber configuration is basic with embodiment 1 Identical, difference is septa thickness for 1.5mm, thermal insulation material is filled in thermal insulation board as ceramic fibre, heat resisting temperature 402 DEG C, heat preservation plate thickness is 35mm, and stainless steel plate wall thickness is 1.0mm, and heat-insulated plate thickness is 30mm.
The main spinning technology parameter of polyester HOY fibers is as follows：The temperature of extrusion is 292 DEG C；The wind-warm syndrome of cooling is 22 ℃；The speed of winding is 6900m/min；The initial pressure of filament spinning component is 120bar, and it is 0.52bar/ days that pressure, which rises Δ P,.Most The aberration Δ E of polyester HOY fibers made from end is 0.150, filament number 0.3dtex, initial modulus 65cN/dtex, line Density variation rate is 0.2%, and fracture strength 3.2cN/dtex, fracture strength CV values are 2.0%, and elongation at break is 50.0%, extension at break CV value are 5.0%, boiling water shrinkage 5.2%, and the lousiness of a spinning cake is 1.
Embodiment 5
A kind of preparation method of polyester HOY fibers, is as follows：
(1) modified poly ester is prepared：
(a) 4,4- diethyl -1,7- heptandiols are prepared；At 92 DEG C, under nitrogen atmosphere, by 4,4- diethyl-butyraldehyde, propionic aldehyde With triethylamine react 20min, then concentrate addition is had in the hydrogenation reactor of thunder girl's Raney nickel, in 2.914MPa hydrogen Pressure and 100 DEG C at react, reaction finish, cooling, catalyst is precipitated, solution spent ion exchange resin processing after, decompression steam water, Separation, purification, obtains 4,4- diethyl -1,7- heptandiols, wherein the structural formula of 4,4- diethyl -1,7- heptandiols is as follows：
(b) esterification；It is 1 by molar ratio:1.6:0.03 terephthalic acid (TPA), ethylene glycol and 4,4- diethyl -1,7- Heptandiol is made into slurry, adds in antimony glycol, titanium dioxide and trimethyl phosphate after mixing, pressurizes in nitrogen atmosphere Esterification is carried out, moulding pressure is normal pressure, and the temperature of esterification is 257 DEG C, when the water quantity of distillate in esterification reaches Theoretical value 92% when for esterification terminal, wherein the addition of antimony glycol is the 0.05% of terephthalic acid (TPA) weight, two The addition of titanium oxide is the 0.20% of terephthalic acid (TPA) weight, and the addition of trimethyl phosphate is terephthalic acid (TPA) weight 0.04%；
(c) polycondensation reaction；After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, Pressure is steadily evacuated to absolute pressure as 450Pa by normal pressure in 33min, reaction temperature is 270 DEG C, reaction time 30min, It then proceedes to vacuumize, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be further reduced to absolute pressure as 95Pa, Reaction temperature is 275 DEG C, reaction time 60min, and modified poly ester is made, and the wherein strand of modified poly ester is included to benzene two Formic acid segment, ethylene glycol segment and 4,4- diethyl -1,7- heptandiol segment, the content of cyclic oligomer is in modified poly ester 0.5wt%, number-average molecular weight 25000, molecular weight distributing index 2.1,4,4- diethyl -1,7- heptandiols in modified poly ester The molar content of segment is the 5% of terephthalic acid (TPA) segment molar content；
(2) by modified poly ester melt through measuring, squeezing out, cooling down, oil is made polyester HOY fibers with high-speed winding, wherein The winding speed of high-speed winding is 6500m/min.While cooling, it keeps longitudinal direction height constant, increases the cross section of slow cooling chamber Product, while slow cooling chamber keeps the plate face temperature of spinneret by the way of heat preservation, slow cooling chamber configuration is basic with embodiment 1 Identical, difference is that it only has thermal insulation board, and thermal insulation board is not superimposed under thermal insulation board.
The main spinning technology parameter of polyester HOY fibers is as follows：The temperature of extrusion is 290 DEG C；The wind-warm syndrome of cooling is 20 ℃；The speed of winding is 6100m/min；The initial pressure of filament spinning component is 120bar, and it is 0.58bar/ days that pressure, which rises Δ P,.Most The aberration Δ E of polyester HOY fibers made from end is 0.175, filament number 0.9dtex, initial modulus 69cN/dtex, line Density variation rate is 0.1%, and fracture strength 3.8cN/dtex, fracture strength CV values are 2.2%, and elongation at break is 46.0%, extension at break CV value are 4.9%, boiling water shrinkage 6.2%, and the lousiness of a spinning cake is 2.
Embodiment 6
A kind of preparation method of polyester HOY fibers, is as follows：
(1) modified poly ester is prepared：
(a) 4,4- bis- (1,-Methylethyl) -1,7- heptandiols are prepared；At 95 DEG C, under nitrogen atmosphere, by (the 1- first of 4,4- bis- Base ethyl)-butyraldehyde, propionic aldehyde and triethylamine react 20min, then concentrate addition is had to the hydrogenation reaction of thunder girl's Raney nickel It in device, is reacted at 2.914MPa hydrogen pressure and 100 DEG C, reaction is finished, and catalyst is precipitated in cooling.Solution spent ion exchange resin After processing, water is steamed in decompression, detaches, and purification obtains 4,4- bis- (1,-Methylethyl) -1,7- heptandiols, wherein 4,4- bis- (1, - Methylethyl) -1,7- heptandiols structural formula it is as follows：
(b) esterification；It is 1 by molar ratio:1.7:0.05 terephthalic acid (TPA), ethylene glycol and 4,4- bis- (1 ,-methyl Ethyl) -1,7- heptandiols are made into slurry, antimony acetate, titanium dioxide and Trimethyl phosphite are added in after mixing, in nitrogen Pressurization carries out esterification in atmosphere, and moulding pressure 0.2MPa, the temperature of esterification is 253 DEG C, when in esterification Water quantity of distillate is esterification terminal when reaching the 96% of theoretical value, and wherein the addition of antimony acetate is terephthalic acid (TPA) weight 0.01%, the addition of titanium dioxide is the 0.20% of terephthalic acid (TPA) weight, and the addition of Trimethyl phosphite is to benzene The 0.05% of dioctyl phthalate weight；
(c) polycondensation reaction；After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, Pressure is steadily evacuated to absolute pressure as 480Pa by normal pressure in 38min, reaction temperature is 262 DEG C, reaction time 38min, It then proceedes to vacuumize, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be further reduced to absolute pressure as 98Pa, Reaction temperature is 279 DEG C, reaction time 80min, and modified poly ester is made, and the wherein strand of modified poly ester is included to benzene two Formic acid segment, ethylene glycol segment and 4,4- bis- (1,-Methylethyl) -1,7- heptandiol segments, cyclic oligomer in modified poly ester Content for 0.55wt%, number-average molecular weight 27000, molecular weight distributing index 2.2,4,4- bis- in modified poly ester (1 ,-first Base ethyl) -1,7- heptandiol segments molar content be terephthalic acid (TPA) segment molar content 4%；
(2) by modified poly ester melt through measuring, squeezing out, cooling down, oil is made polyester HOY fibers with high-speed winding, wherein The winding speed of high-speed winding is 6000m/min.While cooling, it keeps longitudinal direction height constant, increases the cross section of slow cooling chamber Product, while slow cooling chamber keeps the plate face temperature of spinneret by the way of heat preservation, slow cooling chamber configuration is basic with embodiment 2 Identical, difference is that it only has thermal insulation board, and thermal insulation board is not superimposed under thermal insulation board.
The main spinning technology parameter of polyester HOY fibers is as follows：The temperature of extrusion is 297 DEG C；The wind-warm syndrome of cooling is 24 ℃；The speed of winding is 6500m/min；The initial pressure of filament spinning component is 120bar, and it is 0.55bar/ days that pressure, which rises Δ P,.Most The aberration Δ E of polyester HOY fibers made from end is 0.194, filament number 1.8dtex, initial modulus 63cN/dtex, line Density variation rate is 0.12%, and fracture strength 3.6cN/dtex, fracture strength CV values are 2.1%, and elongation at break is 54.0%, extension at break CV value are 4.1%, boiling water shrinkage 4.8%, and the lousiness of a spinning cake is 2.
Embodiment 7
A kind of preparation method of polyester HOY fibers, is as follows：
(1) modified poly ester is prepared：
(a) 3,3- dipropyl -1,5- pentanediols are prepared；At 94 DEG C, under nitrogen atmosphere, by 3,3- dipropyl-propionic aldehyde, acetaldehyde With triethylamine react 20min, then concentrate addition is had in the hydrogenation reactor of thunder girl's Raney nickel, in 2.914MPa hydrogen Pressure and 100 DEG C at react, reaction finish, cooling, catalyst is precipitated.After the processing of solution spent ion exchange resin, water is steamed in decompression, Separation, purification, obtains 3,3- dipropyl -1,5-PD, wherein the structural formula of 3,3- dipropyl -1,5-PD is as follows：
(b) esterification；It is 1 by molar ratio:1.8:0.03 terephthalic acid (TPA), ethylene glycol and 3,3- dipropyl -1,5- Pentanediol is made into slurry, adds in antimony oxide, titanium dioxide and triphenyl phosphate after mixing, adds in nitrogen atmosphere Pressure carries out esterification, and moulding pressure 0.3MPa, the temperature of esterification is 250 DEG C, when the water quantity of distillate in esterification It is esterification terminal when reaching the 90% of theoretical value, wherein the addition of antimony oxide is terephthalic acid (TPA) weight 0.03%, the addition of titanium dioxide is the 0.24% of terephthalic acid (TPA) weight, and the addition of triphenyl phosphate is terephthaldehyde The 0.02% of sour weight；
(c) polycondensation reaction；After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, Pressure is steadily evacuated to absolute pressure as 455Pa by normal pressure in 42min, reaction temperature is 264 DEG C, reaction time 45min, It then proceedes to vacuumize, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be further reduced to absolute pressure as 85Pa, Reaction temperature is 285 DEG C, reaction time 75min, and modified poly ester is made, and the wherein strand of modified poly ester is included to benzene two Formic acid segment, ethylene glycol segment and 3,3- dipropyl -1,5-PD segment, the content of cyclic oligomer is in modified poly ester 0.45wt%, number-average molecular weight 26500, molecular weight distributing index 2.2,3,3- dipropyl -1,5-PD in modified poly ester The molar content of segment is the 4.5% of terephthalic acid (TPA) segment molar content；
(2) by modified poly ester melt through measuring, squeezing out, cooling down, oil is made polyester HOY fibers with high-speed winding, wherein The winding speed of high-speed winding is 6300m/min.While cooling, it keeps longitudinal direction height constant, increases the cross section of slow cooling chamber Product, while slow cooling chamber keeps the plate face temperature of spinneret by the way of heat preservation, slow cooling chamber configuration is basic with embodiment 3 Identical, difference is that it only has thermal insulation board, and thermal insulation board is not superimposed under thermal insulation board.
The main spinning technology parameter of polyester HOY fibers is as follows：The temperature of extrusion is 295 DEG C；The wind-warm syndrome of cooling is 23 ℃；The speed of winding is 6600m/min；The initial pressure of filament spinning component is 120bar, and it is 0.49bar/ days that pressure, which rises Δ P,.Most The aberration Δ E of polyester HOY fibers made from end is 0.180, filament number 1.9dtex, initial modulus 61cN/dtex, line Density variation rate is 0.14%, and fracture strength 3.3cN/dtex, fracture strength CV values are 2.0%, and elongation at break is 50.0%, extension at break CV value are 4.4%, boiling water shrinkage 5.5%, and the lousiness of a spinning cake is 0.
Embodiment 8
A kind of preparation method of polyester HOY fibers, is as follows：
(1) modified poly ester is prepared：
(a) 4,4- dipropyl -1,7- heptandiols are prepared；At 92 DEG C, under nitrogen atmosphere, by 4,4- dipropyl-butyraldehyde, acetaldehyde With triethylamine react 20min, then concentrate addition is had in the hydrogenation reactor of thunder girl's Raney nickel, in 2.914MPa hydrogen Pressure and 100 DEG C at react, reaction finish, cooling, catalyst is precipitated.After the processing of solution spent ion exchange resin, water is steamed in decompression, Separation, purification, obtains 4,4- dipropyl -1,7- heptandiols, wherein the structural formula of 4,4- dipropyl -1,7- heptandiols is as follows：
(b) esterification；It is 1 by molar ratio:1.9:0.04 terephthalic acid (TPA), ethylene glycol and 4,4- dipropyl -1,7- Heptandiol is made into slurry, adds in antimony glycol, titanium dioxide and trimethyl phosphate after mixing, pressurizes in nitrogen atmosphere Esterification is carried out, moulding pressure 0.3MPa, the temperature of esterification is 260 DEG C, when the water quantity of distillate in esterification reaches To theoretical value 93% when for esterification terminal, wherein the addition of antimony glycol is the 0.04% of terephthalic acid (TPA) weight, The addition of titanium dioxide is the 0.21% of terephthalic acid (TPA) weight, and the addition of trimethyl phosphate is terephthalic acid (TPA) weight 0.03%；
(c) polycondensation reaction；After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, Pressure is steadily evacuated to absolute pressure as 475Pa by normal pressure in 45min, reaction temperature is 265 DEG C, reaction time 48min, It then proceedes to vacuumize, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be further reduced to absolute pressure as 88Pa, Reaction temperature is 283 DEG C, reaction time 80min, and modified poly ester is made, and the wherein strand of modified poly ester is included to benzene two Formic acid segment, ethylene glycol segment and 4,4- dipropyl -1,7- heptandiol segment, the content of cyclic oligomer is in modified poly ester 0.6wt%, number-average molecular weight 23000, molecular weight distributing index 2.0,4,4- dipropyl -1,7- heptandiols in modified poly ester The molar content of segment is the 3% of terephthalic acid (TPA) segment molar content；
(2) by modified poly ester melt through measuring, squeezing out, cooling down, oil is made polyester HOY fibers with high-speed winding, wherein The winding speed of high-speed winding is 6800m/min.While cooling, it keeps longitudinal direction height constant, increases the cross section of slow cooling chamber Product, while slow cooling chamber keeps the plate face temperature of spinneret by the way of heat preservation, slow cooling chamber configuration is basic with embodiment 4 Identical, difference is that it only has thermal insulation board, and thermal insulation board is not superimposed under thermal insulation board.
The main spinning technology parameter of polyester HOY fibers is as follows：The temperature of extrusion is 300 DEG C；The wind-warm syndrome of cooling is 25 ℃；The speed of winding is 6200m/min；The initial pressure of filament spinning component is 120bar, and it is 0.6bar/ days that pressure, which rises Δ P,.Most The aberration Δ E of polyester HOY fibers made from end is 0.199, filament number 2.0dtex, initial modulus 64cN/dtex, line Density variation rate is 0.2%, and fracture strength 3.0cN/dtex, fracture strength CV values are 2.4%, and elongation at break is 50.0%, extension at break CV value are 4.3%, boiling water shrinkage 6.3%, and the lousiness of a spinning cake is 2.
Embodiment 9
A kind of preparation method of polyester HOY fibers, is as follows：
(1) modified poly ester is prepared：
(a) 4- methyl -4- (1,1- dimethyl ethyls) -1,7- heptandiols are prepared；At 92 DEG C, under nitrogen atmosphere, by 4- first Then concentrate addition is had thunder girl's nickel to urge by base -4- (1,1- dimethyl ethyl)-butyraldehyde, propionic aldehyde and triethylamine react 20min It in the hydrogenation reactor of agent, is reacted at 2.914MPa hydrogen pressure and 100 DEG C, reaction is finished, and cooling is precipitated catalyst, solution After spent ion exchange resin processing, water is steamed in decompression, detaches, and purification obtains 4- methyl -4- (1,1- dimethyl ethyl) -1,7- heptan The structural formula of glycol, wherein 4- methyl -4- (1,1- dimethyl ethyl) -1,7- heptandiols is as follows：
(b) esterification；It is 1 by molar ratio:2.0:0.05 terephthalic acid (TPA), ethylene glycol and 4- methyl -4- (1,1- Dimethyl ethyl) -1,7- heptandiols are made into slurry, add in antimony acetate, titanium dioxide and trimethyl phosphate after mixing, Pressurization carries out esterification in nitrogen atmosphere, and moulding pressure is normal pressure MPa, and the temperature of esterification is 251 DEG C, when esterification is anti- Water quantity of distillate in answering is esterification terminal when reaching the 96% of theoretical value, and wherein the addition of antimony acetate is terephthaldehyde The 0.05% of sour weight, the addition of titanium dioxide are the 0.22% of terephthalic acid (TPA) weight, and the addition of trimethyl phosphate is The 0.04% of terephthalic acid (TPA) weight；
(c) polycondensation reaction；After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, Pressure is steadily evacuated to absolute pressure as 420Pa by normal pressure in 30min, reaction temperature is 267 DEG C, reaction time 50min, It then proceedes to vacuumize, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be further reduced to absolute pressure as 80Pa, Reaction temperature is 280 DEG C, reaction time 90min, and modified poly ester is made, and the wherein strand of modified poly ester is included to benzene two Formic acid segment, ethylene glycol segment and 4- methyl -4- (1,1- dimethyl ethyl) -1,7- heptandiol segments, it is cyclic annular in modified poly ester The content of oligomer is 0.25wt%, number-average molecular weight 24000, molecular weight distributing index 2.2,4- methyl in modified poly ester- The molar content of 4- (1,1- dimethyl ethyls) -1,7- heptandiol segments is the 4% of terephthalic acid (TPA) segment molar content；
(2) by modified poly ester melt through measuring, squeezing out, cooling down, oil is made polyester HOY fibers with high-speed winding, wherein The winding speed of high-speed winding is 6600m/min.While cooling, it keeps longitudinal direction height constant, increases the cross section of slow cooling chamber Product, while slow cooling chamber keeps the plate face temperature of spinneret by the way of heat preservation, slow cooling chamber configuration is basic with embodiment 1 Identical, difference is septa thickness for 3mm, and filling thermal insulation material is rock wool in thermal insulation board, and heat resisting temperature is 410 DEG C, heat preservation Plate thickness is 50mm, and stainless steel plate wall thickness is 1.5mm, and heat-insulated plate thickness is 45mm.
The main spinning technology parameter of polyester HOY fibers is as follows：The temperature of extrusion is 298 DEG C；The wind-warm syndrome of cooling is 20 ℃；The speed of winding is 6500m/min；The initial pressure of filament spinning component is 120bar, and it is 0.51bar/ days that pressure, which rises Δ P,.Most The aberration Δ E of polyester HOY fibers made from end is 0.160, filament number 0.5dtex, initial modulus 68cN/dtex, line Density variation rate is 0.16%, and fracture strength 3.8cN/dtex, fracture strength CV values are 2.5%, and elongation at break is 54.0%, extension at break CV value are 5.0%, boiling water shrinkage 4.7%, and the lousiness of a spinning cake is 2.
Embodiment 10
A kind of preparation method of polyester HOY fibers, is as follows：
(1) modified poly ester is prepared：
(a) 3- methyl -3- amyls -1,6-HD is prepared；At 90 DEG C, under nitrogen atmosphere, by 3- methyl -3- amyls-the third Then aldehyde, propionic aldehyde and triethylamine react 20min have concentrate addition in the hydrogenation reactor of thunder girl's Raney nickel, 2.914MPa hydrogen press and 100 DEG C at react, reaction finish, cooling, catalyst is precipitated.After the processing of solution spent ion exchange resin, Water is steamed in decompression, detaches, and purification obtains 3- methyl -3- amyl -1,6- hexylene glycols, wherein 3- methyl -3- amyl -1,6- hexylene glycols Structural formula it is as follows：
(b) esterification；It is 1 by molar ratio:1.2:0.06 terephthalic acid (TPA), ethylene glycol and 3- methyl -3- amyls - 1,6- hexylene glycol is made into slurry, antimony glycol, titanium dioxide and Trimethyl phosphite is added in after mixing, in nitrogen atmosphere Middle pressurization carries out esterification, and moulding pressure 0.1MPa, the temperature of esterification is 255 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 92% of theoretical value, and wherein the addition of antimony glycol is terephthalic acid (TPA) weight 0.01%, the addition of titanium dioxide is the 0.20% of terephthalic acid (TPA) weight, and the addition of Trimethyl phosphite is to benzene two The 0.01% of formic acid weight；
(c) polycondensation reaction；After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, Pressure is steadily evacuated to absolute pressure as 490Pa by normal pressure in 50min, reaction temperature is 269 DEG C, reaction time 30min, It then proceedes to vacuumize, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be further reduced to absolute pressure as 100Pa, Reaction temperature is 281 DEG C, reaction time 55min, and modified poly ester is made, and the wherein strand of modified poly ester is included to benzene two Formic acid segment, ethylene glycol segment and 3- methyl -3- amyl -1,6- hexylene glycol segments, the content of cyclic oligomer in modified poly ester For 0.1wt%, number-average molecular weight 20000, molecular weight distributing index 1.9, in modified poly ester 3- methyl -3- amyls -1,6- oneself The molar content of glycol segment is the 3.5% of terephthalic acid (TPA) segment molar content；
(2) by modified poly ester melt through measuring, squeezing out, cooling down, oil is made polyester HOY fibers with high-speed winding, wherein The winding speed of high-speed winding is 6000m/min.While cooling, it keeps longitudinal direction height constant, increases the cross section of slow cooling chamber Product, while slow cooling chamber keeps the plate face temperature of spinneret by the way of heat preservation, slow cooling chamber configuration is basic with embodiment 1 Identical, difference is that it only has thermal insulation board, and thermal insulation board is not superimposed under thermal insulation board.
The main spinning technology parameter of polyester HOY fibers is as follows：The temperature of extrusion is 293 DEG C；The wind-warm syndrome of cooling is 21 ℃；The speed of winding is 6900m/min；The initial pressure of filament spinning component is 120bar, and it is 0.54bar/ days that pressure, which rises Δ P,.Most The aberration Δ E of polyester HOY fibers made from end is 0.195, filament number 0.3dtex, initial modulus 67cN/dtex, line Density variation rate is 0.16%, and fracture strength 3.9cN/dtex, fracture strength CV values are 2.5%, and elongation at break is 50.0%, extension at break CV value are 5.0%, boiling water shrinkage 4.7%, and the lousiness of a spinning cake is 1.
Embodiment 11
A kind of preparation method of polyester HOY fibers, is as follows：
(1) modified poly ester is prepared：
(a) 3,3- diamyl -1,5- pentanediols are prepared；At 95 DEG C, under nitrogen atmosphere, by 3,3- diamyl-propionic aldehyde, acetaldehyde With triethylamine react 20min, then concentrate addition is had in the hydrogenation reactor of thunder girl's Raney nickel, in 2.914MPa hydrogen Pressure and 100 DEG C at react, reaction finish, cooling, catalyst is precipitated.After the processing of solution spent ion exchange resin, water is steamed in decompression, Separation, purification, obtains 3,3- diamyl -1,5-PD, wherein the structural formula of 3,3- diamyl -1,5-PD is as follows：
(b) esterification；It is 1 by molar ratio:2.0:0.03 terephthalic acid (TPA), ethylene glycol and 3,3- diamyl -1,5- Pentanediol is made into slurry, adds in antimony acetate, titanium dioxide and Trimethyl phosphite after mixing, pressurizes in nitrogen atmosphere Esterification is carried out, moulding pressure 0.2MPa, the temperature of esterification is 250 DEG C, when the water quantity of distillate in esterification reaches To theoretical value 97% when for esterification terminal, wherein the addition of antimony acetate is the 0.01% of terephthalic acid (TPA) weight, two The addition of titanium oxide is the 0.23% of terephthalic acid (TPA) weight, and the addition of Trimethyl phosphite is terephthalic acid (TPA) weight 0.05%；
(c) polycondensation reaction；After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, Pressure is steadily evacuated to absolute pressure as 500Pa by normal pressure in 45min, reaction temperature is 260 DEG C, reaction time 40min, It then proceedes to vacuumize, carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be further reduced to absolute pressure as 92Pa, Reaction temperature is 277 DEG C, reaction time 80min, and modified poly ester is made, and the wherein strand of modified poly ester is included to benzene two Formic acid segment, ethylene glycol segment and 3,3- diamyl -1,5-PD segment, the content of cyclic oligomer is in modified poly ester 0.35wt%, number-average molecular weight 25500, molecular weight distributing index 1.8,3,3- diamyl -1,5-PD in modified poly ester The molar content of segment is the 5% of terephthalic acid (TPA) segment molar content；
(2) by modified poly ester melt through measuring, squeezing out, cooling down, oil is made polyester HOY fibers with high-speed winding, wherein The winding speed of high-speed winding is 6800m/min.While cooling, it keeps longitudinal direction height constant, increases the cross section of slow cooling chamber Product, while slow cooling chamber keeps the plate face temperature of spinneret by the way of heat preservation, slow cooling chamber configuration is basic with embodiment 2 Identical, difference is that it only has thermal insulation board, and thermal insulation board is not superimposed under thermal insulation board.
The main spinning technology parameter of polyester HOY fibers is as follows：The temperature of extrusion is 298 DEG C；The wind-warm syndrome of cooling is 23 ℃；The speed of winding is 7000m/min；The initial pressure of filament spinning component is 120bar, and it is 0.56bar/ days that pressure, which rises Δ P,.Most The aberration Δ E of polyester HOY fibers made from end is 0.152, filament number 1.7dtex, initial modulus 66cN/dtex, line Density variation rate is 0.17%, and fracture strength 3.3cN/dtex, fracture strength CV values are 2.2%, and elongation at break is 50.0%, extension at break CV value are 4.7%, boiling water shrinkage 5.5%, and the lousiness of a spinning cake is 2.

Claims (10)

1. a kind of polyester HOY fibers, it is characterized in that：The material of polyester HOY fibers is modified poly ester；
The strand of modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment and branched dihydric alcohol segment, band branch Dihydric alcohol structural formula it is as follows：
In formula, R1And R2It is each independently selected from the straight-chain alkyl-sub that carbon atom number is 1~3, R3It is 1~5 selected from carbon atom number Alkyl, R4Selected from the alkyl that carbon atom number is 2~5；
The aberration Δ E of polyester HOY fibers is less than 0.200.
A kind of 2. polyester HOY fibers according to claim 1, which is characterized in that the filament number of the polyester HOY fibers For 0.3~2.0dtex, initial modulus≤70cN/dtex, line density deviation ratio≤0.2%, fracture strength >=3.0cN/dtex, Fracture strength CV value≤2.5%, elongation at break are 50.0 ± 4.0%, extension at break CV value≤5.0%, and boiling water shrinkage is 5.5 ± 0.8%, lousiness≤2 of a spinning cake.
A kind of 3. polyester HOY fibers according to claim 1 or 2, which is characterized in that cyclic oligomer in the modified poly ester Content≤0.6wt% of object；
The number-average molecular weight 20000~27000 of the modified poly ester, molecular weight distributing index are 1.8~2.2；
In the modified poly ester molar content of branched dihydric alcohol segment for terephthalic acid (TPA) segment molar content 3~ 5%；
The branched dihydric alcohol is 2- Ethyl-2-Methyl -1,3- propylene glycol, 2,2- diethyl -1,3- propylene glycol, 2- fourths Base -2- ethyl -1,3- propylene glycol, 3,3- diethyl -1,5- pentanediols, 4,4- diethyl -1,7- heptandiols, 4,4- bis- (1,-first Base ethyl) -1,7- heptandiols, 3,3- dipropyl -1,5- pentanediols, 4,4- dipropyl -1,7- heptandiols, 4- methyl -4- (1,1- Dimethyl ethyl) -1,7- heptandiols, 3- methyl -3- amyls -1,6-HD or 3,3- diamyl -1,5- pentanediols.
4. a kind of polyester HOY fibers according to claim 3, which is characterized in that the preparation method of the modified poly ester is： Terephthalic acid (TPA), ethylene glycol and the branched dihydric alcohol are successively subjected to esterification after mixing and polycondensation reaction obtains To modified poly ester；It is as follows：
(1) esterification；
Terephthalic acid (TPA), ethylene glycol and the branched dihydric alcohol are made into slurry, add in catalyst, delustering agent and stabilizer After mixing, in nitrogen atmosphere pressurization carry out esterification, moulding pressure be normal pressure~0.3MPa, the temperature of esterification It is 250~260 DEG C, is esterification terminal when the water quantity of distillate in esterification reaches more than 90% theoretical value；
(2) polycondensation reaction；
After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, the staged pressure is in 30~50min Interior to be steadily evacuated to absolute pressure 500Pa hereinafter, reaction temperature is 260~270 DEG C by normal pressure, the reaction time is 30~50min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be further reduced to absolute pressure 100Pa hereinafter, Reaction temperature is 275~285 DEG C, and the reaction time is 50~90min, and modified poly ester is made.
5. a kind of polyester HOY fibers according to claim 4, which is characterized in that in step (1), terephthalic acid (TPA), second two The molar ratio of alcohol and the branched dihydric alcohol is 1:1.2~2.0:0.03~0.06, the addition of the catalyst is pair The 0.01~0.05% of phthalic acid weight, the addition of the delustering agent are the 0.20~0.25% of terephthalic acid (TPA) weight, The addition of the stabilizer is the 0.01~0.05% of terephthalic acid (TPA) weight；
The catalyst is antimony oxide, antimony glycol or antimony acetate, and the delustering agent is titanium dioxide, and the stabilizer is Triphenyl phosphate, trimethyl phosphate or Trimethyl phosphite.
6. a kind of such as method of polyester HOY fibers of Claims 1 to 5 any one of them is prepared, it is characterized in that：By the modification Polyester fondant is through measuring, squeezing out, cooling down, oiling and polyester HOY fibers are made in high speed high-speed winding；
High-speed winding speed >=6000m/min of the high speed high-speed winding；
It during the cooling, keeps longitudinal direction height constant, increases the cross-sectional area of slow cooling chamber, while slow cooling chamber is using heat preservation Mode keeps the plate face temperature of spinneret.
7. according to the method described in claim 6, it is characterized in that, the cross-sectional area of the increase slow cooling chamber refers to keeping Under the premise of the spinneret that is connect with slow cooling chamber is constant, the cross section of slow cooling chamber is changed to rectangle by circle；
The slow cooling chamber is surrounded by thermal insulation board and partition, the embedded bottom for hanging on spinning manifold of thermal insulation board, in thermal insulation board Hollow chamber I is opened up, partition, which is assigned into hollow chamber I, is divided into multiple slow cooling chambers, has one in each slow cooling chamber Block spinneret；
Stainless steel plate of the thermal insulation board for the thermal insulation material of internal 400 DEG C of heatproof of filling or more, the thickness of thermal insulation board for 30~ 50mm, the wall thickness of stainless steel plate is 0.9~1.5mm.
8. the method according to the description of claim 7 is characterized in that the thermal insulation material is rock wool or ceramic fibre；
The thickness of the partition is 1~3mm；
Polylith spinneret in the hollow chamber I is round spinneret, the diameter of polylith spinneret is identical, the center of circle be located at it is same It is on straight line and close adjacent；
The cross section of the hollow chamber I is rectangle, and the side for being parallel to polylith spinneret circle center line connecting is long side, perpendicular to length While while be short side；
The length of the long side is 1.2 times of the sum of the polylith spinneret board diameter, and the length of the short side is the spinneret 1.7 times of diameter.
9. according to the method described in claim 8, it is characterized in that, be superimposed thermal insulation board under the thermal insulation board, the material of thermal insulation board It is identical with thermal insulation board, hollow chamber II is opened up in thermal insulation board, hollow chamber II is identical with the cross-sectional shape of hollow chamber I；
In the position that hollow chamber II connects with hollow chamber I, two sides of II cross section of hollow chamber respectively with hollow chamber I Two short sides of cross section overlap, and the length on two sides is more than two short sides；
The thickness of the thermal insulation board is 25~45mm.
10. according to the method described in claim 9, it is characterized in that, the main spinning technology parameter of the polyester HOY fibers such as Under：
The temperature of extrusion：290~300 DEG C；
The wind-warm syndrome of cooling：20~25 DEG C；
The speed of high-speed winding：6000~7000m/min；
The initial pressure of filament spinning component is 120bar, and pressure rises Δ P≤0.6bar/ days.
CN201711341992.4A 2017-12-14 2017-12-14 Polyester HOY fiber and preparation method thereof Active CN108130614B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711341992.4A CN108130614B (en) 2017-12-14 2017-12-14 Polyester HOY fiber and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711341992.4A CN108130614B (en) 2017-12-14 2017-12-14 Polyester HOY fiber and preparation method thereof

Publications (2)

Publication Number Publication Date
CN108130614A true CN108130614A (en) 2018-06-08
CN108130614B CN108130614B (en) 2020-04-17

Family

ID=62389425

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711341992.4A Active CN108130614B (en) 2017-12-14 2017-12-14 Polyester HOY fiber and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108130614B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109666985A (en) * 2018-12-27 2019-04-23 江苏恒力化纤股份有限公司 A kind of polyester HOY fiber and preparation method thereof
CN109722730A (en) * 2018-12-27 2019-05-07 江苏恒力化纤股份有限公司 Terylene pre-oriented fiber semi-dull and preparation method thereof
CN109735920A (en) * 2018-12-27 2019-05-10 江苏恒力化纤股份有限公司 Soft type polyester fiber and preparation method thereof
CN109853074A (en) * 2018-12-27 2019-06-07 江苏恒力化纤股份有限公司 The siliceous glycol modified polyester fiber and preparation method thereof of main chain
EP3683339A4 (en) * 2017-12-14 2021-06-02 Jiangsu Hengli Chemical Fibre Co., Ltd. One-step spun elastic composite filament and preparation method therefor

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN201648571U (en) * 2010-04-16 2010-11-24 绍兴市云翔化纤有限公司 Slow cooling device of spinning machine
CN102181951A (en) * 2011-04-26 2011-09-14 常熟涤纶有限公司 Processing method of high-strength low-shrinkage nylon 6 fine denier filament
CN203474971U (en) * 2013-09-12 2014-03-12 福建省源威涤锦科技有限公司 Retarded cooling heater
CN106400161A (en) * 2016-08-31 2017-02-15 江苏恒力化纤股份有限公司 Porous polyester fiber HOY filaments and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN201648571U (en) * 2010-04-16 2010-11-24 绍兴市云翔化纤有限公司 Slow cooling device of spinning machine
CN102181951A (en) * 2011-04-26 2011-09-14 常熟涤纶有限公司 Processing method of high-strength low-shrinkage nylon 6 fine denier filament
CN203474971U (en) * 2013-09-12 2014-03-12 福建省源威涤锦科技有限公司 Retarded cooling heater
CN106400161A (en) * 2016-08-31 2017-02-15 江苏恒力化纤股份有限公司 Porous polyester fiber HOY filaments and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张大省等: "《超细纤维生产技术及应用》", 31 January 2007, 中国纺织出版社 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3683339A4 (en) * 2017-12-14 2021-06-02 Jiangsu Hengli Chemical Fibre Co., Ltd. One-step spun elastic composite filament and preparation method therefor
CN109666985A (en) * 2018-12-27 2019-04-23 江苏恒力化纤股份有限公司 A kind of polyester HOY fiber and preparation method thereof
CN109722730A (en) * 2018-12-27 2019-05-07 江苏恒力化纤股份有限公司 Terylene pre-oriented fiber semi-dull and preparation method thereof
CN109735920A (en) * 2018-12-27 2019-05-10 江苏恒力化纤股份有限公司 Soft type polyester fiber and preparation method thereof
CN109853074A (en) * 2018-12-27 2019-06-07 江苏恒力化纤股份有限公司 The siliceous glycol modified polyester fiber and preparation method thereof of main chain
CN109722730B (en) * 2018-12-27 2020-08-14 江苏恒力化纤股份有限公司 Semi-dull terylene pre-oriented yarn and preparation method thereof
CN109666985B (en) * 2018-12-27 2020-10-16 江苏恒力化纤股份有限公司 Polyester HOY fiber and preparation method thereof

Also Published As

Publication number Publication date
CN108130614B (en) 2020-04-17

Similar Documents

Publication Publication Date Title
CN108385186A (en) A kind of polyester POY fibers and preparation method thereof
CN108385194A (en) A kind of metachromia polyester FDY fiber and preparation method thereof
CN108130614A (en) A kind of polyester HOY fibers and preparation method thereof
CN108385195A (en) A kind of polyester DTY fiber and preparation method thereof
CN108130611A (en) It is a kind of high to stretch low-shrinkage type polyester industrial fiber and preparation method thereof
CN108130605B (en) A kind of polyester Wool-Like abnormal contraction composite filament and preparation method thereof
CN108130624A (en) A kind of polyester imitates linen look abnormal contraction composite filament and preparation method thereof
CN108071009A (en) A kind of method for reducing spun polyester thread filoplume
CN107988649A (en) Superfine draw texturing yarn and preparation method thereof
CN108385189A (en) A kind of low-shrinkage high-strength polyester industrial fiber and preparation method thereof
CN108048939B (en) One step spins elastic force composite filament and preparation method thereof
CN108130610A (en) A kind of superelevation strong type polyester industrial fiber and preparation method thereof
CN107936237B (en) Bio-based degradable polyester fiber and preparation method thereof
CN108035011A (en) Fused mass directly spinning colored polyester fiber and preparation method thereof
CN105463619B (en) A kind of low aberration polyester POY silks and preparation method thereof
CN108130609A (en) A kind of lower shrinkage type polyester industrial fiber and preparation method thereof
CN105442082B (en) A kind of low aberration polyester HOY silks and preparation method thereof
CN108035007A (en) Superfine denier polyester drafting silk and preparation method thereof
CN105671675B (en) A kind of low aberration polyester imitates cotton abnormal contraction composite filament and preparation method thereof
CN107987260B (en) Modified polyester and preparation method thereof
CN105648571B (en) A kind of low aberration polyester DTY silks and preparation method thereof
CN105506774B (en) A kind of low aberration polyester abnormal contraction composite filament and preparation method thereof
CN108385418A (en) A kind of high mode and low mode type rigid line rope and preparation method thereof
CN108130743A (en) Ultralow shrinkage type puggaree and preparation method thereof
CN108130615A (en) A kind of method of oligomer in reduction polyester fiber

Legal Events

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