CN108385189A - A kind of low-shrinkage high-strength polyester industrial fiber and preparation method thereof - Google Patents

A kind of low-shrinkage high-strength polyester industrial fiber and preparation method thereof Download PDF

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CN108385189A
CN108385189A CN201711342813.9A CN201711342813A CN108385189A CN 108385189 A CN108385189 A CN 108385189A CN 201711342813 A CN201711342813 A CN 201711342813A CN 108385189 A CN108385189 A CN 108385189A
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finish
fiber
low
thermal insulation
modified poly
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CN108385189B (en
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赵慧荣
杨大矛
张元华
李晓林
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Jiangsu Hengli Chemical Fiber Co Ltd
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Jiangsu Hengli Chemical Fiber Co Ltd
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • 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
    • 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
    • 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
    • D01D5/096—Humidity control, or oiling, of filaments, threads or the like, leaving the spinnerettes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
    • D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/02—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/11—Compounds containing epoxy groups or precursors thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • D06M13/2243—Mono-, di-, or triglycerides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
    • D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (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 low-shrinkage high-strength polyester industrial fibers and preparation method thereof, and preparation method is：Modified poly ester is viscosified through solid phase polycondensation, melts, measure, squeezing out, cooling down, oiling, stretching, thermal finalization and winding, when cooling, keep longitudinal height constant, increase the cross-sectional area of slow cooling chamber and keep the plate face temperature of spinneret by the way of heat preservation, oils with the crown ether containing content for 67.30~85.58wt% in finish.Preparation method of the present invention is simple, it is the modified poly ester that strand includes terephthalic acid (TPA) segment, ethylene glycol segment and branched dihydric alcohol segment that low-shrinkage high-strength polyester industrial fiber material, which is made, fracture strength >=7.3cN/dtex, dry-hot shrinkage under the conditions of 177 DEG C, 10min and 0.05cN/dtex and under the conditions of 190 DEG C, 15min and 0.01cN/dtex is respectively 1.8 ± 0.5% and 3.5 ± 0.5%.

Description

A kind of low-shrinkage high-strength polyester industrial fiber and preparation method thereof
Technical field
The invention belongs to fiber preparation field, it is related to a kind of low-shrinkage high-strength polyester industrial fiber and preparation method thereof.
Background technology
Polyethylene terephthalate (PET) fiber since the advent of the world, obtains fast because of the excellent performance that it has Suddenly develop, yield has become the hat of world's synthetic fibers.Polyester fiber has fracture strength height, elasticity modulus height, returns Elasticity is moderate, thermal finalization is had excellent performance, heat-resisting light resistance is good and a series of excellent performance such as acid-fast alkali-proof good corrosion resistance, And fabric prepared therefrom has many advantages, such as that crease-resistant and stiffness is good, is widely used in fiber, bottle packaging, film and sheet material etc. Field, yield cumulative year after year, position in industry are obviously improved.
But during synthesizing the polycondensation reaction of ethylene terephthalate, especially when generating linear polymer, Since high-temperature oxydation degradation also association linear and cyclic oligomer, cyclic oligomer are in polycondensation phase due to the macromolecular end of the chain Return sting cyclisation and formed, about 70% or more is cyclic trimer in cyclic oligomer, cyclic trimer have easily aggregation, Yi Jie The characteristics such as brilliant, chemistry and heat-resistant stability height, generation cyclic trimer can there are following influences on polyester processing：(1) it can cause The blocking of filament spinning component influences the service life of fondant filter and component；(2) it can be precipitated, deposit in fiber heat-setting process On heating roller, frictional force is caused to increase and heat irregular；(3) dyeing course can make dyestuff centered on cyclic trimer Assemble and be adhered to fiber surface, phenomena such as dyestuff color dot, spot and dyeing defect occurs in fiber surface, influences made of its weaving The feel and coloured light of fabric, the normal flow stream velocity of melt can be limited by being simultaneously filled with the cyclic oligomer of pipeline and valve, be caused Stock-dye is irregular, poor reproducibility；(4) it is adhered to fiber surface, causes, around yarn difficulty, broken yarn occur and thickness is unequal existing As influencing the mechanical properties such as fracture strength and the elongation at break of fiber, seriously affecting product quality.
It, must in spinning process since the dielectric constant of most of PET fiber is smaller, regain is relatively low and friction coefficient is higher Spinning oil must be used.The main component of finish is surfactant, can form oriented attachment layer on chemical fibre surface, i.e., oily Film, on the one hand, the hydrophilic radical of oil film can adsorb the moisture in air towards space, form continuous water on the fiber surface Film makes charged ion that migration occur on it, reduces the accumulation because of electrostatic charge caused by friction between fiber, to reduce The sheet resistance of fiber increases the electric conductivity of fiber, and on the other hand, fiber, which is isolated, in oil film again can generate centainly fiber Affinity makes it be not at random there are certain convergence, and in addition to this, oil film also imparts certain smooth of fiber Property, so that fiber is not damaged in friction process, and have good feel, can be passed through in spinning winding, stretching, The operational sequences such as dry, eliminate the electrostatic interaction during textile process, will not occur bad around apron, roller, cylinder etc. Phenomenon reduces the generation of lousiness and broken end, ensures the quality of fiber product.
After being ruptured under high temperature, high speed and certain pressure due to the oil film of fiber surface, the friction behavior of fiber can be changed, Cause frictional force to increase, fiber is caused the other problems such as lousiness, broken end occur, film strength is higher, is more not easily broken, more advantageous In the spinnability of fiber, when finish equably adsorbs on the fiber surface, surface forms the oil film of distribution uniform, and oil film exists Fiber is rapid after being stretched and uniformly extends, if the viscosity of finish is excessively high, is unfavorable for the dispersion of finish, forms uniform oil Film.And with the development of the high speed of polyester filament, ultrahigh speed and Mobyneb fiber, develop that a kind of heat resistance is good, viscosity The great realistic meaning of finish low, that film strength is high, Lubricity is good and antistatic property is strong.
In PET fiber production technology, it is usually both provided with slow cooling area, 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 because of chilling outside strand, inside because of high temperature, macromolecular is also in unordered State, fiber radial direction architectural difference is big, i.e., so-called " core-skin " effect；Second, one higher temperature of spinning plate surface is maintained, is made Wire vent is smooth, and aperture bulking effect is normal, is unlikely to " melt fracture " formation " weak silk " occur.To the mode of heating master in slow cooling area To be actively to heat, first, as shown in Figure 1, the heating agent using babinet is heated, spinning temperature is once true there are two types of pattern It is fixed, generally no longer adjust, it is relatively more passive, it is difficult to adapt to different application conditions；Another kind is as shown in Fig. 2, using electrically heated Mode is heated, and setting temperature can be higher than babinet heat medium temperature, can also be lower, relatively more flexible, can be according to reality Border situation is configured, but high temperature can aggravate coking of the oligomer on spinneret, is such as cut off the power not if reducing temperature Heating can siphon away amount of heat since the aluminum material that heater is usually the good quality weight of a heat-transfer effect is constituted from babinet, Component chambers outer surrounding heating agent is caused to condense rapidly, heat supplement is insufficient, to make filament spinning component temperature decline, melt flow Dynamic performance is remarkably decreased, and the problems such as a large amount of lousiness drops occurs in product, is produced especially for profiled fibre, and odd-shaped cross section makes It obtains aperture perimeter to obviously increase, coking material is more in aperture accumulating amount, it is easy to strand is scratched, and elbow silk occurs, this flaw Presence, generate single wire fracture in strand high-speed cruising, showed in the form of lousiness drop etc. in cake surface, lousiness is deposited It is brought a great deal of trouble to post-processing unwinding, and tow strength and elongation is made to be affected, avoided as possible in this production Other than the defect of mode of heating, slow cooling area in the prior art is cylindrical chamber there is also a critical defect, i.e. slow cooling area, Oligomer cannot quickly, the loss of unobstructed ground, oligomer is gathered in high-temperature field, must a large amount of cokings on spinneret, cause Spinneret blocks, and shortens the clear plate period, and otherwise coking material is attached to around spinneret orifice, generates elbow silk, product appearance quality Rapid to deteriorate, broken end dramatically increases, and production efficiency declines, and labor intensity is high, especially in production superbright light odd-shaped cross section What is showed on fiber is particularly evident, has seriously affected normal production run, causes production cost and greatly wastes.
Polyester industrial fiber is widely used, can be used for the fields such as clothes, tire and safety belt.But polyester industrial is prepared at this stage The main problem that silk faces has two, first, finish volatilization is very fast and is easily bonded in fiber surface so that fiber obtained is not Rate is higher, and performance is poor；Second is that the volatilization of oligomer remains in the surface of spinneret in fiber, fiber lousiness is caused, is influenced The quality of fiber.
Therefore, polyester industrial fiber that a kind of spinning is uniform and oligomer is few and preparation method thereof how is provided as working as Preceding urgent problem to be solved.
Invention content
The purpose of the invention is to overcome finish volatilization in the prior art fast easily caused by fiber surface bonds The problem of residual oligomer excessively influences fiber quality during fiber is uneven and spinneret provides a kind of spinning uniformly and oligomer contains Measure few low-shrinkage high-strength polyester industrial fiber and preparation method thereof.The introducing of branched dihydric alcohol in modified poly ester of the present invention, Reduce the cyclic oligomer generated in polyester side reaction, improves the quality of fiber；The use of the finish containing crown ether, improves oil The heat resistance and lubricity of agent, improve the quality of fiber, higher since the more conventional smooth agent of crown ether has lower viscosity Volatilization point makes the friction coefficient smaller of finish containing crown ether and more excellent heat-resistant stability, to improve the processing of fiber Performance reduces the appearance of lousiness phenomenon.By the way that cylindrical slow cooling chamber is changed to rectangular cylindrical, spinning oligomer ease is expanded Space is dissipated, and active heated type slow cooling area is changed to non-heated heat preserving type, reduces oligomer gathering on high-temperature spinneret plate Quantity and hardness significantly extend the profiled fibre clear plate period, increase slow cooling chamber area, increase low in fiber Polymers reduces oligomer in fiber to the probability of external diffusion, improves the uniformity of fiber, to improve the product of fiber Matter.
In order to achieve the above object, the technical solution adopted by the present invention is：
The material of a kind of low-shrinkage high-strength polyester industrial fiber, low-shrinkage high-strength polyester industrial fiber is modified poly ester, modified poly- The strand of ester includes terephthalic acid (TPA) segment, ethylene glycol segment and branched dihydric alcohol segment, branched dihydric alcohol Structural formula 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, R4The alkyl for being 2~5 selected from carbon atom number, the purpose that carbon atom number limits：Due to introducing branch in dihydric alcohol Chain structure and backbone can be such that the electronegativity of alkoxy portion weakens, and the carbon atom number of branched structure is too small, to alkoxy Partial electronegativity influence is small, and the generation to reducing cyclic oligomer has little significance；The carbon atom number of branched structure is excessive, meeting Intermolecular entanglement is generated, the distribution of molecular weight is had an impact；
Fracture strength >=7.3cN/dtex of low-shrinkage high-strength polyester industrial fiber, in 177 DEG C, 10min and 0.05cN/dtex Under the conditions of dry-hot shrinkage be 1.8 ± 0.5%, dry-hot shrinkage under the conditions of 190 DEG C, 15min and 0.01cN/dtex is 3.5 ± 0.5%.The dry-hot shrinkage of product of the present invention is used that polyester industrial fiber is low compared with usually.
A kind of low-shrinkage high-strength polyester industrial fiber as described above, the fiber number of the low-shrinkage high-strength polyester industrial fiber are 930~1440dtex, line density deviation ratio are ± 1.5%, fracture strength CV value≤3.0%, and elongation at break central value is 19.0~21.0%, elongation at break deviation ratio is ± 2.0%, and extension at break CV value≤8.0%, network is 6 ± 2/m, is contained Oil cut rate is 0.40~0.80%, full-rolling rate >=99%.The content reduction of oligomer can be such that the plate face of spinneret more cleans, Increase the uniformity of spinning；The use of the finish containing crown ether simultaneously, it is possible to reduce the appearance of the lousiness of polyester fiber and a phenomenon of floaing, Make full-rolling rate >=99%, to improve the quality of product.
A kind of low-shrinkage high-strength polyester industrial fiber as described above, the content of cyclic oligomer in the modified poly ester≤ 0.6wt%, the amount of cyclic oligomer is 1.5~2.1wt% in polyester made from the prior art, and the present invention is compared with the existing technology Significantly reduce 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, modified poly- The molecular weight of ester is higher, and molecular weight distribution is relatively narrow, disclosure satisfy that the demand of spinning processing, and it is excellent to be conducive to processability Fiber；
The molar content of branched dihydric alcohol segment is the 3 of terephthalic acid (TPA) segment molar content in the modified poly ester ~5%, the molar content of branched dihydric alcohol segment is relatively low in modified poly ester, is conducive to the Optimality for keeping polyester itself Energy；
The branched dihydric alcohol is 2- Ethyl-2-Methyl -1,3- propylene glycol, 2,2- diethyl -1,3- propylene glycol, 2- Butyl -2- ethyl -1,3- propylene glycol, 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- pentanediols.
A kind of low-shrinkage high-strength polyester industrial fiber as described above, the preparation method of the modified poly ester are：It will be to benzene two Formic acid, ethylene glycol and the branched dihydric alcohol successively carry out esterification after mixing and polycondensation reaction obtains modified gather Ester；The specific preparation process of the modified poly ester is as follows：
(1) esterification；
Terephthalic acid (TPA), ethylene glycol and the branched dihydric alcohol are made into slurry, catalyst is added and stabilizer is mixed After closing uniformly, pressurization progress esterification, moulding pressure are normal pressure~0.3MPa in nitrogen atmosphere, and the temperature of esterification is 250~260 DEG C, be esterification terminal when the water quantity of distillate in esterification reaches 90% or more of theoretical value；
(2) polycondensation reaction；
After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure 30~ Absolute pressure 500Pa being steadily evacuated to by normal pressure in 50min hereinafter, reaction temperature is 260~270 DEG C, the reaction time is 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 low-shrinkage high-strength polyester industrial fiber as described above, in step (1), terephthalic acid (TPA), ethylene glycol and described The molar ratio of branched dihydric alcohol is 1:1.2~2.0:0.03~0.06, the addition of the catalyst is terephthalic acid (TPA) The 0.01~0.05% of weight, the addition of the stabilizer are the 0.01~0.05% of terephthalic acid (TPA) weight；
The catalyst is antimony oxide, antimony glycol or antimony acetate, and the stabilizer is triphenyl phosphate, tricresyl phosphate Methyl esters or Trimethyl phosphite.
A kind of method of low-shrinkage high-strength polyester industrial fiber as described above is prepared the present invention also provides a kind of, is changed described Property polyester is viscosified through solid phase polycondensation, is melted, measuring, squeezing out, cooling down, oiling, stretching, low-shrinkage high-strength is made in thermal finalization and winding Polyester industrial fiber；
It when described cooling, keeps longitudinal 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 heating agent is usually used in slow cooling chamber in the prior art or electrically heated mode is protected The plate face temperature of spinneret is held, and the present invention substitutes heating agent or electrically heated mode by the way of heat preservation, is saving the energy Meanwhile the temperature in slow cooling area is reduced, oligomer is effectively reduced in the coking degree of spinning plate surface, extends the clear plate period, this Invention solves in traditional terylene spinning technique that coking quantity is more on spinneret with the oligomer of spinning association, speed is fast, matter The hard problem in ground；
Contain crown ether in the finish to oil, and the content of crown ether is 67.30~85.58wt%, finish of the present invention The content of middle crown ether need to be kept in a certain range, and the addition of crown ether is too low, can not be made that viscosity is low, heat resistance is good and The higher finish of film strength, the addition of crown ether is excessively high, other performance indicators of finish can be affected.
Crown ether is a kind of heterocyclic organic compounds, includes multiple ether groups.The wetting ability of crown ether-like surfactant Bigger than corresponding open chain compound, crown ether has preferable solubilising, and salt compounds are relatively low in the solubility of organic compound, but with The solubility for the organic matter of the addition salt compounds of crown ether is improved.Conventional polyester class compound or polyethers in finish Class, since molecular weight is larger and the effect of hydrogen bond, intermolecular effect is larger, and it is larger to show as kinematic viscosity, after crown ether is added, Crown ether can be preferably compatible in polyesters compound or polyethers finish system, into polyesters compound or polyethers molecule Between chain, the active force between strand is shielded, is reduced so as to cause the viscosity of finish system.Preparation medium is antistatic simultaneously Agent is broadly divided into anionic, cationic and amphoteric surfactant, mostly contains metal ion or deposits in a salt form This all makes antistatic agent and polyesters compound in finish or the phase tolerance of polyethers, the addition of crown ether, due to the molten effect of salt It answers, improves antistatic agent and polyesters compound or the compatibility of polyethers, and then improve finish oil film strength, this is right The stability and the product amount of holding of spinning have larger meaning.The index of finish is the embodiment of a composite factor, thus to crown ether Addition propose certain restriction, too low heat resistance, the advantage of film strength to finish embodies inadequate, and excessive other refer to Rotating savings is restricted；
The finish when in use, the emulsion of a concentration of 14~18wt% is configured to water.
As preferred technical solution：
The inherent viscosity of method as described above, the solid phase polycondensation thickening post-modification polyester is 1.0~1.2dL/g；It is special Property viscosity be molecular weight a kind of characteristic manner, inherent viscosity is excessively high, and following process temperature increases, and thermal degradation easily occurs for product； Inherent viscosity is too low, then is difficult to intensity and performance required for reaching；
The cycle stretch-out of spinneret 35~45% is cleared up in replacement cycle >=40 day of filament spinning component；
The cross-sectional area for increasing slow cooling chamber refers in the premise for keeping the spinneret being connect with slow cooling chamber constant Under, the cross section of slow cooling chamber is changed to rectangle by circle, slow cooling chamber in the prior art is cylinder, and cross section is circle Shape, in the case where the spinneret for keeping connecting with slow cooling chamber is constant, rectangle is larger relative to circular area increase, causes to delay The volume of cold chamber increases about 50%, greatly improves the loss speed and quantity of oligomer (spinning association)；
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 assigns into hollow chamber I, is divided into multiple slow cooling chambers, in each slow cooling chamber There is one block of spinneret, by assigning partition, distinguishes ingot number, and sprayed silicone oil when clear plate is avoided to interfere with each other；
The thermal insulation board is the stainless steel plate of the thermal insulation material of internal 400 DEG C of heatproof of filling or more, and the thickness of thermal insulation board is The wall thickness of 30~50mm, stainless steel plate are 0.9~1.5mm, and under the premise of ensureing indeformable, the wall thickness of stainless steel plate will be as possible Ground is small, reduces the load of itself caloric receptivity and babinet heating agent；
The thermal insulation material is rock wool or ceramic fibre, and thermal insulation material is not limited to above two material, other have The material of similar functions is equally applicable to the present invention；
The thickness of the partition is 1~3mm, and the thickness of partition is thin as possible in the case of proof strength, but septa thickness The excessively thin transmission that can not obstruct heat between each slow cooling chamber；
Polylith spinneret in the hollow chamber I is round spinneret, and the diameter of polylith spinneret is identical, the center of circle is located at It is 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, vertically In the side of long side be short side；
The length of the long side is 1.2 times of the sum of described polylith spinneret board diameter, and the length of the short side is the spray 1.7 times of filament plate diameter, setting is to accelerate the volatilization of oligomer to expand the area of evaporation area as far as possible in this way.
Method as described above is superimposed thermal insulation board under the thermal insulation board, and the material of thermal insulation board is identical as thermal insulation board, thermal insulation board Hollow chamber II is inside opened up, hollow chamber II is identical as the cross-sectional shape of hollow chamber I；
In the position that hollow chamber II is connected to 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 so that thermal insulation board is superimposed with thermal insulation board Hollow chamber II and hollow chamber I form a step afterwards, and oligomer is easier to spread, the addition extension of thermal insulation board in the present invention The length of zone of silence, is conducive to the promotion of fiber quality, simultaneously because hollow chamber II inside septumless, it can be utmostly Ground avoids influence of the cool ambient air to the plate face temperature of spinneret；
The thickness of the thermal insulation board is 25~45mm, and thermal insulation board is blocked up, then reduces the area of evaporation area accordingly；It is heat-insulated Plate is excessively thin, then can not be effectively heat-insulated, influences the quality of product.
Method as described above, thermal weight loss is less than 15wt% after the finish heats 2h at 200 DEG C, and crown ether has more The heat resistance of high volatilization point and excellent heat-resistant stability, the finish introduced after crown ether is also obviously improved；
For the finish at (50 ± 0.01) DEG C, kinematic viscosity is 27.5~30.1mm2/ s, the finish are configured to water Kinematic viscosity after the lotion of a concentration of 10wt% is 0.93~0.95mm2/ s, the viscosity that crown ether can reduce finish are mainly Since crown ether oneself viscosity is relatively low and is pearl small molecule, after introducing crown ether in finish system, crown ether can be preferably compatible to In polyesters compound or polyether compound finish system, while entering polyesters compound or polyether compound strand Between, the active force between strand is shielded, to reduce the viscosity of finish system；
The film strength of the finish is 121~127N, and the film strength of finish is relatively low in the prior art, generally in 110N Left and right is mostly contained metal ion this is mainly due to the antistatic agent of preparation medium or is existed in a salt form, causes to resist Electrostatic agent can improve film strength and be mainly with polyesters compound or the poor compatibility of polyether compound in finish, crown ether Salting in effect can be generated after being added due to crown ether, improves antistatic agent and polyesters compound or the compatibility of polyethers, And then improve finish oil film strength；
The surface tension of the finish is 23.2~26.8cN/cm, and specific resistance is 1.0 × 108~1.8 × 108Ω·cm；
After oiling, confficient of static friction between fiber and fiber is 0.250~0.263, the coefficient of kinetic friction is 0.262~ 0.273；
After oiling, confficient of static friction between fiber and metal is 0.202~0.210, the coefficient of kinetic friction is 0.320~ 0.332。
The crown ether is 2- methylols -12-crown-4,15- crown ethers -5 or 2- methylol -15- crown-s 5；
Also contain mineral oil, phosphate kalium salt, trimethylolpropane laurate and sodium alkyl sulfonate in the finish；
The mineral oil is one kind in the mineral oil of 9#~17#；
The phosphate kalium salt is 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, isomerous tridecanol polyoxyethylene ether phosphate kalium salt or ten Tetracosanol phosphate kalium salt；
The sodium alkyl sulfonate is dodecyl sodium sulfate, pentadecyl sulfonic acid sodium or sodium cetanesulfonate；
The preparation method of the finish is：By crown ether and phosphate kalium salt, trimethylolpropane laurate and alkyl sulphur Sour sodium is added in mineral oil after mixing is uniformly mixing to obtain finish；It counts in parts by weight, the addition of each component is as follows：
The mixing carries out at normal temperatures, and the temperature of the stirring is 40~55 DEG C, and the time is 1~3h.
The spinning technology parameter of method as described above, the low-shrinkage high-strength polyester industrial fiber is as follows：
It stretches, the technological parameter of thermal finalization is：
Invention mechanism：
The present invention is first using the modification for including terephthalic acid (TPA) segment, ethylene glycol segment and branched dihydric alcohol segment Polyester, modified poly ester melt is viscosified through solid phase polycondensation then, is melted, is measured, is squeezed out, is cooled down, is oiled, is stretched, thermal finalization and Low-shrinkage high-strength polyester industrial fiber is made in winding, when cooling, keep longitudinal height constant, increases the cross-sectional area of slow cooling chamber, Slow cooling chamber keeps the plate face temperature of spinneret by the way of heat preservation simultaneously, contains crown ether, and crown ether in the finish to oil Content be 67.30~85.58wt%, wherein modified poly ester, finish and slow cooling chamber structure improvement and its between each other Synergistic effect the performance of final low-shrinkage high-strength polyester industrial fiber obtained is influenced it is specific as follows：
The addition of modified poly ester in the present invention, reduces the generation of cyclic oligomer, on the one hand improves the use of component On the other hand service life improves the stability of spinning, improve the uniformity of fiber.In addition the present invention, which also uses, contains crown ether Finish increases the stability of spinning, is mutually cooperateed with modified poly ester, improves the stability of spinning, and then improve fiber Quality.The cross-sectional area for increasing slow cooling chamber, on the one hand reduces the probability that the oligomer diffused out is trapped on spinneret, prolongs It has grown the cleaning frequency of spinneret, on the other hand the oligomer in fiber has further been diffused into air, and changed Property polyester mutually cooperate with, reduce fiber in cyclic oligomer content, improve the strength character of fiber.
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 is logical The common number of degrees indicate that the electronegativity of central atom and coordination atom, can influence the bond angle of molecule in organic compound molecule.When with Central atom bonding coordination atom electronegativity increase when, coordination atom electron-withdrawing ability enhancing, bond electron pair will to The movement of position body direction farther out from central atom makes between key pair because that repulsion reduces is close to each other, so that bond angle also reduces therewith, On the contrary, when the electronegativity for the coordination atom being bonded with central atom reduces, the enhancing of coordination atom electron donation, bonding electrons To will be moved to central atom direction, from central atom closer to making to be located remotely from each other because repulsion increases between key pair, to bond angle Increase 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 i The number of atom in the molecule.Calculating step for more complex Group Electronegativity is mainly：Simple group is calculated first Electronegativity, then regard simple group as electronegativity that quasiatom calculates more complex group again, such successive iteration, finally Obtain the electronegativity of Targeting groups.It should be noted that when calculating the electronegativity of quasiatom, base (for example, group- Base of OH is O atom) in the valence electron of non-bonding regard the valence electron of quasiatom as.
C atoms can be with the O atom knot of hydroxyl in dihydric alcohol after the C-O keys fracture of carboxyl in terephthalic acid (TPA) in the present invention The new C-O keys formed in ester group are closed, the C atoms key C-C formed with C atoms on phenyl ring in ester group and the chemical bond newly formed Bond angle between 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 cyclic, and with The increase of α, the probability of molecule cyclization can decline.Present invention introduces branched dihydric alcohol, structural formula is shown below：
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, R4The alkyl for being 2~5 selected from carbon atom number.The diol structure due to introducing branched structure and backbone, The electronegativity of its alkoxy portion can be made to weaken, can also be obtained in the diol structure with two by the calculation formula of Group Electronegativity The electronegativity of the connected group of carbonyl is between 2.59~2.79 in acid, and the group-being connected with carbonyl in diacid in ethylene glycol OCH2CH2Electronegativity be 3.04, thus its alkoxy is than-the OCH in ethylene glycol2CH2There is stronger electron, because This makes the bond electron pair on the chemical bond C-O keys newly formed that will be moved to center C atomic orientations, from central atom closer to, Make to be located remotely from each other because repulsion increases between key pair, so that bond angle α is more than 109 °, the probability for generating linear polymer increases, The generation of phenomena such as to reduce the generation of cyclic oligomer, advantageously reduce fracture of wire and uneven thickness, advantageously reduces pair The influence that the mechanical properties such as the fracture strength of fiber and elongation at break generate, to improve product quality.
The present invention has been made that a kind of viscosity is low, heat resistance is good and film strength is higher by introducing crown ether in finish Finish.The viscosity of finish is higher mainly due to containing conventional polyester class compound or polyethers chemical combination in finish in the prior art Object, for such compound since molecular weight is larger and the effect of hydrogen bond, the intermolecular larger kinematic viscosity that shows as of effect is larger, Thus cause the viscosity of finish higher, the viscosity of finish can significantly reduce after addition crown ether, mainly since crown ether itself is viscous It spends relatively low and is pearl small molecule, crown ether can be preferably compatible in polyesters compound or polyethers finish system, while into Enter between polyesters compound or polyether compound strand, the active force between strand is shielded, to reduce finish body The viscosity of system.The film strength of finish is relatively low mainly since the antistatic agent of preparation medium mostly contains metal in the prior art Ion exists in a salt form, leads to antistatic agent and the poor compatibility of polyesters compound or polyethers in finish, hat Ether, which can improve after film strength is mainly added due to crown ether, can generate salting in effect, improve antistatic agent and polyesters The compatibility of compound or polyethers, and then improve finish oil film strength.In addition, crown ether has higher volatilization point and excellent The heat resistance of good heat-resistant stability, the finish introduced after crown ether is also obviously improved, since crown ether is with relatively low Viscosity, higher volatilization point, smaller friction coefficient and excellent heat-resistant stability, improve the processing performance of fiber.
The cross section of slow cooling chamber is changed to square by the present invention in the case where keeping longitudinal height constant by current circle Shape increases the cross-sectional area of slow cooling chamber, expands spinning oligomer loss space, while the heat preserving mode of slow cooling chamber will Active heated type is changed to non-heated heat preserving type, while reducing energy consumption, reduces oligomer gathering on high-temperature spinneret plate Quantity and hardness.By the improvement of these two aspects, the present invention significantly extends the profiled fibre clear plate period.This Outside, the present invention can also be superimposed hollow thermal insulation board under thermal insulation board so that after thermal insulation board is superimposed with thermal insulation board inside the two Hollow chamber is formed into a step, and the length of zone of silence is on the one hand extended, and on the other hand accelerates the diffusion speed of oligomer Degree, while insulation can also be played the role of.
Advantageous effect：
(1) a kind of low-shrinkage high-strength polyester industrial fiber and preparation method thereof of the invention, preparation flow advantages of simple are made Polyester industrial fiber have the advantages that fracture strength is high and dry-hot shrinkage is low；
(2) preparation method of a kind of low-shrinkage high-strength polyester industrial fiber of the invention, by introducing band in modified poly ester The dihydric alcohol of branch changes the bond angle of polyester molecule, to significantly reduce the production of cyclic oligomer in process of polyester synthesizing It is raw；
(3) preparation method of a kind of low-shrinkage high-strength polyester industrial fiber of the invention, oil use in the process containing hat The oil agent of ether has the characteristics that viscosity is low, heat resistance is good, film strength is high, Lubricity is good and antistatic property is strong, carries The high stability of spinning and the processing performance of fiber；
(4) preparation method of a kind of low-shrinkage high-strength polyester industrial fiber of the invention, by having made oil in preparation process The improvement in agent, polyester raw material and slow cooling area etc. is prepared with more excellent performance of low-shrinkage high-strength polyester industrial fiber；
(5) preparation method of a kind of low-shrinkage high-strength polyester industrial fiber of the invention, square is changed to by cylindrical slow cooling chamber Shape column expands spinning oligomer loss space, and active heated type slow cooling area is changed to non-heated heat preserving type, reduces low Polymers gathers quantity and hardness on high-temperature spinneret plate, significantly extends the profiled fibre clear plate period；
(6) preparation method of a kind of low-shrinkage high-strength polyester industrial fiber of the invention, greatly improves production efficiency, will Active heated type slow cooling area is changed to non-heated heat preserving type, reduces energy consumption, and 13% is had dropped compared to traditional spinning manifold power consumption Left and right.
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 implementation mode
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Fixed range.
Embodiment 1
A kind of preparation method of low-shrinkage high-strength polyester industrial fiber, 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 Ethyl-2-Methyl -1 2-, 3-propanediol is made into slurry, and antimony oxide, titanium dioxide and triphenyl phosphate is added after mixing, adds in nitrogen atmosphere Pressure carries out esterification, and moulding pressure is normal pressure, and the temperature of esterification is 250 DEG C, when the water quantity of distillate in esterification reaches To theoretical value 90% when be esterification terminal, 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 structural formula of the 0.05% of sour weight, wherein 2- Ethyl-2-Methyl -1,3-PD is as follows：
(b) polycondensation reaction；After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, It is 500Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 30min, and reaction temperature is 260 DEG C, reaction time 40min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be further reduced to absolute pressure be 100Pa, instead It is 275 DEG C, reaction time 70min to answer temperature, and modified poly ester is made.The strand of wherein modified poly ester includes terephthaldehyde Sour segment, ethylene glycol segment and 2- Ethyl-2-Methyl -1,3- propylene glycol segments, the content of cyclic oligomer is in modified poly ester 0.6wt%, number-average molecular weight 20000, molecular weight distributing index 2.0,2- Ethyl-2-Methyls -1,3- the third two in modified poly ester The molar content of alcohol segment is the 3% of terephthalic acid (TPA) segment molar content；
(2) it oils and is prepared with finish；By 2- methylols -12-crown-4 and 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, trimethylolpropane Laurate and dodecyl sodium sulfate are added to after mixing at normal temperatures in 9# mineral oil and in 40 DEG C of uniform stirring 1h Obtain finish；It counts in parts by weight, the addition of each component is as follows：2 parts of 9# mineral oil；Trimethylolpropane laurate 10 Part；2- methylols -90 parts of 12-crown-4；8 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite；3 parts of dodecyl sodium sulfate.The finish prepared The content of middle crown ether is 79.6wt%, and the high temperature resistance of finish is excellent, and thermal weight loss is after heating 2h at 200 DEG C 14.5wt%；The viscosity of finish is relatively low, at (50 ± 0.01) DEG C, kinematic viscosity 29.6mm2/ s is configured to a concentration of with water Kinematic viscosity after the lotion of 10wt% is 0.93mm2/s；The film strength of finish is higher, film strength 125N, finish Surface tension is 24.8cN/cm, and specific resistance is 1.3 × 108Ω cm, after oiling, the static friction between fiber and fiber (F/F) Coefficient (μs) it is 0.255, the coefficient of kinetic friction (μd) it is 0.266, the confficient of static friction (μ between fiber and metal (F/M)s) be 0.203, the coefficient of kinetic friction (μd) it is 0.320, the finish of preparation when in use, the emulsification of a concentration of 15wt% is configured to water Liquid；
(3) modified poly ester viscosified through solid phase polycondensation, melted, measured, squeezed out, cooled down, oiled, stretched, thermal finalization and volume Around obtained low-shrinkage high-strength polyester industrial fiber.Wherein, the inherent viscosity of solid phase polycondensation thickening post-modification polyester is 1.02dL/g；
The replacement cycle of filament spinning component is 40 days, clears up the cycle stretch-out of spinneret 39%.When cooling, keep longitudinal 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, Slow cooling chamber structure schematic diagram is as shown in figure 3, by the embedded bottom for hanging on spinning manifold 1 of thermal insulation board 6, in spinning manifold 1 There is a gas phase heating agent 2, " rectangular-ambulatory-plane " is hollow in thermal insulation board 6, inside opens up hollow chamber I 3, and the cross section of the chamber is rectangle, with The side for being parallel to polylith spinneret circle center line connecting is long side direction, and the length of long side is the 1.2 of the sum of polylith spinneret board diameter Times, using perpendicular to the direction of long side, as short side direction, the length of short side is 1.7 times of spinneret board diameter, thickness be 1mm every Piece, which assigns into hollow chamber I 3, is divided into multiple slow cooling chambers, there is one block of round spinneret in each slow cooling chamber.Respectively The diameter of spinneret is identical and the center of circle is located along the same line and close adjacent.Thermal insulation board 6 is the rock of internal 400 DEG C of heatproof of filling The thickness of the stainless steel plate of cotton, thermal insulation board 6 is 30mm, and the wall thickness of stainless steel plate is 0.9mm.The superposition thickness of thermal insulation board 6 times are The material of the thermal insulation board 7 of 25mm, thermal insulation board 7 is identical as thermal insulation board 6, and hollow chamber II 5, hollow chamber II 5 are opened up in thermal insulation board 7 It is identical as the cross-sectional shape of hollow chamber I 3；Hollow chamber II 5 is identical as the long side length of the cross section of hollow chamber I 3； The position that hollow chamber II 5 is connected to hollow chamber I 3, two sides of II 5 cross section of hollow chamber respectively with hollow chamber I 3 Two short sides of cross section overlap, and the length on two sides is more than two short sides.The square of wherein corresponding single round spinneret Shape column slow cooling area is kept the temperature using thermal insulation board, the embedded bottom for hanging on spinning manifold of thermal insulation board, is equipped in thermal insulation board hollow Chamber I is superimposed thermal insulation board under thermal insulation board, hollow chamber II is offered in thermal insulation board, wherein in hollow chamber II and hollow chamber I The position of connection, two sides of II cross section of hollow chamber are overlapped with two short sides of hollow chamber I cross section respectively, and this two The length on side is more than two short sides, and it is oligomeric to accelerate to form a step for hollow chamber II and hollow chamber I after the superposition of two plates Object is spread.
The spinning technology parameter of low-shrinkage high-strength polyester industrial fiber is shown in Table 1.
Final low-shrinkage high-strength polyester industrial fiber various performance parameters obtained are shown in Table 2.
Embodiment 2
A kind of preparation method of low-shrinkage high-strength polyester industrial fiber, 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, and antimony glycol, titanium dioxide and trimethyl phosphate is added after mixing, pressurize in nitrogen atmosphere into Row esterification, moulding pressure are normal pressure, and the temperature of esterification is 260 DEG C, when the water quantity of distillate in esterification reaches reason By value 91% when be esterification terminal, wherein the addition of antimony glycol be terephthalic acid (TPA) weight 0.02%, dioxy The addition for changing titanium 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-PD is as follows：
(b) polycondensation reaction；After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, It is 490Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 35min, and reaction temperature is 261 DEG C, reaction time 30min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be further reduced to absolute pressure be 100Pa, instead It is 277 DEG C, reaction time 85min to answer temperature, and modified poly ester is made.The strand of wherein modified poly ester includes terephthaldehyde Sour 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 chain in modified poly ester The molar content of section is the 5% of terephthalic acid (TPA) segment molar content；
(2) it oils and is prepared with finish；By 15- crown ethers -5 and isomerous tridecanol polyoxyethylene ether phosphate kalium salt, three hydroxyl first Base propane laurate and pentadecyl sulfonic acid sodium be added to after mixing at normal temperatures in 10# mineral oil and 43 DEG C uniformly Stirring 1.5h obtains finish；It counts in parts by weight, the addition of each component is as follows：2 parts of 10# mineral oil；The trimethylolpropane moon 15 parts of cinnamic acid ester；- 5 70 parts of 15- crown ethers；10 parts of isomerous tridecanol polyoxyethylene ether phosphate kalium salt；Pentadecyl sulfonic acid sodium 7 Part.The content of crown ether is 67.30wt% in the finish prepared, and the high temperature resistance of finish is excellent, heats 2h at 200 DEG C Thermal weight loss is 13wt% afterwards, and the viscosity of finish is relatively low, at (50 ± 0.01) DEG C, kinematic viscosity 28.1mm2/ s, is configured with water It is 0.93mm at the kinematic viscosity after the lotion of a concentration of 10wt%2The film strength of/s, finish are higher, are 123N, finish Surface tension is 25.1cN/cm, and specific resistance is 1.5 × 108Ω cm, after oiling, the static friction between fiber and fiber (F/F) Coefficient (μs) it is 0.257, the coefficient of kinetic friction (μd) it is 0.265, after oiling, the confficient of static friction between fiber and metal (F/M) (μs) it is 0.205, the coefficient of kinetic friction (μd) it is 0.323, the finish of preparation is configured to a concentration of 14wt%'s when in use, with water Emulsion；
Modified poly ester is viscosified through solid phase polycondensation, melts, measure, squeezing out, cooling down, oiling, stretching, thermal finalization and winding are made Obtain low-shrinkage high-strength polyester industrial fiber.Wherein, the inherent viscosity of solid phase polycondensation thickening post-modification polyester is 1.12dL/g；Spinning group The replacement cycle of part is 42 days, clears up the cycle stretch-out of spinneret 40%.It when cooling, keeps longitudinal height constant, increases slow The cross-sectional area of cold chamber, while slow cooling chamber keeps the plate face temperature of spinneret, slow cooling chamber configuration by the way of heat preservation Substantially the same manner as Example 1, difference is that septa thickness is 2mm, and it is ceramic fibre that thermal insulation material is filled in thermal insulation board, heat-resisting Temperature is 405 DEG C, and heat preservation plate thickness is 40mm, and stainless steel plate wall thickness is 1.2mm, and heat-insulated plate thickness is 35mm.
The spinning technology parameter of low-shrinkage high-strength polyester industrial fiber is shown in Table 1.
Final low-shrinkage high-strength polyester industrial fiber various performance parameters obtained are shown in Table 2.
Embodiment 3
A kind of preparation method of low-shrinkage high-strength polyester industrial fiber, 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 ethyl -1 2- butyl -2-, 3-propanediol is made into slurry, and antimony acetate, titanium dioxide and Trimethyl phosphite is added after mixing, pressurizes in nitrogen atmosphere Esterification is carried out, the temperature of moulding pressure 0.1MPa, esterification are 252 DEG C, when the water quantity of distillate in esterification reaches To theoretical value 92% when be esterification terminal, wherein the addition of antimony acetate be terephthalic acid (TPA) weight 0.03%, 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 0.01%, the structural formula of wherein 2- butyl -2- ethyls -1,3-PD is as follows：
(b) polycondensation reaction；After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, It is 495Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 40min, and reaction temperature is 263 DEG C, reaction time 45min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be further reduced to absolute pressure be 95Pa, reaction Temperature is 278 DEG C, reaction time 60min, modified poly ester is made, the strand of wherein modified poly ester includes terephthalic acid (TPA) chain Section, ethylene glycol segment and 2- butyl -2- ethyls -1,3-PD segment, the content of cyclic oligomer is in modified poly ester 0.5wt%, number-average molecular weight 21000, molecular weight distributing index 2.2,2- butyl -2- ethyls -1,3- the third two in modified poly ester The molar content of alcohol segment is the 4% of terephthalic acid (TPA) segment molar content；
(2) it oils and is prepared with finish；By 2- methylol -15- crown-s 5 and ten tetracosanol phosphate kalium salts, trihydroxy methyl third Alkane laurate and pentadecyl sulfonic acid sodium are added to after mixing at normal temperatures in 11# mineral oil and in 48 DEG C of uniform stirrings 3h obtains finish；It counts in parts by weight, the addition of each component is as follows：8 parts of 11# mineral oil；Trimethylolpropane laurate 10 parts；
585 parts of 2- methylol -15- crown-s；Ten 11 parts of tetracosanol phosphate kalium salts；5 parts of pentadecyl sulfonic acid sodium.It prepares The content of crown ether is 70.83wt% in the finish gone out, and the high temperature resistance of finish is excellent, and heat is lost after heating 2h at 200 DEG C Weight is 11wt%, and the viscosity of finish is relatively low, at (50 ± 0.01) DEG C, kinematic viscosity 30.1mm2/ s is configured to concentration with water It is 0.94mm for the kinematic viscosity after the lotion of 10wt%2The film strength of/s, finish are higher, are 125N.The surface of finish Power is 23.2cN/cm, and specific resistance is 1.8 × 108Ω cm, after oiling, the confficient of static friction between fiber and fiber (F/F) (μs) it is 0.250, the coefficient of kinetic friction (μd) it is 0.272, after oiling, the confficient of static friction (μ between fiber and metal (F/M)s) be 0.209, the coefficient of kinetic friction (μd) it is 0.329, the finish of preparation when in use, the emulsification of a concentration of 15wt% is configured to water Liquid；
(3) modified poly ester viscosified through solid phase polycondensation, melted, measured, squeezed out, cooled down, oiled, stretched, thermal finalization and volume Around obtained low-shrinkage high-strength polyester industrial fiber.Wherein, the inherent viscosity of solid phase polycondensation thickening post-modification polyester is 1.10dL/g；It spins The replacement cycle of silk component is 48 days, clears up the cycle stretch-out of spinneret 44%.When cooling, keep longitudinal height constant, increase The cross-sectional area of big slow cooling chamber, while slow cooling chamber keeps the plate face temperature of spinneret, slow cooling chamber by the way of heat preservation Construct substantially the same manner as Example 1, difference is that septa thickness is 3mm, and filling thermal insulation material is rock wool in thermal insulation board, heat-resisting Temperature is 410 DEG C, and heat preservation plate thickness is 50mm, and stainless steel plate wall thickness is 1.5mm, and heat-insulated plate thickness is 45mm.
The spinning technology parameter of low-shrinkage high-strength polyester industrial fiber is shown in Table 1.
Final low-shrinkage high-strength polyester industrial fiber various performance parameters obtained are shown in Table 2.
Embodiment 4
A kind of preparation method of low-shrinkage high-strength polyester industrial fiber, 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 and Triethylamine react 20min, then by concentrate addition have in the hydrogenation reactor of thunder girl's Raney nickel, 2.914MPa hydrogen pressure and It is reacted at 100 DEG C, reaction is finished, cooling, and catalyst is made to be precipitated, and after the processing of solution spent ion exchange resin, is depressurized and is steamed water, separation, Purification, obtains 3,3- diethyl -1,5- pentanediols, 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, and antimony oxide, titanium dioxide and triphenyl phosphate is added after mixing, pressurizes in nitrogen atmosphere Esterification is carried out, the temperature of moulding pressure 0.3MPa, esterification are 255 DEG C, when the water quantity of distillate in esterification reaches To theoretical value 95% when be esterification terminal, 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 of low vacuum stage under condition of negative pressure, It is 400Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 50min, and reaction temperature is 265 DEG C, reaction time 33min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be further reduced to absolute pressure be 90Pa, reaction Temperature is 280 DEG C, reaction time 50min, modified poly ester is made, the strand of wherein modified poly ester includes terephthalic acid (TPA) chain Section, ethylene glycol segment and 3,3- diethyl -1,5-PD segment, the content of cyclic oligomer is 0.2wt% in modified poly ester, Number-average molecular weight 23000, molecular weight distributing index 1.9,3,3- diethyl -1,5-PD segment rubs in modified poly ester Your content is the 3.5% of terephthalic acid (TPA) segment molar content；
(2) it oils and is prepared with finish；By 2- methylols -12-crown-4 and 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, trimethylolpropane Laurate and sodium cetanesulfonate are added to after mixing at normal temperatures in 12# mineral oil and in 40 DEG C of uniform stirrings 2.5h obtains finish；It counts in parts by weight, the addition of each component is as follows：5 parts of 12# mineral oil；2- methylols -12-crown-4 95 Part；9 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite；2 parts of sodium cetanesulfonate.The content of crown ether is in the finish prepared The high temperature resistance of 85.58wt%, finish are excellent, and it is 9wt% to heat thermal weight loss after 2h at 200 DEG C, the viscosity of finish compared with It is low, at (50 ± 0.01) DEG C, kinematic viscosity 29.5mm2/ s, the movement being configured to water after the lotion of a concentration of 10wt% Viscosity is 0.93mm2The film strength of/s, finish are higher, are 121N, the surface tension of finish is 24.3cN/cm, and specific resistance is 1.0×108Ω cm, after oiling, the confficient of static friction (μ between fiber and fiber (F/F)s) it is 0.260, the coefficient of kinetic friction (μd) it is 0.263, after oiling, the confficient of static friction (μ between fiber and metal (F/M)s) it is 0.202, the coefficient of kinetic friction (μd) be 0.330, the finish of preparation when in use, the emulsion of a concentration of 18wt% is configured to water；
(3) modified poly ester viscosified through solid phase polycondensation, melted, measured, squeezed out, cooled down, oiled, stretched, thermal finalization and volume Around obtained low-shrinkage high-strength polyester industrial fiber.Wherein, the inherent viscosity of solid phase polycondensation thickening post-modification polyester is 1.18dL/g；It spins The replacement cycle of silk component is 44 days, clears up the cycle stretch-out of spinneret 35%.When cooling, keep longitudinal height constant, increase The cross-sectional area of big slow cooling chamber, while slow cooling chamber keeps the plate face temperature of spinneret, slow cooling chamber by the way of heat preservation Construct substantially the same manner as Example 1, difference is that septa thickness is 1.5mm, and filling thermal insulation material is ceramic fibre in thermal insulation board, Its heat resisting temperature is 402 DEG C, and heat preservation plate thickness is 35mm, and stainless steel plate wall thickness is 1.0mm, and heat-insulated plate thickness is 30mm.
The spinning technology parameter of low-shrinkage high-strength polyester industrial fiber is shown in Table 1.
Final low-shrinkage high-strength polyester industrial fiber various performance parameters obtained are shown in Table 2.
Embodiment 5
A kind of preparation method of low-shrinkage high-strength polyester industrial fiber, 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 and Triethylamine react 20min, then by concentrate addition have in the hydrogenation reactor of thunder girl's Raney nickel, 2.914MPa hydrogen pressure and It is reacted at 100 DEG C, reaction is finished, cooling, and catalyst is made to be precipitated, and after the processing of solution spent ion exchange resin, is depressurized and is steamed 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, and antimony glycol, titanium dioxide and trimethyl phosphate is added after mixing, pressurize in nitrogen atmosphere into Row esterification, moulding pressure are normal pressure, and the temperature of esterification is 257 DEG C, when the water quantity of distillate in esterification reaches reason By value 92% when be esterification terminal, wherein the addition of antimony glycol be terephthalic acid (TPA) weight 0.05%, dioxy The addition for changing titanium 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 of low vacuum stage under condition of negative pressure, It is 450Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 33min, and reaction temperature is 270 DEG C, reaction time 30min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be further reduced to absolute pressure be 95Pa, reaction Temperature is 275 DEG C, reaction time 60min, modified poly ester is made, the strand of wherein modified poly ester includes terephthalic acid (TPA) chain Section, ethylene glycol segment and 4,4- diethyl -1,7- heptandiol segments, the content of cyclic oligomer is 0.5wt% in modified poly ester, Number-average molecular weight 25000, molecular weight distributing index 2.1,4,4- diethyl -1,7- heptandiol segments rubs in modified poly ester Your content is the 5% of terephthalic acid (TPA) segment molar content.
(2) it oils and is prepared with finish；By 15- crown ethers -5 and isomerous tridecanol polyoxyethylene ether phosphate kalium salt, three hydroxyl first Base propane laurate and dodecyl sodium sulfate be added to after mixing at normal temperatures in 13# mineral oil and 52 DEG C uniformly Stirring 2h obtains finish；It counts in parts by weight, the addition of each component is as follows：10 parts of 13# mineral oil；Trimethylolpropane bay 5 parts of acid esters；- 5 70 parts of 15- crown ethers；8 parts of isomerous tridecanol polyoxyethylene ether phosphate kalium salt；6 parts of dodecyl sodium sulfate.System Content for crown ether in the finish gone out is 70.70wt%, and the high temperature resistance of finish is excellent, heats heat after 2h at 200 DEG C Weightlessness is 13.5wt%, and the viscosity of finish is relatively low, at (50 ± 0.01) DEG C, kinematic viscosity 28.6mm2/ s, is configured to water Kinematic viscosity after the lotion of a concentration of 10wt% is 0.95mm2The film strength of/s, finish are higher, are 126N, the table of finish Face tension is 24.9cN/cm, and specific resistance is 1.2 × 108Ω cm, after oiling, the static friction system between fiber and fiber (F/F) Number (μs) it is 0.251, the coefficient of kinetic friction (μd) it is 0.262, after oiling, the confficient of static friction (μ between fiber and metal (F/M)s) It is 0.202, the coefficient of kinetic friction (μd) it is 0.332, the finish of preparation when in use, the emulsification of a concentration of 15wt% is configured to water Liquid；
(3) modified poly ester viscosified through solid phase polycondensation, melted, measured, squeezed out, cooled down, oiled, stretched, thermal finalization and volume Around obtained low-shrinkage high-strength polyester industrial fiber.Wherein, the inherent viscosity of solid phase polycondensation thickening post-modification polyester is 1.0dL/g；It spins The replacement cycle of silk component is 49 days, clears up the cycle stretch-out of spinneret 36%.When cooling, keep longitudinal height constant, increase The cross-sectional area of big slow cooling chamber, while slow cooling chamber keeps the plate face temperature of spinneret, slow cooling chamber by the way of heat preservation Construct substantially the same manner as Example 1, difference is that it only has thermal insulation board, and thermal insulation board is not superimposed under thermal insulation board.
The spinning technology parameter of low-shrinkage high-strength polyester industrial fiber is shown in Table 1.
Final low-shrinkage high-strength polyester industrial fiber various performance parameters obtained are shown in Table 2.
Embodiment 6
A kind of preparation method of low-shrinkage high-strength polyester industrial fiber, 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- methyl of 4,4- bis- Ethyl)-butyraldehyde, propionic aldehyde and triethylamine react 20min, then concentrate is added to the hydrogenation reactor for having thunder girl's Raney nickel In, it is reacted at 2.914MPa hydrogen pressure and 100 DEG C, reaction is finished, cooling, and catalyst is made to be precipitated.At solution spent ion exchange resin After reason, water is steamed in decompression, detaches, and purification obtains 4,4- bis- (1,-Methylethyl) -1,7- heptandiols, wherein 4,4- bis- (1,-first Base ethyl) -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 second Base) -1,7- heptandiols are made into slurry, antimony acetate, titanium dioxide and Trimethyl phosphite is added after mixing, in nitrogen atmosphere Middle pressurization carries out esterification, and the temperature of moulding pressure 0.2MPa, esterification are 253 DEG C, when the water in esterification evaporates Output 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 two The 0.05% of formic acid weight；
(c) polycondensation reaction；After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, It is 480Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 38min, and reaction temperature is 262 DEG C, reaction time 38min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be further reduced to absolute pressure be 98Pa, reaction Temperature is 279 DEG C, reaction time 80min, modified poly ester is made, the strand of wherein modified poly ester includes terephthalic acid (TPA) chain Section, ethylene glycol segment and 4,4- bis- (1,-Methylethyl) -1,7- heptandiol segments, the content of cyclic oligomer in modified poly ester For 0.55wt%, number-average molecular weight 27000, molecular weight distributing index 2.2,4,4- bis- (1 ,-Methylethyl)-in modified poly ester The molar content of 1,7- heptandiol segments is the 4% of terephthalic acid (TPA) segment molar content；
(2) it oils and is prepared with finish；By 2- methylol -15- crown-s 5 and ten tetracosanol phosphate kalium salts, trihydroxy methyl third Alkane laurate and pentadecyl sulfonic acid sodium are added to after mixing at normal temperatures in 14# mineral oil and in 55 DEG C of uniform stirrings 1h obtains finish；It counts in parts by weight, the addition of each component is as follows：3 parts of 14# mineral oil；Trimethylolpropane laurate 10 parts；5 75 parts of 2- methylol -15- crown-s；Ten 14 parts of tetracosanol phosphate kalium salts；7 parts of pentadecyl sulfonic acid sodium.It prepares Finish in crown ether content be 68.80wt%, the high temperature resistance of finish is excellent, at 200 DEG C heat 2h after thermal weight loss Viscosity for 12wt%, finish is relatively low, at (50 ± 0.01) DEG C, kinematic viscosity 27.5mm2/ s is configured to concentration with water It is 0.95mm for the kinematic viscosity after the lotion of 10wt%2The film strength of/s, finish are higher, are 126N.The surface of finish Power is 25.4cN/cm, and specific resistance is 1.6 × 108Ω cm, after oiling, the confficient of static friction between fiber and fiber (F/F) (μs) it is 0.255, the coefficient of kinetic friction (μd) it is 0.267, after oiling, the confficient of static friction (μ between fiber and metal (F/M)s) It is 0.203, the coefficient of kinetic friction (μd) it is 0.330, the finish of preparation when in use, the emulsification of a concentration of 16wt% is configured to water Liquid；
(3) modified poly ester viscosified through solid phase polycondensation, melted, measured, squeezed out, cooled down, oiled, stretched, thermal finalization and volume Around obtained low-shrinkage high-strength polyester industrial fiber.Wherein, the inherent viscosity of solid phase polycondensation thickening post-modification polyester is 1.0dL/g；It spins The replacement cycle of silk component is 40 days, clears up the cycle stretch-out of spinneret 41%.When cooling, keep longitudinal height constant, increase The cross-sectional area of big slow cooling chamber, while slow cooling chamber keeps the plate face temperature of spinneret, slow cooling chamber by the way of heat preservation Construct substantially the same manner as Example 2, difference is that it only has thermal insulation board, and thermal insulation board is not superimposed under thermal insulation board.
The spinning technology parameter of low-shrinkage high-strength polyester industrial fiber is shown in Table 1.
Final low-shrinkage high-strength polyester industrial fiber various performance parameters obtained are shown in Table 2.
Embodiment 7
A kind of preparation method of low-shrinkage high-strength polyester industrial fiber, 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 and Triethylamine react 20min, then by concentrate addition have in the hydrogenation reactor of thunder girl's Raney nickel, 2.914MPa hydrogen pressure and It is reacted at 100 DEG C, reaction is finished, cooling, and catalyst is made to be precipitated.After the processing of solution spent ion exchange resin, water is steamed in decompression, detaches, Purification, obtains 3,3- dipropyl -1,5- pentanediols, 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, and antimony oxide, titanium dioxide and triphenyl phosphate is added after mixing, pressurizes in nitrogen atmosphere Esterification is carried out, the temperature of moulding pressure 0.3MPa, esterification are 250 DEG C, when the water quantity of distillate in esterification reaches To theoretical value 90% when be esterification terminal, 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 of low vacuum stage under condition of negative pressure, It is 455Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 42min, and reaction temperature is 264 DEG C, reaction time 45min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be further reduced to absolute pressure be 85Pa, reaction Temperature is 285 DEG C, reaction time 75min, modified poly ester is made, the strand of wherein modified poly ester includes terephthalic acid (TPA) chain Section, 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) it oils and is prepared with finish；By 15- crown ethers -5 and 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, trimethylolpropane lauric acid Ester and sodium cetanesulfonate are added in 15# mineral oil and obtain oil in 41 DEG C of uniform stirring 2h after mixing at normal temperatures Agent；It counts in parts by weight, the addition of each component is as follows：8 parts of 15# mineral oil；20 parts of trimethylolpropane laurate；15- 100 parts of crown ether -5；15 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite；2 parts of sodium cetanesulfonate.Crown ether contains in the finish prepared Amount is 68.97wt%, and the high temperature resistance of finish is excellent, and thermal weight loss is 8.5wt% after heating 2h at 200 DEG C, finish Viscosity is relatively low, at (50 ± 0.01) DEG C, kinematic viscosity 28.4mm2/ s, after the lotion of a concentration of 10wt% is configured to water Kinematic viscosity be 0.94mm2The film strength of/s, finish are higher, are 122N.The surface tension of finish is 26.8cN/cm, than Resistance is 1.8 × 108Ω cm, after oiling, the confficient of static friction (μ between fiber and fiber (F/F)s) it is 0.263, dynamic friction Coefficient (μd) it is 0.268, after oiling, the confficient of static friction (μ between fiber and metal (F/M)s) it is 0.210, the coefficient of kinetic friction (μd) it is 0.320, the finish of preparation when in use, the emulsion of a concentration of 17wt% is configured to water；
(3) modified poly ester viscosified through solid phase polycondensation, melted, measured, squeezed out, cooled down, oiled, stretched, thermal finalization and volume Around obtained low-shrinkage high-strength polyester industrial fiber.Wherein, the inherent viscosity of solid phase polycondensation thickening post-modification polyester is 1.2dL/g；It spins The replacement cycle of silk component is 41 days, clears up the cycle stretch-out of spinneret 44%.When cooling, keep longitudinal height constant, increase The cross-sectional area of big slow cooling chamber, while slow cooling chamber keeps the plate face temperature of spinneret, slow cooling chamber by the way of heat preservation Construct substantially the same manner as Example 3, difference is that it only has thermal insulation board, and thermal insulation board is not superimposed under thermal insulation board.
The spinning technology parameter of low-shrinkage high-strength polyester industrial fiber is shown in Table 1.
Final low-shrinkage high-strength polyester industrial fiber various performance parameters obtained are shown in Table 2.
Embodiment 8
A kind of preparation method of low-shrinkage high-strength polyester industrial fiber, 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 and Triethylamine react 20min, then by concentrate addition have in the hydrogenation reactor of thunder girl's Raney nickel, 2.914MPa hydrogen pressure and It is reacted at 100 DEG C, reaction is finished, cooling, and catalyst is made to be precipitated.After the processing of solution spent ion exchange resin, water is steamed in decompression, detaches, 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, and antimony glycol, titanium dioxide and trimethyl phosphate is added after mixing, pressurize in nitrogen atmosphere into The temperature of row esterification, moulding pressure 0.3MPa, esterification is 260 DEG C, when the water quantity of distillate in esterification reaches Theoretical value 93% when be esterification terminal, wherein the addition of antimony glycol be terephthalic acid (TPA) weight 0.04%, 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%；
(c) polycondensation reaction；After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, It is 475Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 45min, and reaction temperature is 265 DEG C, reaction time 48min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be further reduced to absolute pressure be 88Pa, reaction Temperature is 283 DEG C, reaction time 80min, modified poly ester is made, the strand of wherein modified poly ester includes terephthalic acid (TPA) chain Section, ethylene glycol segment and 4,4- dipropyl -1,7- heptandiol segments, the content of cyclic oligomer is 0.6wt% in modified poly ester, Number-average molecular weight 23000, molecular weight distributing index 2.0,4,4- dipropyl -1,7- heptandiol segments rubs in modified poly ester Your content is the 3% of terephthalic acid (TPA) segment molar content；
(2) it oils and is prepared with finish；By 2- methylols -12-crown-4 and ten tetracosanol phosphate kalium salts, trihydroxy methyl third Alkane laurate and pentadecyl sulfonic acid sodium are added to after mixing at normal temperatures in 16# mineral oil and in 45 DEG C of uniform stirrings 3h obtains finish；It counts in parts by weight, the addition of each component is as follows：9 parts of 16# mineral oil；2- methylols -12-crown-4 80 Part；Ten 12 parts of tetracosanol phosphate kalium salts；5 parts of pentadecyl sulfonic acid sodium.The content of crown ether is in the finish prepared The high temperature resistance of 83.33wt%, finish are excellent, and it is 14wt% to heat thermal weight loss after 2h at 200 DEG C, the viscosity of finish compared with It is low, at (50 ± 0.01) DEG C, kinematic viscosity 30.0mm2/ s, the movement being configured to water after the lotion of a concentration of 10wt% Viscosity is 0.93mm2The film strength of/s, finish are higher, are 127N.The surface tension of finish is 23.5cN/cm, and specific resistance is 1.5×108Ω cm, after oiling, the confficient of static friction (μ between fiber and fiber (F/F)s) it is 0.262, the coefficient of kinetic friction (μd) it is 0.273, after oiling, the confficient of static friction (μ between fiber and metal (F/M)s) it is 0.208, the coefficient of kinetic friction (μd) be 0.328, the finish of preparation when in use, the emulsion of a concentration of 18wt% is configured to water；
(3) modified poly ester viscosified through solid phase polycondensation, melted, measured, squeezed out, cooled down, oiled, stretched, thermal finalization and volume Around obtained low-shrinkage high-strength polyester industrial fiber.Wherein, the inherent viscosity of solid phase polycondensation thickening post-modification polyester is 1.15L/g；It spins The replacement cycle of silk component is 44 days, clears up the cycle stretch-out of spinneret 45%.When cooling, keep longitudinal height constant, increase The cross-sectional area of big slow cooling chamber, while slow cooling chamber keeps the plate face temperature of spinneret, slow cooling chamber by the way of heat preservation Construct substantially the same manner as Example 4, difference is that it only has thermal insulation board, and thermal insulation board is not superimposed under thermal insulation board.
The spinning technology parameter of low-shrinkage high-strength polyester industrial fiber is shown in Table 1.
Final low-shrinkage high-strength polyester industrial fiber various performance parameters obtained are shown in Table 2.
Embodiment 9
A kind of preparation method of low-shrinkage high-strength polyester industrial fiber, 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- methyl- Then concentrate addition is had thunder girl's Raney nickel by 4- (1,1- dimethyl ethyl)-butyraldehyde, propionic aldehyde and triethylamine react 20min Hydrogenation reactor in, reacted at 2.914MPa hydrogen pressure and 100 DEG C, reaction is finished, cooling, and catalyst is made to be precipitated, solution with from After sub-exchange resin processing, water is steamed in decompression, detaches, and purification obtains 4- methyl -4- (1,1- dimethyl ethyl) -1,7- heptandiols, The structural formula of wherein 4- methyl -4- (1,1- dimethyl ethyls) -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- bis- Methylethyl) -1,7- heptandiols are made into slurry, antimony acetate, titanium dioxide and trimethyl phosphate is added after mixing, in nitrogen Atmosphere encloses middle pressurization and carries out esterification, and moulding pressure is normal pressure MPa, and the temperature of esterification is 251 DEG C, when in esterification Water quantity of distillate be esterification terminal when reaching the 96% of theoretical value, wherein the addition of antimony acetate is terephthalic acid (TPA) weight 0.05%, the addition of titanium dioxide is the 0.22% of terephthalic acid (TPA) weight, and the addition of trimethyl phosphate is to benzene two The 0.04% of formic acid weight；
(c) polycondensation reaction；After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, It is 420Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 30min, and reaction temperature is 267 DEG C, reaction time 50min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be further reduced to absolute pressure be 80Pa, reaction Temperature is 280 DEG C, reaction time 90min, modified poly ester is made, the strand of wherein modified poly ester includes terephthalic acid (TPA) chain Section, ethylene glycol segment and 4- methyl -4- (1,1- dimethyl ethyl) -1,7- heptandiol segments, cyclic oligomer in modified poly ester Content be 0.25wt%, number-average molecular weight 24000, molecular weight distributing index 2.2,4- methyl -4- (1,1- in modified poly ester Dimethyl ethyl) -1,7- heptandiol segments molar content be terephthalic acid (TPA) segment molar content 4%；
(2) it oils and is prepared with finish；By 2- methylol -15- crown-s 5 and 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, trimethylolpropane Laurate and dodecyl sodium sulfate obtain finish after mixing and in 55 DEG C of uniform stirring 3h at normal temperatures；By weight Number meter, the addition of each component are as follows：15 parts of trimethylolpropane laurate；5 90 parts of 2- methylol -15- crown-s；Dodecane 8 parts of base phosphate kalium salt；7 parts of dodecyl sodium sulfate.The content of crown ether is 81.81wt% in the finish prepared, finish High temperature resistance is excellent, and thermal weight loss is 10wt% after heating 2h at 200 DEG C, and the viscosity of finish is relatively low, in (50 ± 0.01) DEG C when, kinematic viscosity 29.7mm2/ s, it is 0.94mm that the kinematic viscosity after the lotion of a concentration of 10wt% is configured to water2/ s, The film strength of finish is higher, is 126N.The surface tension of finish is 24.8cN/cm, and specific resistance is 1.8 × 108Ω cm, on After oil, the confficient of static friction (μ between fiber and fiber (F/F)s) it is 0.250, the coefficient of kinetic friction (μd) it is 0.264, after oiling, Confficient of static friction (μ between fiber and metal (F/M)s) it is 0.210, the coefficient of kinetic friction (μd) it is 0.321, the finish of preparation exists In use, being configured to the emulsion of a concentration of 14wt% with water；
(3) modified poly ester viscosified through solid phase polycondensation, melted, measured, squeezed out, cooled down, oiled, stretched, thermal finalization and volume Around obtained low-shrinkage high-strength polyester industrial fiber.Wherein, the inherent viscosity of solid phase polycondensation thickening post-modification polyester is 1.09dL/g；It spins The replacement cycle of silk component is 45 days, clears up the cycle stretch-out of spinneret 35%.When cooling, keep longitudinal height constant, increase The cross-sectional area of big slow cooling chamber, while slow cooling chamber keeps the plate face temperature of spinneret, slow cooling chamber by the way of heat preservation Construct substantially the same manner as Example 1, difference is that septa thickness is 3mm, and filling thermal insulation material is rock wool in thermal insulation board, heat-resisting Temperature is 410 DEG C, and heat preservation plate thickness is 50mm, and stainless steel plate wall thickness is 1.5mm, and heat-insulated plate thickness is 45mm.
The spinning technology parameter of low-shrinkage high-strength polyester industrial fiber is shown in Table 1.
Final low-shrinkage high-strength polyester industrial fiber various performance parameters obtained are shown in Table 2.
Embodiment 10
A kind of preparation method of low-shrinkage high-strength polyester industrial fiber, 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-propionic aldehyde, Then propionic aldehyde and triethylamine react 20min have concentrate addition in the hydrogenation reactor of thunder girl's Raney nickel, in 2.914MPa Hydrogen press and 100 DEG C at react, reaction is finished, cooling, and catalyst is made to be precipitated.After the processing of solution spent ion exchange resin, water is steamed in decompression, Separation, purification, obtains 3- methyl -3- amyl -1,6- hexylene glycols, the wherein structural formula of 3- methyl -3- amyl -1,6- hexylene glycols It is as follows：
(b) esterification；It is 1 by molar ratio:1.2:0.06 terephthalic acid (TPA), ethylene glycol and amyl -1 3- methyl -3-, 6- hexylene glycols are made into slurry, and antimony glycol, titanium dioxide and Trimethyl phosphite is added after mixing, add in nitrogen atmosphere Pressure carries out esterification, and the temperature of moulding pressure 0.1MPa, esterification are 255 DEG C, when the water quantity of distillate in esterification It is esterification terminal when reaching the 92% of theoretical value, 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 of low vacuum stage under condition of negative pressure, It is 490Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 50min, and reaction temperature is 269 DEG C, reaction time 30min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be further reduced to absolute pressure be 100Pa, instead It is 281 DEG C, reaction time 55min to answer temperature, modified poly ester is made, the strand of wherein modified poly ester includes terephthaldehyde Sour segment, ethylene glycol segment and 3- methyl -3- amyl -1,6- hexylene glycol segments, the content of cyclic oligomer is in modified poly ester 0.1wt%, number-average molecular weight 20000, molecular weight distributing index 1.9, in modified poly ester 3- methyl -3- amyls -1,6- oneself two The molar content of alcohol segment is the 3.5% of terephthalic acid (TPA) segment molar content；
(2) it oils and is prepared with finish；By 2- methylol -15- crown-s 5 and 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, trimethylolpropane Laurate and dodecyl sodium sulfate obtain finish after mixing and in 55 DEG C of uniform stirring 3h at normal temperatures；By weight Number meter, the addition of each component are as follows：15 parts of trimethylolpropane laurate；5 90 parts of 2- methylol -15- crown-s；Dodecane 8 parts of base phosphate kalium salt；7 parts of dodecyl sodium sulfate.The content of crown ether is 81.81wt% in the finish prepared, finish High temperature resistance is excellent, and thermal weight loss is 10wt% after heating 2h at 200 DEG C, and the viscosity of finish is relatively low, in (50 ± 0.01) DEG C when, kinematic viscosity 29.7mm2/ s, it is 0.94mm that the kinematic viscosity after the lotion of a concentration of 10wt% is configured to water2/ s, The film strength of finish is higher, is 126N, the surface tension of finish is 24.8cN/cm, and specific resistance is 1.8 × 108Ω cm, on After oil, the confficient of static friction (μ between fiber and fiber (F/F)s) it is 0.250, the coefficient of kinetic friction (μd) it is 0.264, after oiling, Confficient of static friction (μ between fiber and metal (F/M)s) it is 0.210, the coefficient of kinetic friction (μd) it is 0.321, the finish of preparation exists In use, being configured to the emulsion of a concentration of 15wt% with water；
(3) modified poly ester viscosified through solid phase polycondensation, melted, measured, squeezed out, cooled down, oiled, stretched, thermal finalization and volume Around obtained low-shrinkage high-strength polyester industrial fiber.Wherein, the inherent viscosity of solid phase polycondensation thickening post-modification polyester is 1.1dL/g；It spins The replacement cycle of silk component is 42 days, clears up the cycle stretch-out of spinneret 35%.When cooling, keep longitudinal height constant, increase The cross-sectional area of big slow cooling chamber, while slow cooling chamber keeps the plate face temperature of spinneret, slow cooling chamber by the way of heat preservation Construct substantially the same manner as Example 1, difference is that it only has thermal insulation board, and thermal insulation board is not superimposed under thermal insulation board.
The spinning technology parameter of low-shrinkage high-strength polyester industrial fiber is shown in Table 1.
Final low-shrinkage high-strength polyester industrial fiber various performance parameters obtained are shown in Table 2.
Embodiment 11
A kind of preparation method of low-shrinkage high-strength polyester industrial fiber, 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 and Triethylamine react 20min, then by concentrate addition have in the hydrogenation reactor of thunder girl's Raney nickel, 2.914MPa hydrogen pressure and It is reacted at 100 DEG C, reaction is finished, cooling, and catalyst is made to be precipitated.After the processing of solution spent ion exchange resin, water is steamed in decompression, detaches, Purification, obtains 3,3- diamyl -1,5- pentanediols, 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, and antimony acetate, titanium dioxide and Trimethyl phosphite is added after mixing, pressurize in nitrogen atmosphere into The temperature of row esterification, moulding pressure 0.2MPa, esterification is 250 DEG C, when the water quantity of distillate in esterification reaches Theoretical value 97% when be esterification terminal, wherein the addition of antimony acetate be terephthalic acid (TPA) weight 0.01%, dioxy The addition for changing titanium 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 of low vacuum stage under condition of negative pressure, It is 500Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 45min, and reaction temperature is 260 DEG C, reaction time 40min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be further reduced to absolute pressure be 92Pa, reaction Temperature is 277 DEG C, reaction time 80min, modified poly ester is made, the strand of wherein modified poly ester includes terephthalic acid (TPA) chain Section, 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) it oils and is prepared with finish；By 2- methylols -12-crown-4 and 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, trimethylolpropane Laurate and dodecyl sodium sulfate are added to after mixing at normal temperatures in 9# mineral oil and in 40 DEG C of uniform stirring 1h Obtain finish；It counts in parts by weight, the addition of each component is as follows：2 parts of 9# mineral oil；Trimethylolpropane laurate 10 Part；2- methylols -90 parts of 12-crown-4；8 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite；3 parts of dodecyl sodium sulfate.The finish prepared The content of middle crown ether is 79.6wt%, and the high temperature resistance of finish is excellent, and thermal weight loss is after heating 2h at 200 DEG C The viscosity of 14.5wt%, finish are relatively low, at (50 ± 0.01) DEG C, kinematic viscosity 29.6mm2/ s is configured to a concentration of with water Kinematic viscosity after the lotion of 10wt% is 0.93mm2The film strength of/s, finish are higher, film strength 125N, finish Surface tension is 24.8cN/cm, and specific resistance is 1.3 × 108Ω cm, after oiling, the static friction between fiber and fiber (F/F) Coefficient (μs) it is 0.255, the coefficient of kinetic friction (μd) it is 0.266, after oiling, the confficient of static friction between fiber and metal (F/M) (μs) it is 0.203, the coefficient of kinetic friction (μd) it is 0.320, the finish of preparation is configured to a concentration of 15wt%'s when in use, with water Emulsion；
(3) modified poly ester viscosified through solid phase polycondensation, melted, measured, squeezed out, cooled down, oiled, stretched, thermal finalization and volume Around obtained low-shrinkage high-strength polyester industrial fiber.Wherein, the inherent viscosity of solid phase polycondensation thickening post-modification polyester is 1.2dL/g；It spins 47 days replacement cycles of silk component, clear up the cycle stretch-out of spinneret 40%.When cooling, keep longitudinal height constant, increase The cross-sectional area of slow cooling chamber, while slow cooling chamber keeps the plate face temperature of spinneret, slow cooling chamber structure by the way of heat preservation Make substantially the same manner as Example 2, difference is that it only has thermal insulation board, and thermal insulation board is not superimposed under thermal insulation board.
The spinning technology parameter of low-shrinkage high-strength polyester industrial fiber is shown in Table 1.
Final low-shrinkage high-strength polyester industrial fiber various performance parameters obtained are shown in Table 2.
Table 1
Table 2

Claims (10)

1. a kind of low-shrinkage high-strength polyester industrial fiber, it is characterized in that：The material of low-shrinkage high-strength polyester industrial fiber is modified poly ester, The strand of modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment and branched dihydric alcohol segment, and branched two The structural formula of first alcohol 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, R4The alkyl for being 2~5 selected from carbon atom number；
Fracture strength >=7.3cN/dtex of low-shrinkage high-strength polyester industrial fiber, in 177 DEG C, 10min and 0.05cN/dtex conditions Under dry-hot shrinkage be 1.8 ± 0.5%, dry-hot shrinkage under the conditions of 190 DEG C, 15min and 0.01cN/dtex is 3.5 ± 0.5%.
2. a kind of low-shrinkage high-strength polyester industrial fiber according to claim 1, which is characterized in that the low-shrinkage high-strength is poly- The fiber number of ester industrial yarn is 930~1440dtex, and line density deviation ratio is ± 1.5%, fracture strength CV value≤3.0%, fracture Elongation central value is 19.0~21.0%, and elongation at break deviation ratio is ± 2.0%, extension at break CV value≤8.0%, network For 6 ± 2/m, oil content is 0.40~0.80%, full-rolling rate >=99%.
3. a kind of low-shrinkage high-strength polyester industrial fiber according to claim 1 or 2, which is characterized in that the modified poly ester Content≤0.6wt% of middle cyclic oligomer；
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 be 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 low-shrinkage high-strength polyester industrial fiber according to claim 3, which is characterized in that the system of the modified poly ester Preparation Method is：By terephthalic acid (TPA), ethylene glycol and the branched dihydric alcohol after mixing successively carry out esterification and Polycondensation reaction obtains modified poly ester；The specific preparation process of the modified poly ester is as follows：
(1) esterification；
Terephthalic acid (TPA), ethylene glycol and the branched dihydric alcohol are made into slurry, catalyst is added and stabilizer mixing is equal After even, the pressurization progress esterification in nitrogen atmosphere, moulding pressure is normal pressure~0.3MPa, and the temperature of esterification is 250 ~260 DEG C, be esterification terminal when the water quantity of distillate in esterification reaches 90% or more of theoretical value；
(2) polycondensation reaction；
After esterification, start the polycondensation reaction of 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, so that reaction pressure is 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 low-shrinkage high-strength polyester industrial fiber according to claim 4, which is characterized in that in step (1), to benzene two The molar ratio of formic acid, ethylene glycol and the branched dihydric alcohol is 1:1.2~2.0:0.03~0.06, the catalyst adds Enter 0.01~0.05% that amount is terephthalic acid (TPA) weight, the addition of the stabilizer be terephthalic acid (TPA) weight 0.01~ 0.05%；
The catalyst is antimony oxide, antimony glycol or antimony acetate, and the stabilizer is triphenyl phosphate, trimethyl phosphate Or Trimethyl phosphite.
6. preparing such as a kind of method of low-shrinkage high-strength polyester industrial fiber of Claims 1 to 5 any one of them, feature to exist In, the modified poly ester is viscosified through solid phase polycondensation, melts, measure, squeezing out, cooling down, oiling, stretching, thermal finalization and winding system Obtain low-shrinkage high-strength polyester industrial fiber；
It when described cooling, keeps longitudinal 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；
Contain crown ether in the finish to oil, and the content of crown ether is 67.30~85.58wt%；
The finish when in use, the emulsion of a concentration of 14~18wt% is configured to water.
7. according to the method described in claim 6, it is characterized in that, the inherent viscosity of solid phase polycondensation thickening post-modification polyester For 1.0~1.2dL/g；
The cycle stretch-out of spinneret 35~45% is cleared up in replacement cycle >=40 day of filament spinning component；
The cross-sectional area for increasing slow cooling chamber refers to being incited somebody to action under the premise of the spinneret for keeping connecting 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 assigns into hollow chamber I, is divided into multiple slow cooling chambers, has one in each slow cooling chamber Block spinneret；
The thermal insulation board is the stainless steel plate of the thermal insulation material of internal 400 DEG C of heatproof of filling or more, the thickness of thermal insulation board is 30~ The wall thickness of 50mm, stainless steel plate are 0.9~1.5mm；
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 described polylith spinneret board diameter, and the length of the short side is the spinneret 1.7 times of diameter.
8. the method according to the description of claim 7 is characterized in that be superimposed thermal insulation board under the thermal insulation board, the material of thermal insulation board It is identical as thermal insulation board, hollow chamber II is opened up in thermal insulation board, hollow chamber II is identical as the cross-sectional shape of hollow chamber I；
In the position that hollow chamber II is connected to 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.
9. according to the method described in claim 8, it is characterized in that, thermal weight loss is small after the finish heats 2h at 200 DEG C In 15wt%；
For the finish at (50 ± 0.01) DEG C, kinematic viscosity is 27.5~30.1mm2/ s, the finish are configured to concentration with water It is 0.93~0.95mm for the kinematic viscosity after the lotion of 10wt%2/s；
The film strength of the finish is 121~127N；
The surface tension of the finish is 23.2~26.8cN/cm, and specific resistance is 1.0 × 108~1.8 × 108Ω·cm；
After oiling, the confficient of static friction between fiber and fiber is 0.250~0.263, and the coefficient of kinetic friction is 0.262~0.273；
After oiling, the confficient of static friction between fiber and metal is 0.202~0.210, and the coefficient of kinetic friction is 0.320~0.332；
The crown ether is 2- methylols -12-crown-4,15- crown ethers -5 or 2- methylol -15- crown-s 5；
Also contain mineral oil, phosphate kalium salt, trimethylolpropane laurate and sodium alkyl sulfonate in the finish；
The mineral oil is one kind in the mineral oil of 9#~17#；
The phosphate kalium salt is 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, isomerous tridecanol polyoxyethylene ether phosphate kalium salt or 12 Tetrol phosphate kalium salt；
The sodium alkyl sulfonate is dodecyl sodium sulfate, pentadecyl sulfonic acid sodium or sodium cetanesulfonate；
The preparation method of the finish is：By crown ether and phosphate kalium salt, trimethylolpropane laurate and sodium alkyl sulfonate It is added in mineral oil after mixing and is uniformly mixing to obtain finish；It counts in parts by weight, the addition of each component is as follows：
The mixing carries out at normal temperatures, and the temperature of the stirring is 40~55 DEG C, and the time is 1~3h.
10. according to the method described in claim 9, it is characterized in that, the spinning technique of the low-shrinkage high-strength polyester industrial fiber Parameter is as follows：
It stretches, the technological parameter of thermal finalization is：
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