CN108385188B - Low-shrinkage activated polyester industrial yarn and preparation method thereof - Google Patents

Low-shrinkage activated polyester industrial yarn and preparation method thereof Download PDF

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CN108385188B
CN108385188B CN201711342804.XA CN201711342804A CN108385188B CN 108385188 B CN108385188 B CN 108385188B CN 201711342804 A CN201711342804 A CN 201711342804A CN 108385188 B CN108385188 B CN 108385188B
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temperature
oil agent
industrial yarn
oiling
modified polyester
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CN108385188A (en
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王丽丽
孙晓华
赵慧荣
窦弘
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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
    • 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
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • 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
    • 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
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    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
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    • 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
    • D06M13/295—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof containing polyglycol moieties; containing neopentyl moieties
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    • 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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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Artificial Filaments (AREA)

Abstract

The invention relates to a low shrinkage activated polyester industrial yarn and a preparation method thereof, wherein the preparation method comprises the following steps: the modified polyester is subjected to solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting, oiling by using an activated oiling agent, winding and pre-activation treatment, wherein the oiling agent contains crown ether, the content of the crown ether is 67.30-85.58 wt%, and the finally prepared polyester industrial yarn is modified polyester with a molecular chain comprising a terephthalic acid chain segment, a glycol chain segment and a dihydric alcohol chain segment with a branched chain. The preparation method is simple and reasonable, and the finally prepared low-shrinkage activated polyester industrial yarn has the dry heat shrinkage rate of 5.5 +/-0.8% under the conditions of 177 ℃, 10min and 0.05cN/dtex, the dry heat shrinkage rate of 2.8-5.8% under the conditions of 190 ℃, 15min and 0.01cN/dtex, and the wicking height of less than or equal to 5 mm.

Description

Low-shrinkage activated polyester industrial yarn and preparation method thereof
Technical Field
The invention belongs to the field of fiber preparation, and relates to a low-shrinkage activated polyester industrial yarn and a preparation method thereof.
Background
Polyethylene terephthalate (PET) fibers have been developed rapidly since the advent due to their excellent properties, and their production has become the world's cap of synthetic fibers. The polyester fiber has a series of excellent performances such as high breaking strength, high elastic modulus, moderate resilience, excellent heat setting performance, good heat and light resistance, good acid, alkali and corrosion resistance and the like, and the fabric prepared from the polyester fiber has the advantages of good crease resistance, good stiffness and the like, and is widely applied to the fields of fibers, bottle packaging, films, sheets and the like, the yield is gradually increased year by year, and the industrial position is remarkably improved.
However, in the polycondensation reaction for synthesizing ethylene terephthalate, especially in the case of linear high polymer, linear and cyclic oligomers are also associated due to high-temperature oxidative degradation, the cyclic oligomers are formed by the back-biting cyclization of the chain ends of macromolecules in the polycondensation stage, about 70% or more of the cyclic oligomers are cyclic trimers, and the cyclic trimers have the characteristics of easy aggregation, easy crystallization, high chemical and heat stability and the like, and the formation of the cyclic trimers has the following influence on the processing of polyester: (1) the spinning assembly can be blocked, and the service life of the melt filter and the assembly is influenced; (2) the fiber can be separated out in the process of heat setting and deposited on a heating roller, so that the friction force is increased and the heating is uneven; (3) the dyeing process takes the cyclic trimer as a center, so that the dye is gathered and adhered to the surface of the fiber, the phenomena of dye color points, spots, color flowers and the like appear on the surface of the fiber, the hand feeling and the color light of the fabric woven by the fiber are influenced, and meanwhile, the normal liquid flow velocity of a melt is limited by the cyclic oligomer filled with a pipeline and a valve, so that the fiber is unevenly dyed, and the reproducibility is poor; (4) the adhesive is adhered to the surface of the fiber, so that the winding is difficult, the phenomena of yarn breakage, uneven thickness and the like occur, the mechanical properties of the fiber such as breaking strength, breaking elongation and the like are influenced, and the product quality is seriously influenced.
Because most PET fibers have small dielectric constant, low moisture regain and high friction coefficient, a spin finish must be used in the spinning process. The main component of the oil agent is surfactant, and can form directional adsorption layer, i.e. oil film, on the surface of chemical fibre, on one hand, the hydrophilic group of the oil film is oriented to space, and can adsorb moisture in the air, and on the fibre surface a continuous water film can be formed, so that the charged ions can be migrated on the surface of the fibre, and the accumulation of static charge produced by friction between the fibres can be reduced, so that the surface resistance of the fibre can be reduced, and the conductivity of fibre can be raised, on the other hand, the oil film isolating fibre can produce a certain affinity for fibre, and can make it possess a certain concentration property and do not scatter, and in addition, the oil film also can give fibre a certain smoothness, so that the fibre can not be damaged in the course of friction, and has good hand feeling, and can smoothly pass through the operation procedures of winding, drawing and drying, etc. when spinning, the electrostatic action in the course of textile processing can be eliminated, and the, The roller, the cylinder and other adverse phenomena reduce the generation of broken filaments and broken ends, and ensure the quality of fiber products.
The friction behavior of the fiber can be changed after the oil film on the surface of the fiber is broken at high temperature, high speed and certain pressure, so that the friction force is increased, and other problems such as broken filaments and broken ends of the fiber are caused. Along with the development of high speed, super high speed and multifunctional fiber of polyester filament, the development of an oil solution with good heat resistance, low viscosity, high oil film strength, good smoothness and strong antistatic property is of great practical significance.
The low shrinkage activated polyester industrial yarn is widely used in the fields of automobiles, household, clothes and the like, but the content of oligomer in the fiber prepared by the prior art is higher, so that the performance of the fiber is reduced, the fiber is not uniform, and the phenomena of broken filaments and the like are generated. In addition, the prior oil agent is easy to decompose and bond at high temperature, and has adverse effect on spinning processing.
Therefore, how to prepare a low-shrinkage activated polyester industrial yarn with low oligomer content and good fiber quality becomes a problem to be solved at present.
Disclosure of Invention
The invention aims to solve the problems that in the prior art, the fiber is not uniform due to the fact that oiling agents are fast in volatilization and easy to adhere to the surface of the fiber, the residual oligomer in a spinneret plate is excessive, the quality of the fiber is affected, and the content of the oligomer in the fiber is high, and provides a low-shrinkage activated polyester industrial yarn with uniform spinning and low oligomer content and a preparation method thereof. The introduction of the dihydric alcohol with the branched chain in the modified polyester reduces the cyclic oligomer generated in the polyester side reaction and improves the quality of the fiber; the crown ether-containing oil agent is used, so that the heat resistance and the lubricity of the oil agent are improved, the quality of fibers is improved, and the crown ether has lower viscosity and higher volatile point compared with the conventional smoothing agent, so that the friction coefficient of the crown ether-containing oil agent is smaller, the heat resistance and the stability are better, the processability of the fibers is improved, and the occurrence of a broken filament phenomenon is reduced.
In order to achieve the purpose, the invention adopts the technical scheme that:
the low-shrinkage activated polyester industrial yarn is made of modified polyester, a molecular chain of the modified polyester comprises a terephthalic acid chain segment, an ethylene glycol chain segment and a dihydric alcohol chain segment with a branched chain, and the structural formula of the dihydric alcohol with the branched chain is as follows:
Figure GDA0001695705660000021
in the formula, R1And R2Each independently selected from linear alkylene having 1 to 3 carbon atoms, R3Selected from alkyl with 1-5 carbon atoms, R4The carbon atom number is 2-5, and the purpose of carbon atom number limitation is as follows: because a branched chain structure and a long chain structure are introduced into the dihydric alcohol, the electronegativity of an alkoxy part is weakened, the number of carbon atoms of the branched chain structure is too small, the electronegativity influence on the alkoxy part is small, and the significance for reducing the generation of cyclic oligomers is not large; the too large number of carbon atoms of the branched chain structure can generate intermolecular entanglement and influence the distribution of molecular weight;
the dry heat shrinkage rate of the low-shrinkage activated polyester industrial yarn under 177 ℃, 10min and 0.05cN/dtex conditions is 5.5 +/-0.8%, the dry heat shrinkage rate under 190 ℃, 15min and 0.01cN/dtex conditions is 2.8-5.8%, and the wicking height is less than or equal to 5 mm. The dry heat shrinkage rate of the invention is lower than that of the common polyester industrial yarn, and the influence on the fiber quality in the preparation process is reduced. The reduced wicking height of the product of the invention benefits from the improved spinning uniformity of the product and the reduced oligomer content in the fiber.
As a preferred technical scheme:
the low shrinkage activated polyester industrial yarn has the fineness of 930-3300 dtex, the deviation rate of linear density is +/-1.5%, the breaking strength is more than or equal to 7.0cN/dtex, the CV value of the breaking strength is less than or equal to 3.0%, the central value of the elongation at break is 20.0-20.5%, the deviation rate of the elongation at break is +/-2%, the CV value of the elongation at break is less than or equal to 8.0%, the number of networks is 4-9/m, the oil content is 0.25-0.97%, and the full-length percentage is more than or equal to 99%. The reduced content of linear oligomers in the technical yarn results in a cleaner spinneret plate on the one hand and also in a significant increase in spinning uniformity on the other hand. The invention also reduces the broken filaments of the polyester fiber and avoids the filaments from floating through the use of the crown ether-containing oil agent, thereby ensuring that the full-package rate is more than or equal to 99 percent and greatly improving the quality of the product.
According to the low-shrinkage activated polyester industrial yarn, the content of cyclic oligomers in the modified polyester is less than or equal to 0.6wt%, the amount of cyclic oligomers in the polyester prepared by the prior art is 1.5-2.1 wt%, and compared with the prior art, the low-shrinkage activated polyester industrial yarn remarkably reduces the generation amount of cyclic oligomers;
the number average molecular weight of the modified polyester is 20000-27000, the molecular weight distribution index is 1.8-2.2, the molecular weight of the modified polyester is higher, the molecular weight distribution is narrower, the spinning processing requirement can be met, and the preparation of fibers with excellent performance is facilitated;
the molar content of the dihydric alcohol chain segment with the branched chain in the modified polyester is 3-5% of that of the terephthalic acid chain segment, and the molar content of the dihydric alcohol chain segment with the branched chain in the modified polyester is lower, so that the excellent performance of the polyester can be maintained.
The polyester industrial yarn with low shrinkage activation is characterized in that the dihydric alcohol with branched chain is 2-ethyl-2-methyl-1, 3-propanediol, 2-diethyl-1, 3-propanediol, 2-butyl-2-ethyl-1, 3-propanediol, 3-diethyl-1, 5-pentanediol, 4-diethyl-1, 7-heptanediol, 4-di (1-methylethyl) -1, 7-heptanediol, 3-dipropyl-1, 5-pentanediol, 4-dipropyl-1, 7-heptanediol, 4-methyl-4- (1, 1-dimethylethyl) -1, 7-heptanediol, 3-methyl-3-pentyl-1, 6-hexanediol or 3, 3-diamyl-1, 5-pentanediol.
The preparation method of the modified polyester comprises the following steps: uniformly mixing terephthalic acid, ethylene glycol and the dihydric alcohol with the branched chain, and then sequentially carrying out esterification reaction and polycondensation reaction to obtain modified polyester; the modified polyester comprises the following specific preparation steps:
(1) performing esterification reaction;
preparing terephthalic acid, ethylene glycol and the dihydric alcohol with the branched chain into slurry, adding a catalyst and a stabilizer, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is normal pressure to 0.3MPa, the esterification reaction temperature is 250-260 ℃, and the esterification reaction endpoint is determined when the distilled amount of water in the esterification reaction reaches more than 90% of a theoretical value;
(2) performing polycondensation reaction;
and after the esterification reaction is finished, starting the polycondensation reaction in a low vacuum stage under the negative pressure condition, stably pumping the pressure in the low vacuum stage from normal pressure to below 500Pa in 30-50 min at the reaction temperature of 260-270 ℃ for 30-50 min, then continuously pumping the vacuum to perform the polycondensation reaction in a high vacuum stage, further reducing the reaction pressure to below 100Pa, controlling the reaction temperature to 275-285 ℃ and the reaction time to be 50-90 min, and thus obtaining the modified polyester.
In the step (1), the molar ratio of the terephthalic acid, the ethylene glycol and the branched diol is 1: 1.2-2.0: 0.03-0.06, the addition amount of the catalyst is 0.01-0.05% of the weight of the terephthalic acid, and the addition amount of the stabilizer is 0.01-0.05% of the weight of the terephthalic acid;
the catalyst is antimony trioxide, ethylene glycol antimony or antimony acetate, and the stabilizer is triphenyl phosphate, trimethyl phosphate or trimethyl phosphite.
The invention also provides a method for preparing the low-shrinkage activated polyester industrial yarn, which is characterized in that the modified polyester is subjected to solid-phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting, oiling of an activated oil agent, winding and pre-activation treatment to prepare the low-shrinkage activated polyester industrial yarn;
the oil agent for oiling contains crown ether, the content of the crown ether is 67.30-85.58 wt%, the content of the crown ether in the oil agent needs to be kept within a certain range, the oil agent with low viscosity, good heat resistance and high oil film strength cannot be prepared if the addition amount of the crown ether is too low, and other performance indexes of the oil agent can be influenced if the addition amount of the crown ether is too high.
Crown ethers are heterocyclic organic compounds containing a plurality of ether groups. The wetting ability of the crown ether surfactant is larger than that of a corresponding open-chain compound, the crown ether has better solubilization, the solubility of the salt compound in the organic compound is lower, but the solubility of the organic matter of the salt compound is improved along with the addition of the crown ether. The common polyester compounds or polyethers in the oil agent have larger intermolecular action due to larger molecular weight and the action of hydrogen bonds, and show larger kinematic viscosity, and after the crown ether is added, the crown ether can be well compatible in the polyester compounds or polyether oil agent system, enters between polyester compounds or polyether molecular chains, shields the acting force between the molecular chains, and thus the viscosity of the oil agent system is reduced. Meanwhile, the antistatic agent of the chemical fiber oiling agent is mainly divided into anionic surfactant, cationic surfactant and amphoteric surfactant, most of which contain metal ions or exist in the form of salt, so that the compatibility of the antistatic agent and polyester compounds or polyethers in the oiling agent is ensured, and the addition of the crown ether improves the compatibility of the antistatic agent and the polyester compounds or polyethers due to the salt dissolution effect, thereby improving the strength of an oiling agent oil film and having great significance on the stability of spinning and the product holding capacity. Indexes of the oil agent are reflected by a comprehensive factor, so that a certain restriction is provided for the addition amount of crown ether, the advantages of heat resistance and oil film strength of the oil agent are not reflected sufficiently when the addition amount is too low, and other indexes are limited when the addition amount is too much.
When the oil agent is used, water is used to prepare an emulsion with the concentration of 10-20 wt%.
The method is characterized in that the intrinsic viscosity of the modified polyester after solid-phase polycondensation and tackifying is 1.0-1.2 dL/g; the intrinsic viscosity is a representation mode of molecular weight, the intrinsic viscosity is too high, the subsequent processing temperature is increased, and the product is easy to be thermally degraded; if the intrinsic viscosity is too low, the required strength and performance are difficult to achieve;
the replacement period of the spinning assembly is more than or equal to 40 days; the longer the replacement period of the components is, the better the stability of the product is, meanwhile, the production cost is reduced, and the economic benefit is improved;
after the oil agent is heated and treated at 200 ℃ for 2 hours, the thermal weight loss is less than 15wt%, the crown ether has a higher volatile point and excellent heat-resistant stability, and the heat-resistant performance of the oil agent introduced with the crown ether is also remarkably improved;
the kinematic viscosity of the oil agent is 27.5-30.1 mm at the temperature of (50 +/-0.01) ° C2The kinematic viscosity of the oil agent prepared from water into 10wt% emulsion is 0.93-0.95 mm2The crown ether can reduce the viscosity of the oil agent mainly because the crown ether has lower viscosity and is a bead-shaped micromolecule, and after the crown ether is introduced into the oil agent system, the crown ether can be well compatible in the polyester compound or polyether compound oil agent system and simultaneously enters between molecular chains of the polyester compound or polyether compound to shield the acting force between the molecular chains, so that the viscosity of the oil agent system is reduced;
the oil film strength of the oil agent is 121-127N, the oil film strength of the oil agent in the prior art is low and is generally about 110N, the main reason is that most of antistatic agents of the chemical fiber oil agent contain metal ions or exist in the form of salt, the compatibility of the antistatic agents and polyester compounds or polyether compounds in the oil agent is poor, and the crown ether can improve the oil film strength is mainly that salt solution effect can be generated after the crown ether is added, so that the compatibility of the antistatic agents and the polyester compounds or polyether compounds is improved, and the oil film strength of the oil agent is further improved;
the surface tension of the oil agent is 23.2-26.8 cN/cm, and the specific resistance is 1.0 × 108～1.8×108Ω·cm；
After oiling, the static friction coefficient between the fibers is 0.250-0.263, and the dynamic friction coefficient is 0.262-0.273;
after oiling, the static friction coefficient between the fiber and the metal is 0.202-0.210, and the dynamic friction coefficient is 0.320-0.332.
The crown ether is 2-hydroxymethyl-12-crown-4, 15-crown ether-5 or 2-hydroxymethyl-15-crown-5;
the oil agent also contains mineral oil, phosphate potassium salt, trimethylolpropane laurate and alkyl sodium sulfonate;
the mineral oil is one of 9# to 17# mineral oil;
the phosphate potassium salt is dodecyl phosphate potassium salt, isomeric tridecanol polyoxyethylene ether phosphate potassium salt or dodecatetradecanol phosphate potassium salt;
the sodium alkyl sulfonate is sodium dodecyl sulfonate, sodium pentadecyl sulfonate or sodium hexadecyl sulfonate.
The preparation method of the oil agent comprises the following steps: uniformly mixing crown ether, phosphate potassium salt, trimethylolpropane laurate and sodium alkyl sulfonate, adding the mixture into mineral oil, and uniformly stirring to obtain an oil agent; the addition amount of each component is as follows according to the parts by weight:
Figure GDA0001695705660000051
Figure GDA0001695705660000061
the mixing is carried out at normal temperature, the stirring temperature is 40-55 ℃, and the stirring time is 1-3 h.
The spinning process parameters of the low shrinkage activated polyester industrial yarn are as follows:
Figure GDA0001695705660000062
the technological parameters of stretching and heat setting are as follows:
Figure GDA0001695705660000063
the invention mechanism is as follows:
the invention firstly adopts modified polyester comprising a terephthalic acid chain segment, an ethylene glycol chain segment and a dihydric alcohol chain segment with a branched chain, and then the modified polyester melt is subjected to solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting, oiling by an activated oil agent, winding and pre-activation treatment to prepare the low-shrinkage activated polyester industrial yarn, wherein the modified polyester and the oil agent have the following specific influences on the performance of the finally prepared low-shrinkage activated polyester industrial yarn: the addition of the modified polyester reduces the generation of cyclic oligomer, thereby improving the service life of the component on one hand and improving the uniformity of the fiber on the other hand; the use of the oil agent containing crown ether increases the stability of spinning, thereby further improving the quality of the fiber.
In organic compounds, the angle between two chemical bonds formed by the same atom in a molecule is called the bond angle, which is usually expressed in degrees, and the electronegativity of the central atom and the coordinating atom in the molecule of the organic compound affects the bond angle of the molecule. When the electronegativity of the coordinating atom bonded to the central atom is increased, the electron-withdrawing ability of the coordinating atom is increased, the bonding electron pair moves toward the ligand and is farther away from the central atom, so that the bond pairs are closer to each other due to the decrease in repulsive force, and the bond angle is decreased, and conversely, when the electronegativity of the coordinating atom bonded to the central atom is decreased, the electron-donating ability of the coordinating atom is increased, the bonding electron pair moves toward the central atom and is closer to the central atom, so that the bond pairs are farther away from each other due to the increase in repulsive force, and the bond angle is increased.
According to Pauling electronegativity scale, the electronegativity of C, H and O atoms are 2.55, 2.20 and 3.44, respectively, and according to valence electron energy equilibrium theory, the calculation formula of the group electronegativity is shown as follows:
Figure GDA0001695705660000071
in the formula, xiIs the electronegativity of the neutral atom of the i atom before bonding, Nve,iIs the number of valence electrons in the i atom, niIs the number of i atoms in the molecule. The calculation steps for the electronegativity of more complex groups are mainly: the electronegativity of the simple group is firstly calculated, then the electronegativity of the more complex group is calculated by taking the simple group as a quasi atom, and the electronegativity of the target group is finally obtained through successive iteration. In calculating the electronegativity of a quasi-atom, the valence electron that is not bonded in a radical atom (for example, the radical atom of a group-OH is an O atom) is regarded as the valence electron of the quasi-atom.
In the invention, C atoms are combined with O atoms of hydroxyl groups in dihydric alcohol to form new C-O bonds in ester groups after C-O bonds of carboxyl groups in terephthalic acid are broken, bond angles between C-C bonds formed by the C atoms in the ester groups and C atoms on a benzene ring and the newly formed chemical bonds C-O are recorded as α, the change of the bond angle α influences the ring forming reaction, when α is less than 109 ℃, molecules are easy to form rings, and the ring forming probability of the molecules is reduced along with the increase of α.
Figure GDA0001695705660000072
In the formula, R1And R2Each independently selected from linear alkylene having 1 to 3 carbon atoms, R3Selected from alkyl with 1-5 carbon atoms, R4Selected from alkyl with 2-5 carbon atoms. The diol structure is introduced with a branched chain structure and a long chain structure, so that the electronegativity of an alkoxy part of the diol structure is weakened, and the electronegativity of a group connected with a carbonyl group in diacid in the diol structure is 2.59-2.79 according to a calculation formula of the electronegativity of the group, and a group-OCH (OCH) group connected with the carbonyl group in the diacid in ethylene glycol2CH2Electronegativity of-was 3.04, so that the alkoxy group was in comparison with-OCH in ethylene glycol2CH2Has a stronger electron donating property, so that the bond-forming electron pair on the newly formed chemical bond C-O bond will be directed toward the centerThe C atom moves in the direction closer to the central atom, so that the bond pairs are far away from each other due to the increase of repulsive force, the bond angle α is larger than 109 degrees, the probability of generating linear polymers is increased, the generation of cyclic oligomers is reduced, the phenomena of yarn breakage, uneven thickness and the like are eliminated, the breaking strength of fibers is increased, the unevenness is reduced, and the product quality is improved.
The crown ether is introduced into the oil agent to prepare the oil agent with low viscosity, good heat resistance and higher oil film strength. In the prior art, the higher viscosity of the oil agent is mainly due to the fact that the oil agent contains a common polyester compound or polyether compound, the intermolecular action of the compound is larger due to the larger molecular weight and the action of hydrogen bonds, the kinematic viscosity is larger, so that the viscosity of the oil agent is higher, the viscosity of the oil agent can be obviously reduced after crown ether is added, the crown ether is mainly due to the fact that the viscosity of the crown ether is lower and is bead-shaped micromolecule, the crown ether can be well compatible in a polyester compound or polyether oil agent system and simultaneously enters between molecular chains of the polyester compound or polyether compound to shield acting force between the molecular chains, and therefore the viscosity of the oil agent system is reduced. In the prior art, the oil film strength of the oil agent is low mainly because the antistatic agent of the chemical fiber oil agent mostly contains metal ions or exists in the form of salt, so that the compatibility of the antistatic agent and polyester compounds or polyethers in the oil agent is poor, and the crown ether can improve the oil film strength mainly because the crown ether can generate a salt solution effect after being added, so that the compatibility of the antistatic agent and the polyester compounds or polyethers is improved, and the oil film strength of the oil agent is further improved. In addition, the crown ether has higher volatile point and excellent heat-resistant stability, the heat-resistant performance of the oil agent introduced with the crown ether is also obviously improved, and the crown ether has lower viscosity and higher volatile point, so that the friction coefficient of the oil agent containing the crown ether is small, the heat-resistant stability is excellent, and the processability of the fiber is improved.
The addition of the modified polyester reduces the generation of cyclic oligomer, thereby prolonging the service life of the assembly, improving the spinning stability and improving the uniformity of the fiber; the use of the oil agent containing crown ether further increases the stability of spinning and improves the quality of fibers.
Has the advantages that:
(1) the low shrinkage activated polyester industrial yarn has the advantages of simple and reasonable preparation process, low dry heat shrinkage rate and low wicking height;
(2) according to the preparation method of the low shrinkage activated polyester industrial yarn, the dihydric alcohol with a branched chain is introduced into the modified polyester, so that the bond angle of polyester molecules is changed, and the generation of cyclic oligomers in the polyester synthesis process is remarkably reduced;
(3) according to the preparation method of the low shrinkage activated polyester industrial yarn, the oiling agent containing the crown ether used in the oiling process has the characteristics of low viscosity, good heat resistance, high oil film strength, good smoothness and strong antistatic property, and the spinning stability and the fiber processability are improved.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of low-shrinkage activated polyester industrial yarn comprises the following steps:
(1) preparing modified polyester;
(a) performing esterification reaction; preparing terephthalic acid, ethylene glycol and 2-ethyl-2-methyl-1, 3-propanediol with a molar ratio of 1:1.2:0.03 into slurry, adding antimony trioxide, titanium dioxide and triphenyl phosphate, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is normal pressure, the esterification reaction temperature is 250 ℃, and the esterification reaction end point is when the distilled water amount in the esterification reaction reaches 90% of a theoretical value, wherein the adding amount of the antimony trioxide is 0.01% of the weight of the terephthalic acid, the adding amount of the titanium dioxide is 0.20% of the weight of the terephthalic acid, and the adding amount of the triphenyl phosphate is 0.05% of the weight of the terephthalic acid, wherein the structural formula of the 2-ethyl-2-methyl-1, 3-propanediol is as follows:
Figure GDA0001695705660000091
(b) performing polycondensation reaction; after the esterification reaction is finished, the polycondensation reaction in the low vacuum stage is started under the condition of negative pressure, the pressure is stably pumped from normal pressure to the absolute pressure of 500Pa within 30min, the reaction temperature is 260 ℃, the reaction time is 40min, then continuously vacuumizing, carrying out polycondensation reaction in a high vacuum stage, further reducing the reaction pressure to 100Pa absolute, the reaction temperature to 275 ℃, and the reaction time to 70min to obtain modified polyester, wherein the molecular chain of the modified polyester comprises a terephthalic acid chain segment, a glycol chain segment and a 2-ethyl-2-methyl-1, 3-propanediol chain segment, the content of cyclic oligomer in the modified polyester is 0.6wt%, the number average molecular weight is 20000, the molecular weight distribution index is 2.0, and the molar content of the 2-ethyl-2-methyl-1, 3-propanediol chain segment in the modified polyester is 3% of the molar content of the terephthalic acid chain segment;
(2) preparing an oiling agent;
uniformly mixing 2-hydroxymethyl-12-crown-4 with dodecyl phosphate potassium salt, trimethylolpropane laurate and sodium dodecyl sulfate at normal temperature, adding the mixture into No. 9 mineral oil, and uniformly stirring the mixture for 1h at 40 ℃ to obtain an oil agent, wherein the adding amount of each component is as follows in parts by weight: 2 parts of No. 9 mineral oil; 10 parts of trimethylolpropane laurate; 90 portions of 2-hydroxymethyl-12-crown-4; 8 parts of dodecyl phosphate potassium salt; 3 parts of sodium dodecyl sulfate; the content of crown ether in the prepared oil agent is 79.6 wt%, the high temperature resistance of the oil agent is excellent, and the thermal weight loss is 14.5 wt% after the oil agent is heated for 2 hours at 200 ℃; the viscosity of the oil agent is low, and the kinematic viscosity is 29.6mm at the temperature of (50 +/-0.01) ° C2(s) a kinematic viscosity of 0.93mm after preparation with water as an emulsion having a concentration of 10% by weight2(s) the oil has high oil film strength of 125N, surface tension of 24.8cN/cm, and specific resistance of 1.3 × 108Omega cm; on the upper partCoefficient of static friction (. mu.) between fibres and fibres (F/F) after oils) 0.255, coefficient of dynamic friction (. mu.)d) Is 0.266; after oiling, the coefficient of static friction (μ) between the fiber and the metal (F/M)s) 0.203, coefficient of dynamic friction (. mu.)d) 0.320, and the prepared oil agent is prepared into an emulsion with the concentration of 15wt% by using water when in use;
(3) the modified polyester is subjected to solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting, oiling by an activated oil agent, winding and pre-activation treatment to prepare the low shrinkage activated polyester industrial yarn, wherein the intrinsic viscosity of the modified polyester after solid phase polycondensation tackifying is 11dL/g, the replacement period of a spinning assembly is 44 days, and the spinning technological parameters of the low shrinkage activated polyester industrial yarn are as follows: the temperature of each area of the screw is 310 ℃; the temperature of the box body is 297 ℃; the head pressure is 170 Bar; the temperature of the cross air blow is 23 ℃; the humidity of the cross air blow is 80%; the air speed of the cross air blow is 0.45 m/s; the oiling rate of the activating oil agent is 0.45 wt%; the pre-network pressure is 0.16 MPa; the network pressure is 0.21 MPa; the winding speed is 3100 m/min; the preactivation treatment temperature is 75 ℃; the pre-activation treatment time is 25 h; the technological parameters of stretching and heat setting are as follows: GR-1 speed is 530 m/min; GR-2 speed is 750 m/min; the GR-2 temperature is 90 ℃; the GR-3 speed is 2100 m/min; the GR-3 temperature is 130 ℃; GR-4 speed is 3200 m/min; GR-4 temperature is 230 ℃; GR-5 speed is 3200 m/min; GR-5 temperature is 235 ℃; GR-6 speed is 3000 m/min; the GR-6 temperature was 180 ℃.
The fineness of the finally prepared low shrinkage activated polyester industrial yarn is 1500dtex, the deviation rate of linear density is-0.1%, the breaking strength is 7.7cN/dtex, the CV value of the breaking strength is 2.7%, the central value of the elongation at break is 20.3%, the deviation rate of the elongation at break is-0.11%, the CV value of the elongation at break is 7.3%, the number of networks is 7/m, the oil content is 0.97%, the full-wrap rate is 99.9%, the dry heat shrinkage rate of the low shrinkage activated polyester industrial yarn under the conditions of 177 ℃, 10min and 0.05cN/dtex is 6.3%, the dry heat shrinkage rate under the conditions of 190 ℃, 15min and 0.01cN/dtex is 5.8%, and the wicking height is 4.5 mm.
Example 2
A preparation method of low-shrinkage activated polyester industrial yarn comprises the following steps:
(1) preparing modified polyester;
(a) performing esterification reaction; preparing terephthalic acid, ethylene glycol and 2, 2-diethyl-1, 3-propanediol with a molar ratio of 1:1.3:0.04 into slurry, adding ethylene glycol antimony, titanium dioxide and trimethyl phosphate, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is normal pressure, the esterification reaction temperature is 260 ℃, and the esterification reaction end point is when the distilled water amount in the esterification reaction reaches 91% of a theoretical value, wherein the adding amount of the ethylene glycol antimony is 0.02% of the weight of the terephthalic acid, the adding amount of the titanium dioxide is 0.21% of the weight of the terephthalic acid, and the adding amount of the trimethyl phosphate is 0.03% of the weight of the terephthalic acid, wherein the structural formula of the 2, 2-diethyl-1, 3-propanediol is as follows:
Figure GDA0001695705660000101
(b) performing polycondensation reaction; after the esterification reaction is finished, the polycondensation reaction in the low vacuum stage is started under the condition of negative pressure, the pressure is stably pumped from normal pressure to the absolute pressure of 490Pa within 35min, the reaction temperature is 261 ℃, the reaction time is 30min, then continuously vacuumizing, carrying out polycondensation reaction in a high vacuum stage, further reducing the reaction pressure to 100Pa absolute, the reaction temperature to 277 ℃, the reaction time to 85min, preparing modified polyester, wherein the molecular chain of the modified polyester comprises a terephthalic acid chain segment, a glycol chain segment and a 2, 2-diethyl-1, 3-propanediol chain segment, the content of cyclic oligomer in the modified polyester is 0.6wt%, the number average molecular weight is 27000, the molecular weight distribution index is 1.8, and the molar content of the 2, 2-diethyl-1, 3-propanediol chain segment in the modified polyester is 5% of the molar content of the terephthalic acid chain segment;
(2) preparing an oiling agent;
uniformly mixing 15-crown ether-5, isotridecanol polyoxyethylene ether phosphate potassium salt, trimethylolpropane laurate and sodium pentadecylsulfonate at normal temperature, adding the mixture into 10# mineral oil, and uniformly stirring the mixture at 43 ℃ for 1.5 hours to obtain an oil agent, wherein the addition amount of the components is as follows in parts by weight: 2 portions of No. 10 mineral oil; trihydroxymethyl group15 parts of propane laurate; 70 portions of 15-crown ether-5; 10 parts of isomeric tridecanol polyoxyethylene ether phosphate potassium salt; 7 parts of sodium pentadecylsulfonate; the content of crown ether in the prepared oil agent is 67.30 wt%, the high temperature resistance of the oil agent is excellent, and the thermal weight loss is 13 wt% after the oil agent is heated for 2 hours at 200 ℃; the viscosity of the oil agent is low, and the kinematic viscosity is 28.1mm at the temperature of (50 +/-0.01) ° C2(s) a kinematic viscosity of 0.93mm after preparation with water as an emulsion having a concentration of 10% by weight2(s) 123N, which is a high oil film strength of the oil agent, 25.1cN/cm, which is a surface tension of the oil agent, and 1.5 × 10 which is a specific resistance8Omega cm; coefficient of static friction (. mu.) between fibres (F/F) after oilings) 0.257, coefficient of dynamic friction (. mu.)d) Is 0.265; after oiling, the coefficient of static friction (μ) between the fiber and the metal (F/M)s) 0.205, coefficient of dynamic friction (. mu.)d) Is 0.323; when the prepared oil agent is used, water is used for preparing emulsion with the concentration of 14 wt%;
(3) the modified polyester is subjected to solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting, oiling by an activated oil agent, winding and pre-activation treatment to prepare the low shrinkage activated polyester industrial yarn, wherein the intrinsic viscosity of the modified polyester after solid phase polycondensation tackifying is 1.0dL/g, the replacement period of a spinning assembly is 40 days, and the spinning technological parameters of the low shrinkage activated polyester industrial yarn are as follows: the temperature of each zone of the screw is 290 ℃; the temperature of the box body is 295 ℃; the head pressure is 165 Bar; the temperature of the cross air blow is 21 ℃; the humidity of the cross air blow is 75 percent; the side blowing wind speed is 0.35 m/s; the oiling rate of the activating oil agent is 0.4 wt%; the pre-network pressure is 0.14 MPa; the network pressure is 0.19 MPa; the winding speed is 2600 m/min; the preactivation treatment temperature is 70 ℃; the pre-activation treatment time is 20 h; the technological parameters of stretching and heat setting are as follows: GR-1 speed is 480 m/min; GR-2 speed is 500 m/min; the GR-2 temperature is 80 ℃; GR-3 speed is 1800 m/min; the GR-3 temperature is 100 ℃; GR-4 speed is 2800 m/min; the GR-4 temperature is 200 ℃; GR-5 speed is 2800 m/min; the GR-5 temperature is 200 ℃; GR-6 speed is 2600 m/min; the GR-6 temperature was 150 ℃.
The fineness of the finally prepared low shrinkage activated polyester industrial yarn is 930dtex, the deviation rate of linear density is-1.5%, the breaking strength is 7.0cN/dtex, the CV value of the breaking strength is 3.0%, the central value of the elongation at break is 20.0%, the deviation rate of the elongation at break is-2%, the CV value of the elongation at break is 8.0%, the number of networks is 4/m, the oil content is 0.25%, the full-wrap rate is 99%, the dry heat shrinkage rate of the low shrinkage activated polyester industrial yarn under the conditions of 177 ℃, 10min and 0.05cN/dtex is 4.7%, the dry heat shrinkage rate under the conditions of 190 ℃, 15min and 0.01cN/dtex is 2.8%, and the wicking height is 5 mm.
Example 3
A preparation method of low-shrinkage activated polyester industrial yarn comprises the following steps:
(1) preparing modified polyester;
(a) performing esterification reaction; preparing terephthalic acid, ethylene glycol and 2-butyl-2-ethyl-1, 3-propanediol with a molar ratio of 1:1.4:0.05 into slurry, adding antimony acetate, titanium dioxide and trimethyl phosphite, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.1MPa, the esterification reaction temperature is 252 ℃, and the esterification reaction end point is when the distilled water amount in the esterification reaction reaches 92% of a theoretical value, wherein the adding amount of the antimony acetate is 0.03% of the weight of the terephthalic acid, the adding amount of the titanium dioxide is 0.23% of the weight of the terephthalic acid, and the adding amount of the trimethyl phosphite is 0.01% of the weight of the terephthalic acid, wherein the structural formula of the 2-butyl-2-ethyl-1, 3-propanediol is as follows:
Figure GDA0001695705660000121
(b) performing polycondensation reaction; after the esterification reaction is finished, the polycondensation reaction in the low vacuum stage is started under the condition of negative pressure, the pressure is smoothly pumped from normal pressure to the absolute pressure of 495Pa within 40min, the reaction temperature is 263 ℃, the reaction time is 45min, then continuously vacuumizing, carrying out polycondensation reaction in a high vacuum stage, further reducing the reaction pressure to 95Pa absolute, 278 ℃ reaction temperature and 60min reaction time, preparing modified polyester, wherein the molecular chain of the modified polyester comprises a terephthalic acid chain segment, a glycol chain segment and a 2-butyl-2-ethyl-1, 3-propanediol chain segment, the content of cyclic oligomer in the modified polyester is 0.5wt%, the number average molecular weight is 21000, the molecular weight distribution index is 2.2, and the molar content of the 2-butyl-2-ethyl-1, 3-propanediol chain segment in the modified polyester is 4% of the molar content of the terephthalic acid chain segment;
(2) preparing an oiling agent;
uniformly mixing 2-hydroxymethyl-15-crown-5 with potassium dodecatetradecanol phosphate, trimethylolpropane laurate and sodium pentadecylsulfonate at normal temperature, adding the mixture into No. 11 mineral oil, and uniformly stirring the mixture at 48 ℃ for 3 hours to obtain an oil agent, wherein the adding amount of each component is as follows in parts by weight: 8 parts of No. 11 mineral oil; 10 parts of trimethylolpropane laurate; 85 parts of 2-hydroxymethyl-15-crown-5; 11 parts of potassium dodecatetradecanol phosphate; 5 parts of sodium pentadecylsulfonate; the content of crown ether in the prepared oil agent is 70.83 wt%, the high temperature resistance of the oil agent is excellent, and the thermal weight loss is 11 wt% after the oil agent is heated for 2 hours at 200 ℃; the viscosity of the oil agent is low, and the kinematic viscosity is 30.1mm at the temperature of (50 +/-0.01) ° C2(s) a kinematic viscosity of 0.94mm after preparation with water as an emulsion having a concentration of 10% by weight2The oil has high oil film strength of 125N, surface tension of 23.2cN/cm, and specific resistance of 1.8 × 108Omega cm; coefficient of static friction (. mu.) between fibres (F/F) after oilings) 0.250, coefficient of dynamic friction (. mu.)d) Is 0.272; after oiling, the coefficient of static friction (μ) between the fiber and the metal (F/M)s) 0.209, coefficient of dynamic friction (. mu.)d) 0.329, and the prepared oil agent is prepared into emulsion with the concentration of 10wt% by using water when in use;
(3) the modified polyester is subjected to solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting, oiling by an activated oil agent, winding and pre-activation treatment to prepare the low shrinkage activated polyester industrial yarn, wherein the intrinsic viscosity of the modified polyester after solid phase polycondensation tackifying is 1.2dL/g, the replacement period of a spinning assembly is 44 days, and the spinning technological parameters of the low shrinkage activated polyester industrial yarn are as follows: the temperature of each area of the screw is 320 ℃; the temperature of the box body is 300 ℃; the head pressure is 175 Bar; the temperature of the cross air blow is 25 ℃; the cross-air humidity is 85%; the air speed of the cross air blow is 0.55 m/s; the oiling rate of the activating oil agent is 0.5 wt%; the pre-network pressure is 0.18 MPa; the network pressure is 0.23 MPa; the winding speed is 3400 m/min; the preactivation treatment temperature is 80 ℃; the pre-activation treatment time is 30 h; the technological parameters of stretching and heat setting are as follows: GR-1 speed is 600 m/min; GR-2 speed is 1000 m/min; GR-2 temperature 100 ℃; GR-3 speed is 2500 m/min; the GR-3 temperature is 150 ℃; GR-4 speed is 3500 m/min; the GR-4 temperature is 250 ℃; GR-5 speed is 3500 m/min; the GR-5 temperature is 250 ℃; the GR-6 speed is 3400 m/min; the GR-6 temperature was 220 ℃.
The fineness of the finally prepared low shrinkage activated polyester industrial yarn is 3300dtex, the deviation rate of linear density is 1.5%, the breaking strength is 7.1cN/dtex, the CV value of the breaking strength is 2.9%, the central value of the elongation at break is 20.5%, the deviation rate of the elongation at break is 2%, the CV value of the elongation at break is 7.9%, the number of networks is 9/m, the oil content is 0.26%, the full-wrap rate is 99.1%, the dry heat shrinkage rate of the low shrinkage activated polyester industrial yarn under the conditions of 177 ℃, 10min and 0.05cN/dtex is 4.8%, the dry heat shrinkage rate under the conditions of 190 ℃, 15min and 0.01cN/dtex is 2.9%, and the wicking height is 4.9 mm.
Example 4
A preparation method of low-shrinkage activated polyester industrial yarn comprises the following steps:
(1) preparing modified polyester;
(a) preparing 3, 3-diethyl-1, 5-pentanediol; reacting 3, 3-diethyl-propionaldehyde, acetaldehyde and triethylamine for 20min at 90 ℃ in a nitrogen atmosphere, then adding the concentrated solution into a hydrogenation reactor with a Raney nickel catalyst, reacting at a hydrogen pressure of 2.914MPa and a temperature of 100 ℃, cooling after the reaction is finished, separating out the catalyst, treating the solution with ion exchange resin, evaporating water under reduced pressure, separating and purifying to obtain 3, 3-diethyl-1, 5-pentanediol, wherein the structural formula of the 3, 3-diethyl-1, 5-pentanediol is as follows:
Figure GDA0001695705660000131
(b) performing esterification reaction; preparing terephthalic acid, ethylene glycol and 3, 3-diethyl-1, 5-pentanediol with the molar ratio of 1:1.5:0.06 into slurry, adding antimony trioxide, titanium dioxide and triphenyl phosphate, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.3MPa, the esterification reaction temperature is 255 ℃, and the esterification reaction end point is when the distilled amount of water in the esterification reaction reaches 95% of a theoretical value, wherein the adding amount of the antimony trioxide is 0.04% of the weight of the terephthalic acid, the adding amount of the titanium dioxide is 0.25% of the weight of the terephthalic acid, and the adding amount of the triphenyl phosphate is 0.01% of the weight of the terephthalic acid;
(c) performing polycondensation reaction; after the esterification reaction is finished, the polycondensation reaction in the low vacuum stage is started under the condition of negative pressure, the pressure is stably pumped from normal pressure to the absolute pressure of 400Pa within 50min, the reaction temperature is 265 ℃, the reaction time is 33min, then continuously vacuumizing, carrying out polycondensation reaction in a high vacuum stage, further reducing the reaction pressure to 90Pa absolute, the reaction temperature is 280 ℃, the reaction time is 50min, preparing modified polyester, wherein the molecular chain of the modified polyester comprises a terephthalic acid chain segment, an ethylene glycol chain segment and a 3, 3-diethyl-1, 5-pentanediol chain segment, the content of cyclic oligomers in the modified polyester is 0.2 wt%, the number average molecular weight is 23000, the molecular weight distribution index is 1.9, and the molar content of the 3, 3-diethyl-1, 5-pentanediol chain segment in the modified polyester is 3.5% of the molar content of the terephthalic acid chain segment;
(2) preparing an oiling agent;
uniformly mixing 2-hydroxymethyl-12-crown-4 with dodecyl phosphate potassium salt, trimethylolpropane laurate and sodium hexadecylsulfonate at normal temperature, adding the mixture into 12# mineral oil, and uniformly stirring the mixture for 2.5 hours at 40 ℃ to obtain an oil agent, wherein the adding amount of each component is as follows in parts by weight: 5 parts of No. 12 mineral oil; 95 parts of 2-hydroxymethyl-12-crown-4; 9 parts of dodecyl phosphate potassium salt; the hexadecyl sodium sulfonate is 2 parts. The content of crown ether in the prepared oil agent is 85.58wt%, the high temperature resistance of the oil agent is excellent, and the thermal weight loss is 9 wt% after the oil agent is heated for 2 hours at 200 ℃; the viscosity of the oil agent is low, and the kinematic viscosity is 29.5mm at the temperature of (50 +/-0.01) ° C2(s) a kinematic viscosity of 0.93mm after preparation with water as an emulsion having a concentration of 10% by weight2(s) the oil film strength of the oil agent is high and is 121N, the surface tension of the oil agent is 24.3cN/cm, and the specific resistance is 1.0 × 108Omega cm; after oiling, fiber and fiberCoefficient of static friction (. mu.) between dimensions (F/F)s) 0.260, coefficient of dynamic friction (. mu.)d) Is 0.263; after oiling, the coefficient of static friction (μ) between the fiber and the metal (F/M)s) 0.202, coefficient of dynamic friction (. mu.)d) 0.330, and the prepared oil agent is prepared into an emulsion with the concentration of 19 wt% by using water when in use;
(3) the modified polyester is subjected to solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting, oiling by an activated oil agent, winding and pre-activation treatment to prepare the low shrinkage activated polyester industrial yarn, wherein the intrinsic viscosity of the modified polyester after solid phase polycondensation tackifying is 1.05dL/g, the replacement period of a spinning assembly is 41 days, and the spinning technological parameters of the low shrinkage activated polyester industrial yarn are as follows: the temperature of each area of the screw is 300 ℃; the temperature of the box body is 298 ℃; the head pressure is 168 Bar; the temperature of the cross air blow is 22 ℃; the cross-air humidity is 78%; the side blowing wind speed is 0.42 m/s; the oiling rate of the activating oil agent is 0.43 wt%; the pre-network pressure is 0.15 MPa; the network pressure is 0.21 MPa; the winding speed is 2800 m/min; the preactivation treatment temperature is 72 ℃; the pre-activation treatment time is 23 h; the technological parameters of stretching and heat setting are as follows: GR-1 speed is 520 m/min; the GR-2 speed is 700 m/min; the GR-2 temperature is 85 ℃; the GR-3 speed is 2100 m/min; the GR-3 temperature is 120 ℃; GR-4 speed is 3000 m/min; GR-4 temperature is 230 ℃; GR-5 speed is 3000 m/min; the GR-5 temperature is 220 ℃; GR-6 speed is 2800 m/min; the GR-6 temperature was 170 ℃.
The fineness of the finally prepared low shrinkage activated polyester industrial yarn is 1100dtex, the deviation rate of linear density is-1.2%, the breaking strength is 7.2cN/dtex, the CV value of the breaking strength is 2.9%, the central value of the elongation at break is 20.3%, the deviation rate of the elongation at break is-1.4%, the CV value of the elongation at break is 7.8%, the number of networks is 5/m, the oil content is 0.5%, the full-wrap rate is 99.3%, the dry heat shrinkage rate of the low shrinkage activated polyester industrial yarn under the conditions of 177 ℃, 10min and 0.05cN/dtex is 4.9%, the dry heat shrinkage rate under the conditions of 190 ℃, 15min and 0.01cN/dtex is 3.8%, and the wicking height is 4.7 mm.
Example 5
A preparation method of low-shrinkage activated polyester industrial yarn comprises the following steps:
(1) preparing modified polyester;
(a) preparing 4, 4-diethyl-1, 7-heptanediol; reacting 4, 4-diethyl-butyraldehyde, propionaldehyde and triethylamine for 20min at 95 ℃ in a nitrogen atmosphere, then adding the concentrated solution into a hydrogenation reactor with a Raney nickel catalyst, reacting at a hydrogen pressure of 2.914MPa and a temperature of 100 ℃, cooling after the reaction is finished, separating out the catalyst, treating the solution with ion exchange resin, evaporating water under reduced pressure, separating and purifying to obtain 4, 4-diethyl-1, 7-heptanediol, wherein the structural formula of the 4, 4-diethyl-1, 7-heptanediol is as follows:
Figure GDA0001695705660000151
(b) performing esterification reaction; preparing terephthalic acid, ethylene glycol and 4, 4-diethyl-1, 7-heptanediol with a molar ratio of 1:1.6:0.03 into slurry, adding ethylene glycol antimony, titanium dioxide and trimethyl phosphate, uniformly mixing, and pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is normal pressure, the esterification reaction temperature is 257 ℃, and the esterification reaction end point is when the distilled amount of water in the esterification reaction reaches 92% of a theoretical value, wherein the adding amount of the ethylene glycol antimony is 0.05% of the weight of the terephthalic acid, the adding amount of the titanium dioxide is 0.20% of the weight of the terephthalic acid, and the adding amount of the trimethyl phosphate is 0.04% of the weight of the terephthalic acid;
(c) performing polycondensation reaction; after the esterification reaction is finished, the polycondensation reaction in the low vacuum stage is started under the condition of negative pressure, the pressure is stably pumped from normal pressure to the absolute pressure of 450Pa within 33min, the reaction temperature is 270 ℃, the reaction time is 30min, then continuously vacuumizing, carrying out polycondensation reaction in a high vacuum stage, further reducing the reaction pressure to 95Pa absolute, the reaction temperature to 275 ℃, and the reaction time to 60min to obtain modified polyester, wherein the molecular chain of the modified polyester comprises a terephthalic acid chain segment, a glycol chain segment and a 4, 4-diethyl-1, 7-heptanediol chain segment, the content of cyclic oligomers in the modified polyester is 0.5wt%, the number average molecular weight is 25000, the molecular weight distribution index is 2.1, and the molar content of the 4, 4-diethyl-1, 7-heptanediol chain segment in the modified polyester is 5% of the molar content of the terephthalic acid chain segment;
(2) preparing an oiling agent;
uniformly mixing 15-crown ether-5, isotridecanol polyoxyethylene ether phosphate potassium salt, trimethylolpropane laurate and sodium dodecyl sulfate at normal temperature, adding the mixture into 13# mineral oil, and uniformly stirring the mixture for 2 hours at 52 ℃ to obtain an oil agent, wherein the adding amount of each component is as follows in parts by weight: 10 parts of No. 13 mineral oil; 5 parts of trimethylolpropane laurate; 70 portions of 15-crown ether-5; 8 parts of isomeric tridecanol polyoxyethylene ether phosphate potassium salt; 6 parts of sodium dodecyl sulfate. The content of crown ether in the prepared oil agent is 70.70 wt%, the high temperature resistance of the oil agent is excellent, and the thermal weight loss is 13.5 wt% after the oil agent is heated for 2 hours at 200 ℃; the viscosity of the oil agent is low, and the kinematic viscosity is 28.6mm at the temperature of (50 +/-0.01) ° C2(s) a kinematic viscosity of 0.95mm after preparation with water as an emulsion having a concentration of 10% by weight2The oil has high oil film strength of 126N, surface tension of 24.9cN/cm, and specific resistance of 1.2 × 108Omega cm; coefficient of static friction (. mu.) between fibres (F/F) after oilings) 0.251, coefficient of dynamic friction (. mu.)d) Is 0.262; after oiling, the coefficient of static friction (μ) between the fiber and the metal (F/M)s) 0.202, coefficient of dynamic friction (. mu.)d) 0.332, and the prepared oil agent is prepared into an emulsion with the concentration of 11 wt% by using water when in use;
(3) the modified polyester is subjected to solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting, oiling by an activated oil agent, winding and pre-activation treatment to prepare the low shrinkage activated polyester industrial yarn, wherein the intrinsic viscosity of the modified polyester after solid phase polycondensation tackifying is 1.15dL/g, the replacement period of a spinning assembly is 43 days, and the spinning technological parameters of the low shrinkage activated polyester industrial yarn are as follows: the temperature of each area of the screw is 312 ℃; the temperature of the box body is 298 ℃; the head pressure is 172 Bar; the temperature of the cross air blow is 24 ℃; the cross-air humidity is 82%; the air speed of the cross air blow is 0.5 m/s; the oiling rate of the activating oil agent is 0.48 wt%; the pre-network pressure is 0.17 MPa; the network pressure is 0.21 MPa; the winding speed is 3200 m/min; the preactivation treatment temperature is 78 ℃; the pre-activation treatment time is 28 h; the technological parameters of stretching and heat setting are as follows: GR-1 speed is 560 m/min; GR-2 speed is 800 m/min; the GR-2 temperature is 90 ℃; GR-3 speed is 2300 m/min; the GR-3 temperature is 130 ℃; GR-4 speed is 3200 m/min; GR-4 temperature is 230 ℃; GR-5 speed is 3200 m/min; the GR-5 temperature is 240 ℃; GR-6 speed is 3100 m/min; the GR-6 temperature was 210 ℃.
The fineness of the finally prepared low shrinkage activated polyester industrial yarn is 3000dtex, the deviation rate of linear density is 1.1%, the breaking strength is 6.6cN/dtex, the CV value of the breaking strength is 2.8%, the central value of the elongation at break is 20.4%, the deviation rate of the elongation at break is 1.2%, the CV value of the elongation at break is 7.4%, the number of networks is 8/m, the oil content is 0.90%, the full-wrap rate is 99.7%, the dry heat shrinkage rate of the low shrinkage activated polyester industrial yarn under the conditions of 177 ℃, 10min and 0.05cN/dtex is 6.2%, the dry heat shrinkage rate under the conditions of 190 ℃, 15min and 0.01cN/dtex is 4.8%, and the wicking height is 4.55 mm.
Example 6
A preparation method of low-shrinkage activated polyester industrial yarn comprises the following steps:
(1) preparing modified polyester;
(a) preparing 4, 4-di (1-methylethyl) -1, 7-heptanediol; reacting 4, 4-di (1-methylethyl) -butyraldehyde, propionaldehyde and triethylamine for 20min at 92 ℃ in a nitrogen atmosphere, then adding the concentrated solution into a hydrogenation reactor with a Raney nickel catalyst, reacting at the hydrogen pressure of 2.914MPa and the temperature of 100 ℃, and cooling to separate out the catalyst after the reaction. After the solution is treated by ion exchange resin, water is evaporated under reduced pressure, and the 4, 4-di (1-methylethyl) -1, 7-heptanediol is separated and purified, wherein the structural formula of the 4, 4-di (1-methylethyl) -1, 7-heptanediol is as follows:
Figure GDA0001695705660000171
(b) performing esterification reaction; preparing terephthalic acid, ethylene glycol and 4, 4-di (1-methylethyl) -1, 7-heptanediol into slurry with the molar ratio of 1:1.7:0.05, adding antimony acetate, titanium dioxide and trimethyl phosphite, uniformly mixing, and pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.2MPa, the temperature of the esterification reaction is 253 ℃, and the end point of the esterification reaction is determined when the distilled amount of water in the esterification reaction reaches 96% of a theoretical value, wherein the adding amount of the antimony acetate is 0.01% of the weight of the terephthalic acid, the adding amount of the titanium dioxide is 0.20% of the weight of the terephthalic acid, and the adding amount of the trimethyl phosphite is 0.05% of the weight of the terephthalic acid;
(c) performing polycondensation reaction; after the esterification reaction is finished, the polycondensation reaction in the low vacuum stage is started under the condition of negative pressure, the pressure is stably pumped from normal pressure to the absolute pressure of 480Pa within 38min, the reaction temperature is 262 ℃, the reaction time is 38min, then continuously vacuumizing, carrying out polycondensation reaction in a high vacuum stage, further reducing the reaction pressure to 98Pa absolute, the reaction temperature to 279 ℃, and the reaction time to 80min to obtain modified polyester, wherein the molecular chain of the modified polyester comprises a terephthalic acid chain segment, a glycol chain segment and a 4, 4-di (1-methylethyl) -1, 7-heptanediol chain segment, the content of cyclic oligomer in the modified polyester is 0.55 wt%, the number average molecular weight is 27000, the molecular weight distribution index is 2.2, and the molar content of the 4, 4-di (1-methylethyl) -1, 7-heptanediol chain segment in the modified polyester is 4% of the molar content of the terephthalic acid chain segment;
(2) preparing an oiling agent;
uniformly mixing 2-hydroxymethyl-15-crown-5 with potassium dodecatetradecanol phosphate, trimethylolpropane laurate and sodium pentadecylsulfonate at normal temperature, adding the mixture into No. 14 mineral oil, and uniformly stirring the mixture at 55 ℃ for 1h to obtain an oil agent, wherein the adding amount of each component is as follows in parts by weight: 3 parts of No. 14 mineral oil; 10 parts of trimethylolpropane laurate; 75 parts of 2-hydroxymethyl-15-crown-5; 14 parts of potassium dodecatetradecanol phosphate; and 7 parts of sodium pentadecylsulfonate. The content of crown ether in the prepared oil agent is 68.80 wt%, the high temperature resistance of the oil agent is excellent, and the thermal weight loss is 12 wt% after the oil agent is heated for 2 hours at 200 ℃; the viscosity of the oil agent is low, and the kinematic viscosity is 27.5mm at the temperature of (50 +/-0.01) ° C2(s) a kinematic viscosity of 0.95mm after preparation with water as an emulsion having a concentration of 10% by weight2The oil has high oil film strength of 126N, surface tension of 25.4cN/cm, and specific resistance of 1.6 × 108Omega cm; coefficient of static friction (. mu.) between fibres (F/F) after oilings) 0.255, coefficient of dynamic friction (. mu.)d) Is 0.267; after oiling, the coefficient of static friction (μ) between the fiber and the metal (F/M)s) 0.203, coefficient of dynamic friction (. mu.)d) 0.330, and the prepared oil agent is prepared into an emulsion with the concentration of 20wt% by using water when in use;
(3) the modified polyester is subjected to solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting, oiling by an activated oil agent, winding and pre-activation treatment to prepare the low shrinkage activated polyester industrial yarn, wherein the intrinsic viscosity of the modified polyester after solid phase polycondensation tackifying is 1.08dL/g, the replacement period of a spinning assembly is 41 days, and the spinning technological parameters of the low shrinkage activated polyester industrial yarn are as follows: the temperature of each area of the screw is 300 ℃; the temperature of the box body is 298 ℃; the head pressure is 168 Bar; the temperature of the cross air blow is 22 ℃; the cross-air humidity is 78%; the side blowing wind speed is 0.42 m/s; the oiling rate of the activating oil agent is 0.43 wt%; the pre-network pressure is 0.15 MPa; the network pressure is 0.21 MPa; the winding speed is 3050 m/min; the preactivation treatment temperature is 72 ℃; the pre-activation treatment time is 23 h; the technological parameters of stretching and heat setting are as follows: GR-1 speed is 520 m/min; the GR-2 speed is 700 m/min; the GR-2 temperature is 85 ℃; the GR-3 speed is 2100 m/min; the GR-3 temperature is 120 ℃; GR-4 speed is 3100 m/min; GR-4 temperature is 230 ℃; GR-5 speed is 3100 m/min; the GR-5 temperature is 220 ℃; GR-6 speed is 2800 m/min; the GR-6 temperature was 170 ℃.
The fineness of the finally prepared low shrinkage activated polyester industrial yarn is 1500dtex, the deviation rate of linear density is-1.0%, the breaking strength is 7.2cN/dtex, the CV value of the breaking strength is 2.9%, the central value of the elongation at break is 20.3%, the deviation rate of the elongation at break is-1.1%, the CV value of the elongation at break is 7.4%, the number of networks is 5/m, the oil content is 0.65%, the full-wrap rate is 99.4%, the dry heat shrinkage rate of the low shrinkage activated polyester industrial yarn under the conditions of 177 ℃, 10min and 0.05cN/dtex is 4.9%, the dry heat shrinkage rate under the conditions of 190 ℃, 15min and 0.01cN/dtex is 3.9%, and the wicking height is 4.5 mm.
Example 7
A preparation method of low-shrinkage activated polyester industrial yarn comprises the following steps:
(1) preparing modified polyester;
(a) preparing 3, 3-dipropyl-1, 5-pentanediol; reacting 3, 3-dipropyl-propionaldehyde, acetaldehyde and triethylamine for 20min at 93 ℃ in a nitrogen atmosphere, then adding the concentrated solution into a hydrogenation reactor with a Raney nickel catalyst, reacting at the hydrogen pressure of 2.914MPa and the temperature of 100 ℃, cooling after the reaction is finished, and separating out the catalyst. After the solution is treated by ion exchange resin, water is evaporated under reduced pressure, and the 3, 3-dipropyl-1, 5-pentanediol is separated and purified, wherein the structural formula of the 3, 3-dipropyl-1, 5-pentanediol is as follows:
Figure GDA0001695705660000181
(b) performing esterification reaction; preparing terephthalic acid, ethylene glycol and 3, 3-dipropyl-1, 5-pentanediol with the molar ratio of 1:1.8:0.03 into slurry, adding antimony trioxide, titanium dioxide and triphenyl phosphate, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.3MPa, the esterification reaction temperature is 250 ℃, and the esterification reaction end point is when the distilled amount of water in the esterification reaction reaches 90% of a theoretical value, wherein the adding amount of the antimony trioxide is 0.03% of the weight of the terephthalic acid, the adding amount of the titanium dioxide is 0.24% of the weight of the terephthalic acid, and the adding amount of the triphenyl phosphate is 0.02% of the weight of the terephthalic acid;
(c) performing polycondensation reaction; after the esterification reaction is finished, the polycondensation reaction in the low vacuum stage is started under the condition of negative pressure, the pressure is smoothly pumped from normal pressure to the absolute pressure of 455Pa within 42min, the reaction temperature is 264 ℃, the reaction time is 45min, then continuously vacuumizing, carrying out polycondensation reaction in a high vacuum stage, further reducing the reaction pressure to 85Pa absolute, the reaction temperature to 285 ℃, the reaction time to 75min, preparing modified polyester, wherein the molecular chain of the modified polyester comprises a terephthalic acid chain segment, an ethylene glycol chain segment and a 3, 3-dipropyl-1, 5-pentanediol chain segment, the content of cyclic oligomers in the modified polyester is 0.45 wt%, the number average molecular weight is 26500, the molecular weight distribution index is 2.2, and the molar content of the 3, 3-dipropyl-1, 5-pentanediol chain segment in the modified polyester is 4.5 percent of the molar content of the terephthalic acid chain segment;
(2) preparing an oiling agent;
uniformly mixing 15-crown ether-5 with dodecyl phosphate potassium salt, trimethylolpropane laurate and sodium hexadecylsulfonate at normal temperature, adding the mixture into 15# mineral oil, and uniformly stirring the mixture for 2 hours at 41 ℃ to obtain an oil agent, wherein the adding amount of each component is as follows in parts by weight: 8 parts of No. 15 mineral oil; 20 parts of trimethylolpropane laurate; 100 portions of 15-crown ether-5; 15 parts of dodecyl phosphate potassium salt; the hexadecyl sodium sulfonate is 2 parts. The content of crown ether in the prepared oil agent is 68.97 wt%, the high temperature resistance of the oil agent is excellent, and the thermal weight loss is 8.5 wt% after the oil agent is heated for 2 hours at 200 ℃; the viscosity of the oil agent is low, and the kinematic viscosity is 28.4mm at the temperature of (50 +/-0.01) ° C2(s) a kinematic viscosity of 0.94mm after preparation with water as an emulsion having a concentration of 10% by weight2(s) the oil film strength of the oil agent is high and is 122N, the surface tension of the oil agent is 26.8cN/cm, and the specific resistance is 1.8 × 108Omega cm; coefficient of static friction (. mu.) between fibres (F/F) after oilings) 0.263, coefficient of dynamic friction (. mu.)d) Is 0.268; after oiling, the coefficient of static friction (μ) between the fiber and the metal (F/M)s) 0.210, coefficient of dynamic friction (. mu.)d) 0.320, and the prepared oil agent is prepared into an emulsion with the concentration of 13 wt% by using water when in use;
(3) the modified polyester is subjected to solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting, oiling by an activated oil agent, winding and pre-activation treatment to prepare the low shrinkage activated polyester industrial yarn, wherein the intrinsic viscosity of the modified polyester after solid phase polycondensation tackifying is 1.09dL/g, the replacement period of a spinning assembly is 41 days, and the spinning technological parameters of the low shrinkage activated polyester industrial yarn are as follows: the temperature of each area of the screw is 300 ℃; the temperature of the box body is 298 ℃; the head pressure is 168 Bar; the temperature of the cross air blow is 22 ℃; the cross-air humidity is 78%; the side blowing wind speed is 0.42 m/s; the oiling rate of the activating oil agent is 0.43 wt%; the pre-network pressure is 0.15 MPa; the network pressure is 0.21 MPa; the winding speed is 3100 m/min; the preactivation treatment temperature is 72 ℃; the pre-activation treatment time is 23 h; the technological parameters of stretching and heat setting are as follows: GR-1 speed is 520 m/min; the GR-2 speed is 700 m/min; the GR-2 temperature is 85 ℃; the GR-3 speed is 2100 m/min; the GR-3 temperature is 120 ℃; GR-4 speed is 2900 m/min; GR-4 temperature is 230 ℃; GR-5 speed is 2900 m/min; the GR-5 temperature is 210 ℃; GR-6 speed is 2800 m/min; the GR-6 temperature was 170 ℃.
The fineness of the finally prepared low shrinkage activated polyester industrial yarn is 1800dtex, the deviation rate of linear density is-0.8%, the breaking strength is 7.2cN/dtex, the CV value of the breaking strength is 2.9%, the central value of the elongation at break is 20.3%, the deviation rate of the elongation at break is-0.7%, the CV value of the elongation at break is 7.3%, the number of networks is 5/m, the oil content is 0.85%, the full-wrap rate is 99.7%, the dry heat shrinkage rate of the low shrinkage activated polyester industrial yarn under the conditions of 177 ℃, 10min and 0.05cN/dtex is 6.1%, the dry heat shrinkage rate under the conditions of 190 ℃, 15min and 0.01cN/dtex is 4.8%, and the wicking height is 4.7 mm.
Example 8
A preparation method of low-shrinkage activated polyester industrial yarn comprises the following steps:
(1) preparing modified polyester;
(a) preparing 4, 4-dipropyl-1, 7-heptanediol; reacting 4, 4-dipropyl-butyraldehyde, acetaldehyde and triethylamine for 20min at 92.5 ℃ in a nitrogen atmosphere, then adding the concentrated solution into a hydrogenation reactor with a Raney nickel catalyst, reacting at the hydrogen pressure of 2.914MPa and the temperature of 100 ℃, cooling after the reaction is finished, and separating out the catalyst. Treating the solution with ion exchange resin, evaporating water under reduced pressure, separating, and purifying to obtain 4, 4-dipropyl-1, 7-heptanediol, wherein the structural formula of the 4, 4-dipropyl-1, 7-heptanediol is as follows:
Figure GDA0001695705660000201
(b) performing esterification reaction; preparing terephthalic acid, ethylene glycol and 4, 4-dipropyl-1, 7-heptanediol with a molar ratio of 1:1.9:0.04 into slurry, adding ethylene glycol antimony, titanium dioxide and trimethyl phosphate, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.3MPa, the esterification reaction temperature is 260 ℃, and the esterification reaction endpoint is determined when the water distillation amount in the esterification reaction reaches 93% of a theoretical value, wherein the adding amount of the ethylene glycol antimony is 0.04% of the weight of the terephthalic acid, the adding amount of the titanium dioxide is 0.21% of the weight of the terephthalic acid, and the adding amount of the trimethyl phosphate is 0.03% of the weight of the terephthalic acid;
(c) performing polycondensation reaction; after the esterification reaction is finished, the polycondensation reaction in the low vacuum stage is started under the condition of negative pressure, the pressure is stably pumped from 0.3MPa to 475Pa in absolute pressure within 45min, the reaction temperature is 265 ℃, the reaction time is 48min, then continuously vacuumizing, carrying out polycondensation reaction in a high vacuum stage, further reducing the reaction pressure to 88Pa absolute, 283 ℃ reaction temperature, and 80min reaction time to obtain modified polyester, wherein the molecular chain of the modified polyester comprises a terephthalic acid chain segment, a glycol chain segment and a 4, 4-dipropyl-1, 7-heptanediol chain segment, the content of cyclic oligomer in the modified polyester is 0.6wt%, the number average molecular weight is 23000, the molecular weight distribution index is 2.0, and the molar content of the 4, 4-dipropyl-1, 7-heptanediol chain segment in the modified polyester is 3% of the molar content of the terephthalic acid chain segment;
(2) preparing an oiling agent;
uniformly mixing 2-hydroxymethyl-12-crown-4 with potassium dodecatetradecanol phosphate, trimethylolpropane laurate and sodium pentadecylsulfonate at normal temperature, adding the mixture into No. 16 mineral oil, and uniformly stirring the mixture at 45 ℃ for 3 hours to obtain an oil agent, wherein the adding amount of each component is as follows in parts by weight: 9 parts of No. 16 mineral oil; 80 portions of 2-hydroxymethyl-12-crown-4; 12 parts of potassium dodecatetradecanol phosphate; 5 parts of sodium pentadecylsulfonate. The content of crown ether in the prepared oil agent is 83.33 wt%, the high temperature resistance of the oil agent is excellent, and the thermal weight loss is 14 wt% after the oil agent is heated for 2 hours at 200 ℃; the viscosity of the oil agent is low, and the kinematic viscosity is 30.0mm at the temperature of (50 +/-0.01) ° C2(s) a kinematic viscosity of 0.93mm after preparation with water as an emulsion having a concentration of 10% by weight2The oil has high oil film strength of 127N, surface tension of 23.5cN/cm, and specific resistance of 1.5 × 108Omega cm; coefficient of static friction (. mu.) between fibres (F/F) after oilings) 0.262, coefficient of dynamic friction (. mu.)d) Is 0.273; after oiling, the coefficient of static friction (μ) between the fiber and the metal (F/M)s) 0.208, coefficient of dynamic friction (. mu.)d) 0.328, and the prepared oil agent is prepared into emulsion with the concentration of 18 wt% by using water when in use;
(3) the modified polyester is subjected to solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting, oiling by an activated oil agent, winding and pre-activation treatment to prepare the low shrinkage activated polyester industrial yarn, wherein the intrinsic viscosity of the modified polyester after solid phase polycondensation tackifying is 1.12dL/g, the replacement period of a spinning assembly is 41 days, and the spinning technological parameters of the low shrinkage activated polyester industrial yarn are as follows: the temperature of each area of the screw is 300 ℃; the temperature of the box body is 298 ℃; the head pressure is 168 Bar; the temperature of the cross air blow is 22 ℃; the cross-air humidity is 78%; the side blowing wind speed is 0.42 m/s; the oiling rate of the activating oil agent is 0.43 wt%; the pre-network pressure is 0.15 MPa; the network pressure is 0.21 MPa; the winding speed is 3200 m/min; the preactivation treatment temperature is 72 ℃; the pre-activation treatment time is 23 h; the technological parameters of stretching and heat setting are as follows: GR-1 speed is 520 m/min; the GR-2 speed is 700 m/min; the GR-2 temperature is 85 ℃; the GR-3 speed is 2100 m/min; the GR-3 temperature is 120 ℃; GR-4 speed is 3300 m/min; GR-4 temperature is 230 ℃; GR-5 speed is 3300 m/min; GR-5 temperature is 230 ℃; GR-6 speed is 2800 m/min; the GR-6 temperature was 170 ℃.
The fineness of the finally prepared low-shrinkage activated polyester industrial yarn is 1900dtex, the deviation rate of linear density is-1.2%, the breaking strength is 7.2cN/dtex, the CV value of the breaking strength is 2.9%, the central value of the elongation at break is 20.3%, the deviation rate of the elongation at break is-1.4%, the CV value of the elongation at break is 7.8%, the number of networks is 5/m, the oil content is 0.5%, the full-wrap rate is 99.3%, the dry heat shrinkage rate of the low-shrinkage activated polyester industrial yarn under the conditions of 177 ℃, 10min and 0.05cN/dtex is 5.2%, the dry heat shrinkage rate under the conditions of 190 ℃, 15min and 0.01cN/dtex is 4.7%, and the wicking height is 4.6 mm.
Example 9
A preparation method of low-shrinkage activated polyester industrial yarn comprises the following steps:
(1) preparing modified polyester;
(a) preparing 4-methyl-4- (1, 1-dimethylethyl) -1, 7-heptanediol; reacting 4-methyl-4- (1, 1-dimethylethyl) -butyraldehyde, propionaldehyde and triethylamine for 20min at 91 ℃ under the nitrogen atmosphere, then adding the concentrated solution into a hydrogenation reactor with a Raney nickel catalyst, reacting at the hydrogen pressure of 2.914MPa and the temperature of 100 ℃, cooling after the reaction is finished, separating the catalyst out, treating the solution with ion exchange resin, evaporating water under reduced pressure, separating and purifying to obtain 4-methyl-4- (1, 1-dimethylethyl) -1, 7-heptanediol, wherein the structural formula of the 4-methyl-4- (1, 1-dimethylethyl) -1, 7-heptanediol is as follows:
Figure GDA0001695705660000221
(b) performing esterification reaction; preparing terephthalic acid, ethylene glycol and 4-methyl-4- (1, 1-dimethylethyl) -1, 7-heptanediol with the molar ratio of 1:2.0:0.05 into slurry, adding antimony acetate, titanium dioxide and trimethyl phosphate, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is normal pressure, the temperature of the esterification reaction is 251 ℃, and the end point of the esterification reaction is determined when the distilled amount of water in the esterification reaction reaches 96% of a theoretical value, wherein the adding amount of the antimony acetate is 0.05% of the weight of the terephthalic acid, the adding amount of the titanium dioxide is 0.22% of the weight of the terephthalic acid, and the adding amount of the trimethyl phosphate is 0.04% of the weight of the terephthalic acid;
(c) performing polycondensation reaction; after the esterification reaction is finished, starting the polycondensation reaction in the low vacuum stage under the condition of negative pressure, smoothly pumping the pressure from normal pressure to the absolute pressure of 420Pa within 30min, the reaction temperature is 267 ℃, the reaction time is 50min, then continuing to pump the vacuum, carrying out the polycondensation reaction in the high vacuum stage, further reducing the reaction pressure to the absolute pressure of 80Pa, the reaction temperature is 280 ℃, and the reaction time is 90min, thus obtaining the modified polyester, wherein the molecular chain of the modified polyester comprises a terephthalic acid chain segment, a glycol chain segment and a 4-methyl-4- (1, 1-dimethylethyl) -1, 7-heptanediol chain segment, the content of cyclic oligomer in the modified polyester is 0.25 wt%, the number average molecular weight is 24000, the molecular weight distribution index is 2.2, and the 4-methyl-4- (1, 1-dimethylethyl) -1 in the modified polyester, the molar content of the 7-heptanediol chain segment is 4 percent of the molar content of the terephthalic acid chain segment;
(2) preparing an oiling agent;
uniformly mixing 2-hydroxymethyl-15-crown-5 with dodecyl phosphate potassium salt, trimethylolpropane laurate and sodium dodecyl sulfate at normal temperature, and uniformly stirring at 55 ℃ for 3 hours to obtain an oil agent, wherein the adding amount of each component is as follows in parts by weight: 15 parts of trimethylolpropane laurate; 90 portions of 2-hydroxymethyl-15-crown-5; 8 parts of dodecyl phosphate potassium salt; 7 parts of sodium dodecyl sulfate. The content of crown ether in the prepared oil agent is 81.81 wt%, the high temperature resistance of the oil agent is excellent, and the thermal weight loss is 10wt% after the oil agent is heated for 2 hours at 200 ℃; the viscosity of the oil agent is low, and the kinematic viscosity is 29.7mm at the temperature of (50 +/-0.01) ° C2(s) a kinematic viscosity of 0.94mm after preparation with water as an emulsion having a concentration of 10% by weight2The oil has high oil film strength of 126N, surface tension of 24.8cN/cm, and specific resistance of 1.8 × 108Omega cm; coefficient of static friction (. mu.) between fibres (F/F) after oilings) 0.250, coefficient of dynamic friction (. mu.)d) Is 0.264; after oiling, the coefficient of static friction (μ) between the fiber and the metal (F/M)s) 0.210, coefficient of dynamic friction (. mu.)d) 0.321, when the prepared oil agent is used, water is used for preparing emulsion with the concentration of 10 wt%;
(3) the modified polyester is subjected to solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting, oiling by an activated oil agent, winding and pre-activation treatment to prepare the low shrinkage activated polyester industrial yarn, wherein the intrinsic viscosity of the modified polyester after solid phase polycondensation tackifying is 1.17dL/g, the replacement period of a spinning assembly is 43 days, and the spinning technological parameters of the low shrinkage activated polyester industrial yarn are as follows: the temperature of each area of the screw is 312 ℃; the temperature of the box body is 298 ℃; the head pressure is 175 Bar; the temperature of the cross air blow is 23 ℃; the cross-air humidity is 82%; the air speed of the cross air blow is 0.5 m/s; the oiling rate of the activating oil agent is 0.48 wt%; the pre-network pressure is 0.17 MPa; the network pressure is 0.21 MPa; the winding speed is 3200 m/min; the preactivation treatment temperature is 78 ℃; the pre-activation treatment time is 28 h; the technological parameters of stretching and heat setting are as follows: GR-1 speed is 560 m/min; GR-2 speed is 800 m/min; the GR-2 temperature is 90 ℃; GR-3 speed is 2300 m/min; the GR-3 temperature is 130 ℃; GR-4 speed is 3200 m/min; GR-4 temperature is 230 ℃; GR-5 speed is 3200 m/min; the GR-5 temperature is 210 ℃; GR-6 speed is 3100 m/min; the GR-6 temperature was 210 ℃.
The fineness of the finally prepared low shrinkage activated polyester industrial yarn is 2800dtex, the deviation rate of linear density is 0.25%, the breaking strength is 6.5cN/dtex, the CV value of the breaking strength is 2.85%, the central value of the elongation at break is 20.4%, the deviation rate of the elongation at break is 0.4%, the CV value of the elongation at break is 7.5%, the number of networks is 8/m, the oil content is 0.95%, the full-wrap rate is 99.7%, the dry heat shrinkage rate of the low shrinkage activated polyester industrial yarn under the conditions of 177 ℃, 10min and 0.05cN/dtex is 6.1%, the dry heat shrinkage rate under the conditions of 190 ℃, 15min and 0.01cN/dtex is 5.1%, and the wicking height is 4.65 mm.
Example 10
A preparation method of low-shrinkage activated polyester industrial yarn comprises the following steps:
(1) preparing modified polyester;
(a) preparing 3-methyl-3-pentyl-1, 6-hexanediol; reacting 3-methyl-3-pentyl-propionaldehyde, propionaldehyde and triethylamine for 20min at 94 ℃ in a nitrogen atmosphere, then adding the concentrated solution into a hydrogenation reactor with a Raney nickel catalyst, reacting at the hydrogen pressure of 2.914MPa and the temperature of 100 ℃, cooling after the reaction is finished, and separating out the catalyst. After the solution is treated by ion exchange resin, water is evaporated under reduced pressure, and the 3-methyl-3-pentyl-1, 6-hexanediol is obtained through separation and purification, wherein the structural formula of the 3-methyl-3-pentyl-1, 6-hexanediol is as follows:
Figure GDA0001695705660000231
(b) performing esterification reaction; preparing terephthalic acid, ethylene glycol and 3-methyl-3-pentyl-1, 6-hexanediol into slurry with a molar ratio of 1:1.2:0.06, adding ethylene glycol antimony, titanium dioxide and trimethyl phosphite, uniformly mixing, and pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.1MPa, the esterification reaction temperature is 255 ℃, and the esterification reaction end point is when the water distillation amount in the esterification reaction reaches 92% of a theoretical value, wherein the adding amount of the ethylene glycol antimony is 0.01% of the weight of the terephthalic acid, the adding amount of the titanium dioxide is 0.20% of the weight of the terephthalic acid, and the adding amount of the trimethyl phosphite is 0.01% of the weight of the terephthalic acid;
(c) performing polycondensation reaction; after the esterification reaction is finished, the polycondensation reaction in the low vacuum stage is started under the condition of negative pressure, the pressure is stably pumped from normal pressure to the absolute pressure of 490Pa within 50min, the reaction temperature is 269 ℃, the reaction time is 30min, then continuously vacuumizing, carrying out polycondensation reaction in a high vacuum stage, further reducing the reaction pressure to 100Pa absolute, the reaction temperature to 281 ℃, the reaction time to 55min, preparing modified polyester, wherein the molecular chain of the modified polyester comprises a terephthalic acid chain segment, an ethylene glycol chain segment and a 3-methyl-3-amyl-1, 6-hexanediol chain segment, the content of cyclic oligomer in the modified polyester is 0.1 wt%, the number average molecular weight is 20000, the molecular weight distribution index is 1.9, and the molar content of the 3-methyl-3-amyl-1, 6-hexanediol chain segment in the modified polyester is 3.5 percent of the molar content of the terephthalic acid chain segment;
(2) preparing an oiling agent;
uniformly mixing 2-hydroxymethyl-12-crown-4 with dodecyl phosphate potassium salt, trimethylolpropane laurate and sodium dodecyl sulfate at normal temperature, adding the mixture into No. 9 mineral oil, and uniformly stirring the mixture for 1h at 40 ℃ to obtain an oil agent, wherein the adding amount of each component is as follows in parts by weight: 2 parts of No. 9 mineral oil; 10 parts of trimethylolpropane laurate; 90 portions of 2-hydroxymethyl-12-crown-4; 8 parts of dodecyl phosphate potassium salt; 3 parts of sodium dodecyl sulfate; the content of crown ether in the prepared oil agent is 79.6 wt%, the high temperature resistance of the oil agent is excellent, and the thermal weight loss is 14.5 wt% after the oil agent is heated for 2 hours at 200 ℃; the viscosity of the oil agent is low, and the kinematic viscosity is 29.6mm at the temperature of (50 +/-0.01) ° C2(s) a kinematic viscosity of 0.93mm after preparation with water as an emulsion having a concentration of 10% by weight2(s) the oil has high oil film strength of 125N, surface tension of 24.8cN/cm, and specific resistance of 1.3 × 108Omega cm; coefficient of static friction (. mu.) between fibres (F/F) after oilings) 0.255, coefficient of dynamic friction (. mu.)d) Is 0.266; after oiling, the coefficient of static friction (μ) between the fiber and the metal (F/M)s) 0.203, coefficient of dynamic friction (. mu.)d) 0.320, and the prepared oil agent is prepared into an emulsion with the concentration of 15wt% by using water when in use;
(3) the modified polyester is subjected to solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting, oiling by an activated oil agent, winding and pre-activation treatment to prepare the low shrinkage activated polyester industrial yarn, wherein the intrinsic viscosity of the modified polyester after solid phase polycondensation tackifying is 1.14dL/g, the replacement period of a spinning assembly is 43 days, and the spinning technological parameters of the low shrinkage activated polyester industrial yarn are as follows: the temperature of each area of the screw is 312 ℃; the temperature of the box body is 298 ℃; the head pressure is 175 Bar; the temperature of the cross air blow is 24 ℃; the cross-air humidity is 82%; the air speed of the cross air blow is 0.5 m/s; the oiling rate of the activating oil agent is 0.48 wt%; the pre-network pressure is 0.17 MPa; the network pressure is 0.21 MPa; the winding speed is 3200 m/min; the preactivation treatment temperature is 78 ℃; the pre-activation treatment time is 28 h; the technological parameters of stretching and heat setting are as follows: GR-1 speed is 560 m/min; the GR-2 speed is 700 m/min; the GR-2 temperature is 90 ℃; GR-3 speed is 2300 m/min; the GR-3 temperature is 130 ℃; GR-4 speed is 3200 m/min; GR-4 temperature is 230 ℃; GR-5 speed is 3200 m/min; GR-5 temperature is 230 ℃; GR-6 speed is 3100 m/min; the GR-6 temperature was 210 ℃.
The fineness of the finally prepared low shrinkage activated polyester industrial yarn is 2300dtex, the deviation rate of linear density is 0.4%, the breaking strength is 6.4cN/dtex, the CV value of the breaking strength is 2.9%, the central value of the elongation at break is 20.4%, the deviation rate of the elongation at break is 0.5%, the CV value of the elongation at break is 7.4%, the number of networks is 8/m, the oil content is 0.90%, the full-wrap rate is 99.7%, the dry heat shrinkage rate of the low shrinkage activated polyester industrial yarn under the conditions of 177 ℃, 10min and 0.05cN/dtex is 6.1%, the dry heat shrinkage rate under the conditions of 190 ℃, 15min and 0.01cN/dtex is 5.0%, and the wicking height is 4.58 mm.
Example 11
A preparation method of low-shrinkage activated polyester industrial yarn comprises the following steps:
(1) preparing modified polyester;
(a) preparing 3, 3-diamyl-1, 5-pentanediol; reacting 3, 3-diamyl-propionaldehyde, acetaldehyde and triethylamine for 20min at 95 ℃ in a nitrogen atmosphere, then adding the concentrated solution into a hydrogenation reactor with a Raney nickel catalyst, reacting at the hydrogen pressure of 2.914MPa and the temperature of 100 ℃, and cooling to separate out the catalyst after the reaction is finished. After the solution is treated by ion exchange resin, water is evaporated under reduced pressure, and the 3, 3-diamyl-1, 5-pentanediol is obtained by separation and purification, wherein the structural formula of the 3, 3-diamyl-1, 5-pentanediol is as follows:
Figure GDA0001695705660000251
(b) performing esterification reaction; preparing terephthalic acid, ethylene glycol and 3, 3-diamyl-1, 5-pentanediol with the molar ratio of 1:2.0:0.03 into slurry, adding antimony acetate, titanium dioxide and trimethyl phosphite, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.2MPa, the esterification reaction temperature is 250 ℃, and the esterification reaction end point is when the distilled amount of water in the esterification reaction reaches 97% of a theoretical value, wherein the adding amount of the antimony acetate is 0.01% of the weight of the terephthalic acid, the adding amount of the titanium dioxide is 0.23% of the weight of the terephthalic acid, and the adding amount of the trimethyl phosphite is 0.05% of the weight of the terephthalic acid;
(c) performing polycondensation reaction; after the esterification reaction is finished, the polycondensation reaction in the low vacuum stage is started under the condition of negative pressure, the pressure is stably pumped from normal pressure to the absolute pressure of 500Pa within 45min, the reaction temperature is 260 ℃, the reaction time is 40min, then continuously vacuumizing, carrying out polycondensation reaction in a high vacuum stage, further reducing the reaction pressure to 92Pa absolute, the reaction temperature to 277 ℃, reacting for 80min, preparing modified polyester, wherein the molecular chain of the modified polyester comprises a terephthalic acid chain segment, an ethylene glycol chain segment and a 3, 3-diamyl-1, 5-pentanediol chain segment, the content of cyclic oligomer in the modified polyester is 0.35 wt%, the number average molecular weight is 25500, the molecular weight distribution index is 1.8, and the molar content of the 3, 3-diamyl-1, 5-pentanediol chain segment in the modified polyester is 5 percent of the molar content of the terephthalic acid chain segment;
(2) preparing an oiling agent;
mixing 2-hydroxymethyl-12-crown-4 with potassium dodecyl phosphate, trimethylolpropane laurate and hexadecyl sulfonateThe sodium sulfate is uniformly mixed at normal temperature, then added into No. 12 mineral oil and uniformly stirred at 40 ℃ for 2.5 hours to obtain an oil agent, and the addition amount of each component is as follows according to parts by weight: 5 parts of No. 12 mineral oil; 95 parts of 2-hydroxymethyl-12-crown-4; 9 parts of dodecyl phosphate potassium salt; the hexadecyl sodium sulfonate is 2 parts. The content of crown ether in the prepared oil agent is 85.58wt%, the high temperature resistance of the oil agent is excellent, and the thermal weight loss is 9 wt% after the oil agent is heated for 2 hours at 200 ℃; the viscosity of the oil agent is low, and the kinematic viscosity is 29.5mm at the temperature of (50 +/-0.01) ° C2(s) a kinematic viscosity of 0.93mm after preparation with water as an emulsion having a concentration of 10% by weight2(s) the oil film strength of the oil agent is high and is 121N, the surface tension of the oil agent is 24.3cN/cm, and the specific resistance is 1.0 × 108Omega cm; coefficient of static friction (. mu.) between fibres (F/F) after oilings) 0.260, coefficient of dynamic friction (. mu.)d) Is 0.263; after oiling, the coefficient of static friction (μ) between the fiber and the metal (F/M)s) 0.202, coefficient of dynamic friction (. mu.)d) 0.330, and the prepared oil agent is prepared into an emulsion with the concentration of 19 wt% by using water when in use;
(3) the modified polyester is subjected to solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting, oiling by an activated oil agent, winding and pre-activation treatment to prepare the low shrinkage activated polyester industrial yarn, wherein the intrinsic viscosity of the modified polyester after solid phase polycondensation tackifying is 1.18dL/g, the replacement period of a spinning assembly is 43 days, and the spinning technological parameters of the low shrinkage activated polyester industrial yarn are as follows: the temperature of each area of the screw is 312 ℃; the temperature of the box body is 298 ℃; the head pressure is 170 Bar; the temperature of the cross air blow is 24 ℃; the cross-air humidity is 82%; the air speed of the cross air blow is 0.5 m/s; the oiling rate of the activating oil agent is 0.48 wt%; the pre-network pressure is 0.17 MPa; the network pressure is 0.21 MPa; the winding speed is 3200 m/min; the preactivation treatment temperature is 78 ℃; the pre-activation treatment time is 28 h; the technological parameters of stretching and heat setting are as follows: GR-1 speed is 560 m/min; the GR-2 speed is 900 m/min; the GR-2 temperature is 90 ℃; GR-3 speed is 2300 m/min; the GR-3 temperature is 130 ℃; GR-4 speed is 3200 m/min; GR-4 temperature is 230 ℃; GR-5 speed is 3200 m/min; the GR-5 temperature is 240 ℃; GR-6 speed is 3100 m/min; the GR-6 temperature was 210 ℃.
The fineness of the finally prepared low shrinkage activated polyester industrial yarn is 3200dtex, the linear density deviation rate is 0.35%, the breaking strength is 6.6cN/dtex, the CV value of the breaking strength is 2.8%, the central value of the elongation at break is 20.4%, the deviation rate of the elongation at break is 0.4%, the CV value of the elongation at break is 7.4%, the number of networks is 8/m, the oil content is 0.97%, the full-wrap rate is 99.7%, the dry heat shrinkage rate of the low shrinkage activated polyester industrial yarn under the conditions of 177 ℃, 10min and 0.05cN/dtex is 6.2%, the dry heat shrinkage rate under the conditions of 190 ℃, 15min and 0.01cN/dtex is 4.9%, and the wicking height is 4.59 mm.

Claims (9)

1. A preparation method of low-shrinkage activated polyester industrial yarn is characterized in that modified polyester is subjected to solid-phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting, oiling of activated oil, winding and pre-activation treatment to prepare the low-shrinkage activated polyester industrial yarn;
the molecular chain of the modified polyester comprises a terephthalic acid chain segment, an ethylene glycol chain segment and a dihydric alcohol chain segment with a branched chain, wherein the dihydric alcohol with the branched chain is 2-ethyl-2-methyl-1, 3-propanediol, 2-diethyl-1, 3-propanediol or 2-butyl-2-ethyl-1, 3-propanediol; the molar content of the dihydric alcohol chain segment with the branched chain in the modified polyester is 3-5% of that of the terephthalic acid chain segment;
the oiling oil agent contains crown ether, and the content of the crown ether is 67.30-85.58 wt%;
the crown ether is 2-hydroxymethyl-12-crown-4, 15-crown ether-5 or 2-hydroxymethyl-15-crown-5;
when the oil agent is used, preparing an emulsion with the concentration of 10-20 wt% by using water;
the content of cyclic oligomer in the modified polyester is less than or equal to 0.6 wt%.
2. The method for preparing the low-shrinkage activated polyester industrial yarn as claimed in claim 1, wherein the intrinsic viscosity of the modified polyester after solid-phase polycondensation and viscosity increase is 1.0-1.2 dL/g;
the replacement period of the spinning assembly is more than or equal to 40 days;
the thermal weight loss of the oil agent after heating treatment for 2 hours at 200 ℃ is less than 15 wt%;
the kinematic viscosity of the oil agent is 27.5-30.1 mm at the temperature of (50 +/-0.01) ° C2The kinematic viscosity of the oil agent prepared from water into 10wt% emulsion is 0.93-0.95 mm2/s；
The oil film strength of the oil agent is 121-127N;
the surface tension of the oil agent is 23.2-26.8 cN/cm, and the specific resistance is 1.0 × 108~1.8×108Ω·cm；
After oiling, the static friction coefficient between the fibers is 0.250-0.263, and the dynamic friction coefficient is 0.262-0.273;
after oiling, the static friction coefficient between the fiber and the metal is 0.202-0.210, and the dynamic friction coefficient is 0.320-0.332;
the oil agent also contains mineral oil, phosphate potassium salt, trimethylolpropane laurate and alkyl sodium sulfonate;
the mineral oil is one of 9# -17 # mineral oil;
the phosphate potassium salt is dodecyl phosphate potassium salt, isomeric tridecanol polyoxyethylene ether phosphate potassium salt or dodecatetradecanol phosphate potassium salt;
the sodium alkyl sulfonate is sodium dodecyl sulfonate, sodium pentadecyl sulfonate or sodium hexadecyl sulfonate.
3. The method for preparing the low shrinkage activated polyester industrial yarn according to claim 2, wherein the preparation method of the oil agent is as follows: uniformly mixing crown ether, phosphate potassium salt, trimethylolpropane laurate and sodium alkyl sulfonate, adding the mixture into mineral oil, and uniformly stirring to obtain an oil agent; the addition amount of each component is as follows according to the parts by weight:
0-10 parts of mineral oil;
0-20 parts of trimethylolpropane laurate;
70-100 parts of crown ether;
8-15 parts of phosphate potassium salt;
2-7 parts of sodium alkylsulfonate;
the mixing is carried out at normal temperature, the stirring temperature is 40-55 ℃, and the stirring time is 1-3 h.
4. The method for preparing the low shrinkage activated polyester industrial yarn according to claim 3, wherein the spinning process parameters of the low shrinkage activated polyester industrial yarn are as follows:
the temperature of each area of the screw is 290-320 ℃;
the temperature of the box body is 295-300 ℃;
the head pressure is 170 +/-5 Bar;
the temperature of the cross air blow is 23 +/-2 ℃;
the humidity of the cross air blow is 80 plus or minus 5 percent;
the side blowing wind speed is 0.45 +/-0.10 m/s;
the oiling rate of the activating oil agent is 0.4-0.5 wt%;
the pre-network pressure is 0.16 +/-0.02 MPa;
the network pressure is 0.21 +/-0.02 MPa;
the winding speed is 2600-3400 m/min;
the pre-activation treatment temperature is 70-80 ℃;
the pre-activation treatment time is 20-30 h;
the technological parameters of stretching and heat setting are as follows:
GR-1 speed is 480-600 m/min;
GR-2 speed is 500-1000 m/min; the GR-2 temperature is 80-100 ℃;
GR-3 speed is 1800-2500 m/min; the GR-3 temperature is 100-150 ℃;
GR-4 speed 2800-3500 m/min; GR-4 temperature is 200-250 ℃;
GR-5 speed 2800-3500 m/min; GR-5 temperature is 200-250 ℃;
GR-6 speed is 2600-3400 m/min; the GR-6 temperature is 150-220 ℃.
5. The method for preparing low shrinkage activated polyester industrial yarn according to claim 1, wherein: the low shrinkage activated polyester industrial yarn is made of modified polyester, the dry heat shrinkage rate of the low shrinkage activated polyester industrial yarn is 5.5 +/-0.8% under 177 ℃, 10min and 0.05cN/dtex conditions, the dry heat shrinkage rate is 2.8-5.8% under 190 ℃, 15min and 0.01cN/dtex conditions, and the wicking height is less than or equal to 5 mm.
6. The method for preparing the low shrinkage activated polyester industrial yarn as claimed in claim 5, wherein the fineness of the low shrinkage activated polyester industrial yarn is 930 to 3300dtex, the deviation rate of linear density is ± 1.5%, the breaking strength is not less than 7.0cN/dtex, the CV value of the breaking strength is not more than 3.0%, the central value of the breaking elongation is 20.0 to 20.5%, the deviation rate of the breaking elongation is ± 2%, the CV value of the breaking elongation is not more than 8.0%, the number of networks is 4 to 9/m, the oil content is 0.25 to 0.97%, and the full-package rate is not less than 99%.
7. The method for preparing low shrinkage activated polyester industrial yarn according to claim 5 or 6, wherein the modified polyester has a number average molecular weight of 20000 to 27000 and a molecular weight distribution index of 1.8 to 2.2.
8. The method for preparing the low shrinkage activated polyester industrial yarn according to claim 1, wherein the method for preparing the modified polyester comprises the following steps: uniformly mixing terephthalic acid, ethylene glycol and the dihydric alcohol with the branched chain, and then sequentially carrying out esterification reaction and polycondensation reaction to obtain modified polyester; the modified polyester comprises the following specific preparation steps:
(1) performing esterification reaction;
preparing terephthalic acid, ethylene glycol and the dihydric alcohol with the branched chain into slurry, adding a catalyst and a stabilizer, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is normal pressure to 0.3MPa, the esterification reaction temperature is 250-260 ℃, and the esterification reaction endpoint is determined when the distilled amount of water in the esterification reaction reaches more than 90% of a theoretical value;
(2) performing polycondensation reaction;
and after the esterification reaction is finished, starting the polycondensation reaction in a low vacuum stage under the negative pressure condition, stably pumping the pressure in the low vacuum stage from normal pressure to below 500Pa in 30-50 min at the reaction temperature of 260-270 ℃ for 30-50 min, then continuously pumping the vacuum to perform the polycondensation reaction in a high vacuum stage, further reducing the reaction pressure to below 100Pa, controlling the reaction temperature to 275-285 ℃ and the reaction time to be 50-90 min, and thus obtaining the modified polyester.
9. The method for preparing the low shrinkage activated polyester industrial yarn according to claim 8, wherein in the step (1), the molar ratio of the terephthalic acid, the ethylene glycol and the branched diol is 1: 1.2-2.0: 0.03-0.06, the addition amount of the catalyst is 0.01-0.05% of the weight of the terephthalic acid, and the addition amount of the stabilizer is 0.01-0.05% of the weight of the terephthalic acid;
the catalyst is antimony trioxide, ethylene glycol antimony or antimony acetate, and the stabilizer is triphenyl phosphate, trimethyl phosphate or trimethyl phosphite.
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