CN108385196B - High-strength colored polyester industrial yarn and preparation method thereof - Google Patents

High-strength colored polyester industrial yarn and preparation method thereof Download PDF

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CN108385196B
CN108385196B CN201711342802.0A CN201711342802A CN108385196B CN 108385196 B CN108385196 B CN 108385196B CN 201711342802 A CN201711342802 A CN 201711342802A CN 108385196 B CN108385196 B CN 108385196B
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modified polyester
industrial yarn
oil agent
strength
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CN108385196A (en
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汤方明
张烨
杨大矛
蒋丽波
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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
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • D—TEXTILES; PAPER
    • 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
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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
    • D06M13/10—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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
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    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—Polyethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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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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  • Chemical & Material Sciences (AREA)
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  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)

Abstract

The invention relates to a high-strength colored polyester industrial yarn and a preparation method thereof, wherein modified polyester and color master batch are mixed and then subjected to solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting and winding to prepare the high-strength colored polyester industrial yarn, an oiling agent for oiling contains crown ether, the content of the crown ether is 67.30-85.58 wt%, the main material of the industrial yarn is the modified polyester, 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, and the structural formula of the dihydric alcohol with the branched chain is as follows:
Figure DDA0001508768820000011
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 of the alkyl is 2-5, and the breaking strength of the prepared industrial yarn is more than or equal to 7.0 cN/dtex. The method is simple and reasonable, and the prepared industrial yarn has the advantages of high breaking strength and good uniformity.

Description

High-strength colored polyester industrial yarn and preparation method thereof
Technical Field
The invention belongs to the field of fiber preparation, and relates to a high-strength colored 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 resistance, light resistance, acid resistance, alkali resistance, corrosion resistance and the like, and the fabric prepared from the polyester fiber has the advantages of good crease resistance, good stiffness and smoothness and the like, so the polyester fiber is widely applied to the fields of clothing, home textiles and the like.
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.
The preparation of the high-strength colored polyester industrial yarn at the present stage has three main problems, namely, the oiling agent is quick to volatilize and easy to bond on the surface of the fiber, so that the prepared fiber has high unevenness rate and poor performance; secondly, the volatile residue of the oligomer in the fiber is on the surface of the spinneret plate, which causes fiber broken filaments and influences the quality of the fiber; thirdly, the oil absorption is increased after the pigment is added into the raw materials, and the spinnability of the colored silk is reduced.
Therefore, how to provide a preparation method of high-strength colored polyester industrial yarn which has uniform spinning and less oligomer generation and can obviously improve the quality of the industrial yarn 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 quality of the fiber is affected due to excessive residual oligomers in a spinneret plate, and the spinnability is affected due to the addition of pigments, and provides a preparation method of high-strength colored polyester industrial yarn, which is uniform in spinning, low in oligomer generation amount and capable of remarkably improving the quality of the industrial yarn. The introduction of the dihydric alcohol with the branched chain in the modified polyester reduces the cyclic oligomer generated in the side reaction of the polyester and improves the quality of the product; 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 and the heat resistance and stability are better, the processing performance of the fibers is improved, the occurrence of the phenomenon of broken filaments is reduced, and the quality of the prepared fibers is higher;
in order to achieve the purpose, the invention adopts the technical scheme that:
the high-strength colored polyester industrial yarn is mainly 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 GDA0001695738250000021
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 reduction of the ring shape is realizedThe oligomer generation is of little significance; the too large number of carbon atoms of the branched chain structure can generate intermolecular entanglement and influence the distribution of molecular weight;
the breaking strength of the high-strength colored polyester industrial yarn is more than or equal to 7.0cN/dtex, and the color is black, red, yellow or blue.
As a preferred technical scheme:
the high-strength colored polyester industrial yarn has the fineness of 700-3300 dtex, the deviation rate of linear density of +/-1.5%, the CV value of breaking strength of not more than 3.0%, the center value of elongation at break of 13.0-16.5%, the deviation rate of elongation at break of +/-1.5%, the CV value of elongation at break of not more than 8.0%, the center value of elongation at 4.0cN/dtex load of 5.5-7.0%, the deviation rate of elongation at 4.0cN/dtex load of +/-0.8%, the dry heat shrinkage rate under the conditions of 177 ℃, 10min and 0.05cN/dtex of 2.8-9.2%, the network of (5-8) +/-2/m, the oil content of 0.6 +/-0.2% and the full-up rate of not less than 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 high-strength colored 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 generation amount of cyclic oligomers is remarkably reduced;
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 is maintained;
the dihydric alcohol with a branch 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-dipentyl-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 high-strength colored polyester industrial yarn, which comprises the steps of mixing the modified polyester and the color master batch, and then carrying out solid-phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting and winding to obtain the high-strength colored polyester industrial yarn;
the oiling oil agent contains crown ether, and the content of the crown ether is 67.30-85.58 wt%;
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 due to too low amount, and other indexes are limited;
when the oil agent is used, water is used to prepare an emulsion with the concentration of 10-20 wt%.
As a preferred technical scheme:
according to the method, the content of the pigment in the color master batch is 20-40 wt%, and the addition amount of the color master batch is 2-3 wt% of the modified polyester; the intrinsic viscosity of the modified polyester after solid-phase polycondensation and tackifying is 1.0-1.2 dL/g; the replacement period of the spinning assembly is more than or equal to 30 days.
According to the method, the thermal weight loss of the oil agent after the oil agent is heated and treated at 200 ℃ for 2h 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 GDA0001695738250000061
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 high-strength colored polyester industrial yarn are as follows:
Figure GDA0001695738250000062
the technological parameters of stretching and heat setting are as follows:
Figure GDA0001695738250000063
the invention mechanism is as follows:
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 GDA0001695738250000071
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 GDA0001695738250000072
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 glycol2CH2The carbon fiber has stronger electron donating property, so that bond-forming electron pairs on newly formed chemical bond C-O bonds move towards the central C atom and are closer to the central atom, the bond angles α are larger than 109 degrees due to the increase of repulsive force, the probability of generating linear polymers is increased, the generation of cyclic oligomers is reduced, the phenomena of filament breakage, uneven thickness and fineness are eliminated, the influence of the oligomers on mechanical properties such as breaking strength and breaking elongation of the fiber is reduced, and the product quality is improved.
The oiling agent disclosed by the invention is an oiling 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 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 obviously improved.
Has the advantages that:
(1) the high-strength colored polyester industrial yarn has the advantages of high breaking strength and good uniformity, and has great market prospect;
(2) the preparation method of the high-strength colored polyester industrial yarn is simple and reasonable, prolongs the board cleaning period and improves the production efficiency;
(3) according to the preparation method of the high-strength colored polyester industrial yarn, disclosed by the invention, 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 obviously reduced.
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 high-strength colored 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 GDA0001695738250000091
(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; sodium dodecyl sulfate is 3 parts(ii) a 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) mixing modified polyester and color master batch, and then performing solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting and winding to obtain the high-strength colored polyester industrial yarn, wherein the content of pigment in the color master batch is 30 wt%, the addition amount of the color master batch is 2.5 wt% of the modified polyester, the intrinsic viscosity of the modified polyester after solid phase polycondensation tackifying is 1.15dL/g, the replacement cycle of a spinning assembly is 33 days, and the spinning process parameters of the high-strength colored polyester industrial yarn are as follows: the temperature of each area of the screw is 310 ℃; the temperature of the box body is 298 ℃; the head pressure is 140 Bar; the temperature of the cross air blow is 22 ℃; the humidity of the cross air blow is 80%; the air speed of the cross air blow is 0.6 m/s; the winding speed is 2800 m/min; the technological parameters of stretching and heat setting are as follows: GR-1 speed is 550 m/min; the GR-1 temperature is 80 ℃; GR-2 speed is 570 m/min; the GR-2 temperature is 95 ℃; GR-3 speed is 2200 m/min; the GR-3 temperature is 132 ℃; GR-4 speed is 3000 m/min; GR-4 temperature is 230 ℃; GR-5 speed is 3000 m/min; the GR-5 temperature was 160 ℃.
The finally prepared high-strength colored polyester industrial yarn is yellow, the breaking strength is 7.7cN/dtex, the fineness is 2200dtex, the deviation rate of linear density is 0.1%, the breaking strength CV value is 2.80%, the central value of elongation at break is 14.5%, the deviation rate of elongation at break is 0.1%, the CV value of elongation at break is 7.2%, the central value of elongation at 4.0cN/dtex load is 6.0%, the deviation rate of elongation at 4.0cN/dtex load is 0.05%, the dry heat shrinkage rate under the conditions of 177 ℃, 10min and 0.05cN/dtex is 9.2%, the network is 10/m, the oil content is 0.8%, and the full-up rate is 99.9%.
Example 2
A preparation method of high-strength colored 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 GDA0001695738250000111
(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; 15 parts of trimethylolpropane 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) mixing modified polyester and color master batch, and then performing solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting and winding to obtain the high-strength colored polyester industrial yarn, wherein the content of pigment in the color master batch is 20wt%, the addition amount of the color master batch is 2 wt% of the modified polyester, the intrinsic viscosity of the modified polyester after solid phase polycondensation tackifying is 1.0dL/g, the replacement cycle of a spinning assembly is 30 days, and the spinning process parameters of the high-strength colored 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 140 Bar; the temperature of the cross air blow is 22 ℃; the humidity of the cross air blow is 75 percent; the air speed of the cross air blow is 0.5 m/s; the winding speed is 2600 m/min; the technological parameters of stretching and heat setting are as follows: the GR-1 speed is 440 m/min; the GR-1 temperature is 75 ℃; GR-2 speed is 460 m/min; the GR-2 temperature is 90 ℃; GR-3 speed is 1900 m/min; the GR-3 temperature is 125 ℃; GR-4 speed is 2700 m/min; the GR-4 temperature is 220 ℃; GR-5 speed is 2500 m/min; the GR-5 temperature was 150 ℃.
The finally prepared high-strength colored polyester industrial yarn is yellow, the breaking strength is 7.0cN/dtex, the fineness is 700dtex, the deviation rate of linear density is-1.5%, the CV value of breaking strength is 3.0%, the central value of elongation at break is 13.0%, the deviation rate of elongation at break is-1.5%, the CV value of elongation at break is 8.0%, the central value of elongation at 4.0cN/dtex load is 5.5%, the deviation rate of elongation at 4.0cN/dtex load is-0.8%, the dry heat shrinkage rate under the conditions of 177 ℃, 10min and 0.05cN/dtex is 2.8%, the network is 3/m, the oil content is 0.4%, and the full-lap rate is 99.1%.
Example 3
A preparation method of high-strength colored 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 GDA0001695738250000121
(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 0.5 wt%, 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) mixing modified polyester and color master batch, and then performing solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting and winding to obtain the high-strength colored polyester industrial yarn, wherein the content of pigment in the color master batch is 40wt%, the addition amount of the color master batch is 3wt% of the modified polyester, the intrinsic viscosity of the modified polyester after solid phase polycondensation tackifying is 1.2dL/g, the replacement cycle of a spinning assembly is 31 days, and the spinning process parameters of the high-strength colored 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 140 Bar; the temperature of the cross air blow is 22 ℃; the cross-air humidity is 85%; the air speed of the cross air blow is 0.7 m/s; the winding speed is 3600 m/min; the technological parameters of stretching and heat setting are as follows: GR-1 speed is 650 m/min; the GR-1 temperature is 85 ℃; the GR-2 speed is 680 m/min; the GR-2 temperature is 100 ℃; GR-3 speed is 2400 m/min; the GR-3 temperature is 140 ℃; GR-4 speed is 3600 m/min; the GR-4 temperature is 250 ℃; GR-5 speed is 3600 m/min; the GR-5 temperature was 170 ℃.
The finally prepared high-strength colored polyester industrial yarn is red, the breaking strength is 7.05cN/dtex, the fineness is 3300dtex, the deviation rate of linear density is 1.5%, the CV value of breaking strength is 2.9%, the central value of elongation at break is 16.5%, the deviation rate of elongation at break is 1.5%, the CV value of elongation at break is 7.9%, the central value of elongation at 4.0cN/dtex load is 7.0%, the deviation rate of elongation at 4.0cN/dtex load is 0.8%, the dry heat shrinkage rate under the conditions of 177 ℃, 10min and 0.05cN/dtex is 2.9%, the network is 10/m, the oil content is 0.45%, and the full-lap rate is 99.2%.
Example 4
A preparation method of high-strength colored 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 95 ℃ under nitrogen atmosphere, 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 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 GDA0001695738250000141
(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 121N, and the surface tension of the oil agent is 24.3cNcm, specific resistance of 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) mixing modified polyester and color master batch, and then performing solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting and winding to obtain the high-strength colored polyester industrial yarn, wherein the content of pigment in the color master batch is 22 wt%, the addition amount of the color master batch is 2.2 wt% of the modified polyester, the intrinsic viscosity of the modified polyester after solid phase polycondensation tackifying is 1.12dL/g, the replacement cycle of a spinning assembly is 31 days, and the spinning process parameters of the high-strength colored polyester industrial yarn are as follows: the temperature of each area of the screw is 295 ℃; the temperature of the box body is 295 ℃; the head pressure is 140 Bar; the temperature of the cross air blow is 22 ℃; the cross-air humidity is 78%; the air speed of the cross air blow is 0.55 m/s; the winding speed is 2600 m/min; the technological parameters of stretching and heat setting are as follows: GR-1 speed is 480 m/min; the GR-1 temperature is 78 ℃; GR-2 speed is 485 m/min; the GR-2 temperature is 92 ℃; GR-3 speed is 1950 m/min; the GR-3 temperature is 128 ℃; GR-4 speed is 2800 m/min; GR-4 temperature is 230 ℃; GR-5 speed is 2600 m/min; the GR-5 temperature was 155 ℃.
The finally prepared high-strength colored polyester industrial yarn is black in color, the breaking strength is 7.2cN/dtex, the fineness is 1000dtex, the deviation rate of linear density is-1.2%, the CV value of breaking strength is 2.95%, the central value of elongation at break is 13.3%, the deviation rate of elongation at break is-1.2%, the CV value of elongation at break is 7.9%, the central value of elongation at 4.0cN/dtex load is 5.6%, the deviation rate of elongation at 4.0cN/dtex load is-0.6%, the dry heat shrinkage rate under the conditions of 177 ℃, 10min and 0.05cN/dtex is 3.0%, the network is 4/m, the oil content is 0.6%, and the full-lap rate is 99.4%.
Example 5
A preparation method of high-strength colored 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 92 ℃ under 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 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 GDA0001695738250000161
(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 0.5 wt%, 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) mixing modified polyester and color master batch, and then performing solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting and winding to obtain the high-strength colored polyester industrial yarn, wherein the content of pigment in the color master batch is 24 wt%, the addition amount of the color master batch is 2.5 wt% of the modified polyester, the intrinsic viscosity of the modified polyester after solid phase polycondensation tackifying is 1.15dL/g, the replacement period of a spinning assembly is 31 days, and the spinning process parameters of the high-strength colored polyester industrial yarn are as follows: the temperature of each area of the screw is 300 ℃; the temperature of the box body is 296 ℃; the head pressure is 140 Bar; the temperature of the cross air blow is 22 ℃; the cross-air humidity is 79%; the side blowing wind speed is 0.56 m/s; the winding speed is 2700 m/min; the technological parameters of stretching and heat setting are as follows: GR-1 speed is 500 m/min; GR-1 temperature is 79 ℃; GR-2 speed is 550 m/min; GR-2 temperature 93 ℃; the GR-3 speed is 2000 m/min; the GR-3 temperature is 129 ℃; GR-4 speed is 2950 m/min; GR-4 temperature is 230 ℃; GR-5 speed is 2700 m/min; the GR-5 temperature was 160 ℃.
The finally prepared high-strength colored polyester industrial yarn is blue, the breaking strength is 7.3cN/dtex, the fineness is 1500dtex, the deviation rate of linear density is-1.0%, the CV value of breaking strength is 2.88%, the central value of elongation at break is 13.8%, the deviation rate of elongation at break is-1.1%, the CV value of elongation at break is 7.8%, the central value of elongation at 4.0cN/dtex load is 6.0%, the deviation rate of elongation at 4.0cN/dtex load is-0.4%, the dry heat shrinkage rate under the conditions of 177 ℃, 10min and 0.05cN/dtex is 4.2%, the network is 5/m, the oil content is 0.65%, and the full-lap rate is 99.4%.
Example 6
A preparation method of high-strength colored 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 90 ℃ under 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 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 GDA0001695738250000181
(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) mixing modified polyester and color master batch, and then performing solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting and winding to obtain the high-strength colored polyester industrial yarn, wherein the content of pigment in the color master batch is 28 wt%, the addition amount of the color master batch is 2.5 wt% of the modified polyester, the intrinsic viscosity of the modified polyester after solid phase polycondensation tackifying is 1.15dL/g, the replacement period of a spinning assembly is 31 days, and the spinning process parameters of the high-strength colored polyester industrial yarn are as follows: the temperature of each zone of the screw is 296 ℃; the temperature of the box body is 296 ℃; the head pressure is 140 Bar; the temperature of the cross air blow is 22 ℃; the humidity of the cross air blow is 80%; the side blowing wind speed is 0.57 m/s; the winding speed is 2800 m/min; the technological parameters of stretching and heat setting are as follows: GR-1 speed is 520 m/min; GR-1 temperature is 82 ℃; GR-2 speed is 570 m/min; the GR-2 temperature is 95 ℃; the GR-3 speed is 2000 m/min; the GR-3 temperature is 130 ℃; GR-4 speed is 2900 m/min; GR-4 temperature is 230 ℃; GR-5 speed is 2800 m/min; the GR-5 temperature was 165 ℃.
The finally prepared high-strength colored polyester industrial yarn is red, the breaking strength is 7.4cN/dtex, the fineness is 1600dtex, the deviation rate of linear density is-0.8%, the CV value of breaking strength is 2.85%, the central value of elongation at break is 14.5%, the deviation rate of elongation at break is-0.8%, the CV value of elongation at break is 7.7%, the central value of elongation at 4.0cN/dtex load is 6.0%, the deviation rate of elongation at 4.0cN/dtex load is-0.4%, the dry heat shrinkage rate under the conditions of 177 ℃, 10min and 0.05cN/dtex is 6.2%, the network is 10/m, the oil content is 0.7%, and the full-lap rate is 99.5%.
Example 7
A preparation method of high-strength colored 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 ℃ under nitrogen atmosphere, 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 GDA0001695738250000201
(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, 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 addition of the components is calculated according to parts by weightThe amount of the additive is as follows: 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) mixing modified polyester and color master batch, and then performing solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting and winding to obtain the high-strength colored polyester industrial yarn, wherein the content of pigment in the color master batch is 32 wt%, the addition amount of the color master batch is 2.8 wt% of the modified polyester, the intrinsic viscosity of the modified polyester after solid phase polycondensation tackifying is 1.16dL/g, the replacement cycle of a spinning assembly is 32 days, and the spinning technological parameters of the high-strength colored polyester industrial yarn are as follows: the temperature of each zone of the screw is 305 ℃; the temperature of the box body is 297 ℃; the head pressure is 140 Bar; the temperature of the cross air blow is 22 ℃; the cross-air humidity is 81%; the air speed of the cross air blow is 0.65 m/s; the winding speed is 2850 m/min; the technological parameters of stretching and heat setting are as follows: GR-1 speed is 540 m/min; GR-1 temperature is 79 ℃; GR-2 speed is 560 m/min; the GR-2 temperature is 90-100 ℃; the GR-3 speed is 2100 m/min; the GR-3 temperature is 131 ℃; GR-4 speed is 3100 m/min; GR-4 temperature is 235 ℃; GR-5 speed is 2850 m/min; the GR-5 temperature was 166 ℃.
The finally prepared high-strength colored polyester industrial yarn is black in color, the breaking strength is 7.5cN/dtex, the fineness is 2000dtex, the deviation rate of linear density is 1.0%, the CV value of breaking strength is 2.8%, the central value of elongation at break is 14.8%, the deviation rate of elongation at break is 1.0%, the CV value of elongation at break is 7.5%, the central value of elongation at 4.0cN/dtex load is 6.6%, the deviation rate of elongation at 4.0cN/dtex load is 0.4%, the dry heat shrinkage rate under the conditions of 177 ℃, 10min and 0.05cN/dtex is 7.2%, the network is 10/m, the oil content is 0.6%, and the full-lap rate is 99.5%.
Example 8
A preparation method of high-strength colored 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 94 ℃ in nitrogen atmosphere, 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 GDA0001695738250000221
(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 normal pressure to the absolute pressure of 475Pa 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) mixing modified polyester and color master batch, and then performing solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting and winding to obtain the high-strength colored polyester industrial yarn, wherein the content of pigment in the color master batch is 35 wt%, the addition amount of the color master batch is 2.8 wt% of the modified polyester, the intrinsic viscosity of the modified polyester after solid phase polycondensation tackifying is 1.1dL/g, the replacement cycle of a spinning assembly is 32 days, and the spinning process parameters of the high-strength colored polyester industrial yarn are as follows: the temperature of each area of the screw is 310 ℃; the temperature of the box body is 298 ℃; the head pressure is 140 Bar; the temperature of the cross air blow is 22 ℃; the cross-air humidity is 83%; the air speed of the cross air blow is 0.67 m/s; the winding speed is 3200 m/min; the technological parameters of stretching and heat setting are as follows: GR-1 speed is 560 m/min; the GR-1 temperature is 84 ℃; GR-2 speed is 580 m/min; the GR-2 temperature is 96 ℃; GR-3 speed is 2200 m/min; the GR-3 temperature is 133 ℃; GR-4 speed is 3300 m/min; GR-4 temperature 240 ℃; GR-5 speed is 3200 m/min; the GR-5 temperature was 162 ℃.
The finally prepared high-strength colored polyester industrial yarn is red, the breaking strength is 7.6cN/dtex, the fineness is 2500dtex, the deviation rate of linear density is 0.5%, the CV value of breaking strength is 2.8%, the central value of elongation at break is 15.5%, the deviation rate of elongation at break is 0.5%, the CV value of elongation at break is 7.3%, the central value of elongation at 4.0cN/dtex load is 6.7%, the deviation rate of elongation at 4.0cN/dtex load is 0.3%, the dry heat shrinkage rate under the conditions of 177 ℃, 10min and 0.05cN/dtex is 8.4%, the network is 10/m, the oil content is 0.68%, and the full-lap rate is 99.6%.
Example 9
A preparation method of high-strength colored 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 95 ℃ under 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 GDA0001695738250000231
(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 MPa, the esterification reaction temperature is 251 ℃, and the esterification reaction end point 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 lower and is (50 +/-r)0.01) DEG C, the kinematic viscosity is 29.7mm2(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) mixing modified polyester and color master batch, and then performing solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting and winding to obtain the high-strength colored polyester industrial yarn, wherein the content of pigment in the color master batch is 36 wt%, the addition amount of the color master batch is 2.9 wt% of the modified polyester, the intrinsic viscosity of the modified polyester after solid phase polycondensation tackifying is 1.2dL/g, the replacement cycle of a spinning assembly is 33 days, and the spinning process parameters of the high-strength colored 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 140 Bar; the temperature of the cross air blow is 22 ℃; the cross-air humidity is 84%; the air speed of the cross air blow is 0.6 m/s; the winding speed is 3300 m/min; the technological parameters of stretching and heat setting are as follows: the GR-1 speed is 610 m/min; the GR-1 temperature is 84 ℃; GR-2 speed is 630 m/min; the GR-2 temperature is 90 ℃; GR-3 speed is 2200 m/min; the GR-3 temperature is 135 ℃; the GR-4 speed is 3400 m/min; GR-4 temperature was 238 deg.C; GR-5 speed is 3300 m/min; GR-5 temperature was 167 ℃.
The finally prepared high-strength colored polyester industrial yarn has the color of blue, the breaking strength of 7.55cN/dtex, the fineness of 2800dtex, the deviation rate of linear density of 0.3 percent, the CV value of the breaking strength of 2.75 percent, the central value of elongation at break of 15.5 percent, the deviation rate of elongation at break of 0.3 percent, the CV value of elongation at break of 7.4 percent, the central value of elongation at 4.0cN/dtex load of 6.8 percent, the deviation rate of elongation at 4.0cN/dtex load of 0.2 percent, the dry heat shrinkage rate under the conditions of 177 ℃, 10min and 0.05cN/dtex of 9.0 percent, the network of 5 pieces/m, the oil content of 0.8 percent and the full-up rate of 99.4 percent.
Example 10
A preparation method of high-strength colored 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 93 ℃ under a nitrogen atmosphere, 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-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 GDA0001695738250000251
(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) mixing modified polyester and color master batch, and then performing solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting and winding to obtain the high-strength colored polyester industrial yarn, wherein the pigment content in the color master batch is 39 wt%, the addition amount of the color master batch is 2.9 wt% of the modified polyester, the intrinsic viscosity of the modified polyester after solid phase polycondensation tackifying is 1.0dL/g, the replacement cycle of a spinning assembly is 33 days, and the spinning process parameters of the high-strength colored polyester industrial yarn are as follows: the temperature of each zone of the screw is 290 ℃; the temperature of the box body is 299 ℃; the head pressure is 140 Bar; the temperature of the cross air blow is 22 ℃; the cross-air humidity is 85%; the air speed of the cross air blow is 0.7 m/s; the winding speed is 3400 m/min; the technological parameters of stretching and heat setting are as follows: the GR-1 speed is 610 m/min; the GR-1 temperature is 84 ℃; GR-2 speed is 640 m/min; the GR-2 temperature is 98 ℃; GR-3 speed is 2200 m/min; GR-3 temperature is 138 ℃; GR-4 speed is 3500 m/min; GR-4 temperature was 245 ℃; the GR-5 speed is 3400 m/min; the GR-5 temperature was 165 ℃.
The finally prepared high-strength colored polyester industrial yarn is yellow in color, the breaking strength is 7.6N/dtex, the fineness is 3000dtex, the deviation rate of linear density is 0.1%, the CV value of the breaking strength is 2.75%, the central value of the elongation at break is 16.3%, the deviation rate of the elongation at break is 0.1%, the CV value of the elongation at break is 7.3%, the central value of the elongation at 4.0cN/dtex load is 7.0%, the deviation rate of the elongation at 4.0cN/dtex load is 0.15%, the dry heat shrinkage rate under the conditions of 177 ℃, 10min and 0.05cN/dtex is 9.1%, the network is 10/m, the oil content is 0.8%, and the full-up rate is 99.7%.
Example 11
A preparation method of high-strength colored 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 90 ℃ under nitrogen atmosphere, 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 GDA0001695738250000271
(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;
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; coefficient of static friction (. mu.) between fibres (F/F) after oilings) 0.260, coefficient of dynamic friction (. mu.)d) Is 0.263; after oilingCoefficient of static friction (. mu.) between fiber and 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) mixing modified polyester and color master batch, and then performing solid phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting and winding to obtain the high-strength colored polyester industrial yarn, wherein the content of pigment in the color master batch is 38 wt%, the addition amount of the color master batch is 2 wt% of the modified polyester, the intrinsic viscosity of the modified polyester after solid phase polycondensation tackifying is 1.0dL/g, the replacement cycle of a spinning assembly is 3 days, and the spinning process parameters of the high-strength colored 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 140 Bar; the temperature of the cross air blow is 22 ℃; the cross-air humidity is 83%; the air speed of the cross air blow is 0.7 m/s; the winding speed is 3400 m/min; the technological parameters of stretching and heat setting are as follows: GR-1 speed is 625 m/min; the GR-1 temperature is 83 ℃; GR-2 speed is 645 m/min; the GR-2 temperature is 99 ℃; GR-3 speed is 2300 m/min; GR-3 temperature is 138 ℃; GR-4 speed is 3500 m/min; GR-4 temperature 240 ℃; the GR-5 speed is 3400 m/min; the GR-5 temperature was 166 ℃.
The finally prepared high-strength colored polyester industrial yarn is blue, the breaking strength is 7.6cN/dtex, the fineness is 3100dtex, the deviation rate of linear density is 0.2%, the CV value of the breaking strength is 2.7%, the central value of elongation at break is 16.4%, the deviation rate of elongation at break is 0.2%, the CV value of elongation at break is 7.2%, the central value of elongation at 4.0cN/dtex load is 7.0%, the deviation rate of elongation at 4.0cN/dtex load is 0.22%, the dry heat shrinkage rate under the conditions of 177 ℃, 10min and 0.05cN/dtex is 9.2%, the network is 3/m, the oil content is 0.8%, and the full-up rate is 99.8%.

Claims (10)

1. A high-strength colored polyester industrial yarn is characterized in that: the main material of the high-strength colored polyester industrial yarn is modified polyester, the molecular chain of the modified polyester comprises a terephthalic acid chain segment, a glycol chain segment and a dihydric alcohol chain segment with a branched chain, and 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 preparation process of the high-strength colored polyester industrial yarn comprises an oiling process;
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%;
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 breaking strength of the high-strength colored polyester industrial yarn is more than or equal to 7.0cN/dtex, and the color is black, red, yellow or blue.
2. The high-strength colored polyester industrial yarn as claimed in claim 1, wherein the fineness of the high-strength colored polyester industrial yarn is 700 to 3300dtex, the deviation of linear density is ± 1.5%, the breaking strength CV value is less than or equal to 3.0%, the central value of elongation at break is 13.0 to 16.5%, the deviation of elongation at break is ± 1.5%, the elongation at break CV value is less than or equal to 8.0%, the central value of elongation at 4.0cN/dtex load is 5.5 to 7.0%, the deviation of elongation at 4.0cN/dtex load is ± 0.8%, the dry heat shrinkage rate under 177 ℃, 10min and 0.05cN/dtex conditions is 2.8 to 9.2%, the network is (5 to 8) ± 2/m, the oil content is 0.6 ± 0.2%, and the full-up rate is more than or equal to 99%.
3. The high-strength colored polyester industrial yarn as claimed in claim 1 or 2, 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.
4. The high-strength colored polyester industrial yarn as claimed in claim 3, wherein 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.
5. The high-strength colored polyester industrial yarn as claimed in claim 4, 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.
6. A method for preparing the high-strength colored polyester industrial yarn as claimed in any one of claims 1 to 5, which is characterized in that: mixing the modified polyester and the color master batch, and then carrying out solid-phase polycondensation tackifying, melting, metering, extruding, cooling, oiling, stretching, heat setting and winding to obtain the high-strength colored polyester industrial yarn;
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, water is used to prepare an emulsion with the concentration of 10-20 wt%.
7. The method of claim 6, wherein the pigment content in the color master batch is 20-40 wt%, and the addition amount of the color master batch is 2-3 wt% of the modified polyester; the intrinsic viscosity of the modified polyester after solid-phase polycondensation and tackifying is 1.0-1.2 dL/g; the replacement period of the spinning assembly is more than or equal to 30 days.
8. The method according to claim 7, characterized in that the oil agent has a weight loss under heat of less than 15wt% after heat treatment at 200 ℃ for 2 h;
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.
9. The method according to claim 8, characterized in that 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.
10. The method of claim 9, wherein the spinning process parameters of the high tenacity colored 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 ℃;
a handpiece pressure 140 Bar;
the temperature of the cross air blow is 22 ℃;
the humidity of the cross air blow is 80 plus or minus 5 percent;
the air speed of the cross air blow is 0.5-0.7 m/s;
the winding speed is 2600-3600 m/min;
the technological parameters of stretching and heat setting are as follows:
the GR-1 speed is 440 to 650 m/min; GR-1 temperature 80 plus or minus 5 ℃;
GR-2 speed is 460-680 m/min; the GR-2 temperature is 90-100 ℃;
GR-3 at the speed of 1900-2400 m/min; the GR-3 temperature is 125-140 ℃;
GR-4 at 2700-3600 m/min; the GR-4 temperature is 220-250 ℃;
GR-5 speed is 2500-3600 m/min; the GR-5 temperature is 150-170 ℃.
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