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CN108035007B - Superfine denier polyester drawn yarn and preparation method thereof - Google Patents

Superfine denier polyester drawn yarn and preparation method thereof Download PDF

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Publication number
CN108035007B
CN108035007B CN201711340289.1A CN201711340289A CN108035007B CN 108035007 B CN108035007 B CN 108035007B CN 201711340289 A CN201711340289 A CN 201711340289A CN 108035007 B CN108035007 B CN 108035007B
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temperature
oil agent
terephthalic acid
superfine denier
pressure
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CN108035007A (en
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王山水
魏德新
丁竹君
卓怀智
晏金龙
张建光
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Jiangsu Hengli Chemical Fiber Co Ltd
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Jiangsu Hengli Chemical Fiber Co Ltd
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
    • D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/02—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/11—Compounds containing epoxy groups or precursors thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • D06M13/2243—Mono-, di-, or triglycerides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
    • D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters

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  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Artificial Filaments (AREA)
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Abstract

The invention relates to a superfine denier polyester drawn yarn and a preparation method thereof, modified polyester is subjected to metering, extrusion, cooling, oiling, stretching, heat setting and winding to prepare the superfine denier polyester drawn yarn, wherein an oiling agent for oiling contains crown ether, the content of the crown ether is 67.30-85.58 wt%, a modified polyester molecular chain 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 DDA0001508223600000011
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 single filament number of the prepared superfine denier polyester drawn yarn is 0.2-0.3 dtex. The method is simple and reasonable, and the prepared superfine denier polyester drawn yarns are soft, fine and high in quality.

Description

Superfine denier polyester drawn yarn and preparation method thereof
Technical Field
The invention belongs to the field of fiber preparation, and relates to a superfine denier polyester drawn 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.
In order to reduce the generation of cyclic oligomers in the polycondensation reaction of polyesters, researchers at home and abroad have conducted a great deal of research. The main methods for reducing cyclic oligomers in polyesters are: (1) pentavalent phosphorus compound or ether compound is added to combine with metal catalyst in the polyester synthesis process, or the amount of heat stabilizer is increased, so as to generate stabilization effect on polyester, and thus the generation of cyclic trimer can be inhibited under high temperature melting; (2) the residence time of the polyester melt at high temperature is reduced. However, the above-mentioned method causes a decrease in the molecular weight and a broadening of the distribution of the polyester, affecting the quality of the finally obtained fiber, while the effect of reducing the cyclic trimer oligomers is not significant.
With the increasing production of polyester fiber, the quality requirement of fiber is increased, and particularly with the rapid development of fine denier polyester fiber, the market puts higher requirement on the quality of fiber. Softness is an important property for fibers, the fibers with good softness have the advantages of fine and uniform fineness, high strength, elasticity, soft texture, smooth and fine hand feeling and the like, and fabrics spun by the fibers have the characteristics of soft hand feeling and elegant wearing, however, the fibers are difficult to spin finely due to the high oligomer content in the fibers in the prior art, and oil used in the spinning process is difficult to meet the conditions required for producing superfine fibers, so that the obtained fibers have low quality and poor softness.
Therefore, it is a problem to be solved at present to prepare a PET fiber having good flexibility and high quality.
Disclosure of Invention
The invention aims to overcome the problems of poor fiber softness and low quality in the prior art, and provides a melt direct spinning polyester super-soft composite yarn with good softness and high quality and a preparation method thereof. The introduction of the dihydric alcohol with the branched chain in the modified polyester reduces the cyclic oligomer generated in the side reaction of the polyester, improves the level-dyeing property of the fiber, enables the fiber to be spun more finely and further improves the softness of the fiber; the use of the crown ether-containing oil agent improves the heat resistance and the lubricity of the oil agent, thereby improving the spinnability of the fiber, reducing the phenomenon of fiber yarn breakage caused by static electricity in the spinning process, improving the quality of the prepared fiber and ensuring that the finally prepared superfine denier polyester drawn yarn has excellent soft and fine performance.
In order to achieve the purpose, the invention adopts the technical scheme that:
the superfine denier polyester drawn yarns are made of 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, wherein the structural formula of the dihydric alcohol with the branched chain is as follows:
Figure GDA0001605145150000021
in the formula, R1And R2Each independently selected from linear alkylene having 1 to 3 carbon atoms, R3Selected from alkyl with 1-5 carbon atoms, R4The carbon atom number is 2-5, and the purpose of carbon atom number limitation is as follows: because a branched chain structure and a long chain structure are introduced into the dihydric alcohol, the electronegativity of an alkoxy part is weakened, the number of carbon atoms of the branched chain structure is too small, the electronegativity influence on the alkoxy part is small, and the significance for reducing the generation of cyclic oligomers is not large; the too large number of carbon atoms of the branched chain structure can generate intermolecular entanglement and influence the distribution of molecular weight;
the filament number of the superfine denier polyester drawn yarns is 0.2-0.3 dtex.
As a preferred technical scheme:
the superfine denier polyester drawn yarn has the fineness of 50-75 dtex, the breaking strength of more than or equal to 3.6cN/dtex, the elongation at break of 40.0 +/-3.0 percent, the breaking strength CV value of less than or equal to 5.0 percent, the elongation at break CV value of less than or equal to 10.0 percent, the boiling water shrinkage of 7.5 +/-0.5 percent, the oil content of 0.90 +/-0.20 percent and the number of broken filaments of one spinning cake of less than or equal to 2.
According to the superfine denier polyester drawn yarn, the content of cyclic oligomers in the modified polyester is less than or equal to 0.6 wt%, 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 production 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 can be maintained.
The drawn ultrafine denier polyester yarn as described above, wherein the branched diol 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-bis (1, -methylethyl) -1, 7-heptanediol, 3-dipropyl-1, 5-pentanediol, 4-dipropyl-1, 7-heptanediol, 4-methyl-4- (1, 1-dimethylethyl) -1, 7-heptanediol, a poly (ethylene glycol) and a poly (ethylene glycol) ether, a poly (ethylene glycol), a, 3-methyl-3-pentyl-1, 6-hexanediol or 3, 3-diamyl-1, 5-pentanediol.
The preparation method of the modified polyester comprises the following steps: uniformly mixing terephthalic acid, ethylene glycol and the dihydric alcohol with the branched chain, and then sequentially carrying out esterification reaction and polycondensation reaction to obtain modified polyester; the method comprises the following specific steps:
(1) performing esterification reaction;
preparing terephthalic acid, ethylene glycol and the dihydric alcohol with the branched chain into slurry, adding a catalyst, a delustering agent 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.
According to the drawn superfine denier polyester yarn, in the step (1), the molar ratio of terephthalic acid to ethylene glycol to 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, the addition amount of the flatting agent is 0.20-0.25% 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, the flatting agent is titanium dioxide, and the stabilizer is triphenyl phosphate, trimethyl phosphate or trimethyl phosphite.
The invention also provides a method for preparing the superfine denier polyester drawn yarn as described in any one of claims 1 to 6, wherein the modified polyester is subjected to metering, extrusion, cooling, oiling, stretching, heat setting and winding to prepare the superfine denier polyester drawn yarn;
the oil agent for oiling contains crown ether, the content of the crown ether is 67.30-85.58 wt%, the content of the crown ether in the oil agent needs to be kept within a certain range, the oil agent with low viscosity, good heat resistance and high oil film strength cannot be prepared if the addition amount of the crown ether is too low, and other performance indexes of the oil agent can be influenced if the addition amount of the crown ether is too high.
Crown ethers are heterocyclic organic compounds containing a plurality of ether groups. The wetting ability of the crown ether surfactant is larger than that of a corresponding open-chain compound, the crown ether has better solubilization, the solubility of the salt compound in the organic compound is lower, but the solubility of the organic matter of the salt compound is improved along with the addition of the crown ether. The common polyester compounds or polyethers in the oil agent have larger intermolecular action due to larger molecular weight and the action of hydrogen bonds, and show larger kinematic viscosity, and after the crown ether is added, the crown ether can be well compatible in the polyester compounds or polyether oil agent system, enters between polyester compounds or polyether molecular chains, shields the acting force between the molecular chains, and thus the viscosity of the oil agent system is reduced. Meanwhile, the antistatic agent of the chemical fiber oiling agent is mainly divided into anionic surfactant, cationic surfactant and amphoteric surfactant, most of which contain metal ions or exist in the form of salt, so that the compatibility of the antistatic agent and polyester compounds or polyethers in the oiling agent is ensured, and the addition of the crown ether improves the compatibility of the antistatic agent and the polyester compounds or polyethers due to the salt dissolution effect, thereby improving the strength of an oiling agent oil film and having great significance on the stability of spinning and the product holding capacity. Indexes of the oil agent are reflected by a comprehensive factor, so that a certain restriction is provided for the addition amount of crown ether, the advantages of heat resistance and oil film strength of the oil agent are not reflected sufficiently when the addition amount is too low, and other indexes are limited when the addition amount is too much.
As a preferred technical scheme:
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 15 wt%, 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 10 wt% 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 x 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 method as described above, wherein the crown ether is 2-hydroxymethyl-12-crown-4, 15-crown-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;
when the oil agent is used, preparing an emulsion with the concentration of 10-20 wt% by using water;
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 GDA0001605145150000061
the mixing is carried out at normal temperature, the stirring temperature is 40-55 ℃, and the stirring time is 1-3 h.
According to the method, the spinning process parameters of the drawn superfine denier polyester yarn are as follows:
spinning temperature: 287-295 ℃;
cooling temperature: 20-25 ℃;
network pressure: 0.20 to 0.30 MPa;
a roll speed: 3100 to 3200m/min
First roll temperature: 88 to 93 ℃;
two roll speed: 3900 to 4100 m/min;
temperature of the two rolls: 120-130 ℃;
speed of winding: 3800-4000 m/min;
the initial pressure of the spinning assembly is 120bar, and the pressure rise delta P is less than or equal to 0.6 bar/day.
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 GDA0001605145150000071
in the formula, xiIs the electronegativity of the neutral atom of the i atom prior to bonding,
Figure DA00016051451557533
is 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 GDA0001605145150000073
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 bond-forming electron pairs on the newly formed chemical bond C-O bond are moved to the central C atom and are closer to the central atom, so that the bond angles α are larger than 109 degrees, the probability of generating linear polymers is increased, the generation of cyclic oligomers is reduced, the fiber can be spun particularly finely, and the softness of the fiber is improved.
The crown ether is introduced into the oil agent to prepare the oil agent with low viscosity, good heat resistance and higher oil film strength. In the prior art, the higher viscosity of the oil agent is mainly due to the fact that the oil agent contains a common polyester compound or polyether compound, the intermolecular action of the compound is larger due to the larger molecular weight and the action of hydrogen bonds, the kinematic viscosity is larger, so that the viscosity of the oil agent is higher, the viscosity of the oil agent can be obviously reduced after crown ether is added, the crown ether is mainly due to the fact that the viscosity of the crown ether is lower and is bead-shaped micromolecule, the crown ether can be well compatible in a polyester compound or polyether oil agent system and simultaneously enters between molecular chains of the polyester compound or polyether compound to shield acting force between the molecular chains, and therefore the viscosity of the oil agent system is reduced. In the prior art, the oil film strength of the oil agent is low mainly because the antistatic agent of the chemical fiber oil agent mostly contains metal ions or exists in the form of salt, so that the compatibility of the antistatic agent and polyester compounds or polyethers in the oil agent is poor, and the crown ether can improve the oil film strength mainly because the crown ether can generate a salt solution effect after being added, so that the compatibility of the antistatic agent and the polyester compounds or polyethers is improved, and the oil film strength of the oil agent is further improved. In addition, the crown ether has higher volatile point and excellent heat-resistant stability, the heat-resistant performance of an oiling agent introduced with the crown ether is also obviously improved, the oiling agent disclosed by the invention has low viscosity and good lubricity, so that the precursor can smoothly pass through spinning, in addition, a layer of protective film with high strength can be formed on the surface of the fiber precursor by the oiling agent, the damage of the precursor in the spinning process and the generation of the surface defects of the fiber precursor are prevented, the phenomena of quality reduction, performance reduction and the like of the precursor are prevented, the phenomenon of fiber yarn breakage caused by electrostatic problems in the spinning process is reduced, and the finally prepared superfine denier polyester drawn yarn has excellent soft and fine performance.
Has the advantages that:
(1) the superfine denier polyester drawn yarn has the advantages of simple and reasonable preparation process, and the prepared drawn yarn has the characteristics of softness, fineness and high quality;
(2) according to the superfine denier polyester drawn yarn, the oiling agent containing the crown ether used in the oiling process has the characteristics of low viscosity, good heat resistance, high oil film strength, good smoothness and strong antistatic property, and the spinning stability and the fiber processability are improved;
(3) according to the preparation method of the superfine denier polyester drawn 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 method for preparing superfine denier polyester drawn yarns 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 GDA0001605145150000091
(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 0.6 wt%, the number average molecular weight is 20000, the molecular weight distribution index is 2.0, and the molar content of the 2-ethyl-2-methyl-1, 3-propanediol chain segment in the modified polyester is 3% of the molar content of the terephthalic acid chain segment;
(2) preparing an oiling agent;
uniformly mixing 2-hydroxymethyl-12-crown-4 with dodecyl phosphate potassium salt, trimethylolpropane laurate and sodium dodecyl sulfate at normal temperature, adding the mixture into No. 9 mineral oil, and uniformly stirring the mixture for 1h at 40 ℃ to obtain an oil agent, wherein the adding amount of each component is as follows in parts by weight: 2 parts of No. 9 mineral oil; 10 parts of trimethylolpropane laurate; 90 portions of 2-hydroxymethyl-12-crown-4; 8 parts of dodecyl phosphate potassium salt; 3 parts of sodium dodecyl sulfate; the content of crown ether in the prepared oil agent is 79.6 wt%, the high temperature resistance of the oil agent is excellent, and the thermal weight loss is 14.5 wt% after the oil agent is heated for 2 hours at 200 ℃; the viscosity of the oil agent is low, and the kinematic viscosity is 29.6mm at the temperature of (50 +/-0.01) ° C2(s) a kinematic viscosity of 0.93mm after preparation with water as an emulsion having a concentration of 10% by weight2(s) the oil has high oil film strength of 125N, surface tension of 24.8cN/cm, and specific resistance of 1.3X 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 15 wt% by using water when in use;
(3) the modified polyester is subjected to metering, extrusion, cooling, oiling, stretching, heat setting and winding to prepare the superfine denier polyester drawn yarn, wherein the spinning process parameters of the superfine denier polyester drawn yarn are as follows: spinning temperature: 290 ℃; cooling temperature: 22 ℃; network pressure: 0.25 MPa; a roll speed: 3150 m/min; first roll temperature: 90 ℃; two roll speed: 4000 m/min; temperature of the two rolls: 125 ℃; speed of winding: 3900 m/min; the initial pressure of the spin pack was 120bar and the pressure rise Δ P was 0.54 bar/day.
The filament number of the finally prepared superfine denier polyester drawn yarn is 0.25dtex, the filament number is 65dtex, the breaking strength is 4.5cN/dtex, the elongation at break is 40.0%, the breaking strength CV value is 5.0%, the elongation at break CV value is 9.0%, the boiling water shrinkage rate is 7.5%, the oil content is 1.1%, and the number of broken filaments of one spinning cake is 0.
Example 2
A method for preparing superfine denier polyester drawn yarns 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 GDA0001605145150000101
(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 0.6 wt%, 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, 25.1cN/cm, which is a surface tension of the oil, and 1.5X 10 of specific resistance8Omega cm; coefficient of static friction (. mu.) between fibres (F/F) after oilings) 0.257, coefficient of dynamic friction (. mu.)d) Is 0.265; after oiling, the coefficient of static friction (μ) between the fiber and the metal (F/M)s) 0.205, coefficient of dynamic friction (. mu.)d) Is 0.323; when the prepared oil agent is used, water is used for preparing emulsion with the concentration of 14 wt%;
(3) the modified polyester is subjected to metering, extrusion, cooling, oiling, stretching, heat setting and winding to prepare the superfine denier polyester drawn yarn, wherein the spinning process parameters of the superfine denier polyester drawn yarn are as follows: spinning temperature: 287 deg.C; cooling temperature: 20 ℃; network pressure: 0.20 MPa; a roll speed: 3100 m/min; first roll temperature: 88 ℃; two roll speed: 3900 m/min; temperature of the two rolls: 120 ℃; speed of winding: 3800 m/min; the initial pressure of the spin pack was 120bar and the pressure rise Δ P was 0.6 bar/day.
The filament number of the finally prepared superfine denier polyester drawn yarn is 0.2dtex, the filament number is 50dtex, the breaking strength is 4.0cN/dtex, the elongation at break is 43.0%, the breaking strength CV value is 5.0%, the elongation at break CV value is 9.2%, the boiling water shrinkage rate is 7.0%, the oil content is 0.7%, and 2 broken filaments of one spinning cake are provided.
Example 3
A method for preparing superfine denier polyester drawn yarns 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 GDA0001605145150000121
(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;
mixing 2-hydroxymethyl-15-crown-5 with potassium dodecatetradecanol phosphate and trihydroxy phosphateThe methyl propane laurate and the sodium pentadecylsulfonate are uniformly mixed at normal temperature, added into the No. 11 mineral oil and uniformly stirred for 3 hours at 48 ℃ to obtain an oil agent, and the addition amount of the components is as follows according to 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 weight2(s) 125N, the oil film strength of the oil agent is high, the surface tension of the oil agent is 23.2cN/cm, and the specific resistance is 1.8 x 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 10 wt% by using water when in use;
(3) the modified polyester is subjected to metering, extrusion, cooling, oiling, stretching, heat setting and winding to prepare the superfine denier polyester drawn yarn, wherein the spinning process parameters of the superfine denier polyester drawn yarn are as follows: spinning temperature: 295 ℃; cooling temperature: 25 ℃; network pressure: 0.30 MPa; a roll speed: 3200 m/min; first roll temperature: 93 ℃; two roll speed: 4100 m/min; temperature of the two rolls: 130 ℃; speed of winding: 4000 m/min; the initial pressure of the spin pack was 120bar and the pressure rise Δ P was 0.59 bar/day.
The filament number of the finally prepared superfine denier polyester drawn yarn is 0.3dtex, the filament number is 75dtex, the breaking strength is 3.9cN/dtex, the elongation at break is 43.0%, the breaking strength CV value is 4.5%, the elongation at break CV value is 9.5%, the boiling water shrinkage rate is 8.0%, the oil content is 0.75%, and 2 broken filaments of one spinning cake are provided.
Example 4
A method for preparing superfine denier polyester drawn yarns comprises the following steps:
(1) preparing modified polyester;
(a) preparing 3, 3-diethyl-1, 5-pentanediol; reacting 3, 3-diethyl-propionaldehyde, acetaldehyde and triethylamine for 20min at 90 ℃ in a nitrogen atmosphere, then adding the concentrated solution into a hydrogenation reactor with a Raney nickel catalyst, reacting at a hydrogen pressure of 2.914MPa and a temperature of 100 ℃, cooling after the reaction is finished, separating out the catalyst, treating the solution with ion exchange resin, evaporating water under reduced pressure, separating and purifying to obtain 3, 3-diethyl-1, 5-pentanediol, wherein the structural formula of the 3, 3-diethyl-1, 5-pentanediol is as follows:
Figure GDA0001605145150000131
(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 85.58 wt%, 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 1.0X 108Omega cm; coefficient of static friction (. mu.) between fibres (F/F) after oilings) 0.260, coefficient of dynamic friction (. mu.)d) Is 0.263; after oiling, the coefficient of static friction (μ) between the fiber and the metal (F/M)s) 0.202, coefficient of dynamic friction (. mu.)d) 0.330, and the prepared oil agent is prepared into an emulsion with the concentration of 19 wt% by using water when in use;
(3) the modified polyester is subjected to metering, extrusion, cooling, oiling, stretching, heat setting and winding to prepare the superfine denier polyester drawn yarn, wherein the spinning process parameters of the superfine denier polyester drawn yarn are as follows: spinning temperature: 288 ℃; cooling temperature: 21 ℃; network pressure: 0.23 MPa; a roll speed: 3120 m/min; first roll temperature: 89 ℃; two roll speed: 3920 m/min; temperature of the two rolls: 122 ℃; speed of winding: 3830 m/min; the initial pressure of the spin pack was 120bar and the pressure rise Δ P was 0.58 bar/day.
The filament number of the finally prepared superfine denier polyester drawn yarn is 0.21dtex, the filament number is 55dtex, the breaking strength is 3.6cN/dtex, the elongation at break is 37.0%, the breaking strength CV value is 4.0%, the elongation at break CV value is 10.0%, the boiling water shrinkage rate is 8.0%, the oil content is 0.8%, and the number of the broken filaments in one spinning cake is 1.
Example 5
A method for preparing superfine denier polyester drawn yarns comprises the following steps:
(1) preparing modified polyester;
(a) preparing 4, 4-diethyl-1, 7-heptanediol; reacting 4, 4-diethyl-butyraldehyde, propionaldehyde and triethylamine for 20min at 95 ℃ in a nitrogen atmosphere, then adding the concentrated solution into a hydrogenation reactor with a Raney nickel catalyst, reacting at a hydrogen pressure of 2.914MPa and a temperature of 100 ℃, cooling after the reaction is finished, separating out the catalyst, treating the solution with ion exchange resin, evaporating water under reduced pressure, separating and purifying to obtain 4, 4-diethyl-1, 7-heptanediol, wherein the structural formula of the 4, 4-diethyl-1, 7-heptanediol is as follows:
Figure GDA0001605145150000151
(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 weight2(s) 126N, which is a high oil film strength of the oil agent, 24.9cN/cm, which is a surface tension of the oil agent, and 1.2X 10 which is a specific resistance8Omega cm; coefficient of static friction (. mu.) between fibres (F/F) after oilings) 0.251, coefficient of dynamic friction (. mu.)d) Is 0.262; after oiling, the coefficient of static friction (μ) between the fiber and the metal (F/M)s) 0.202, coefficient of dynamic friction (. mu.)d) 0.332, and the prepared oil agent is prepared into an emulsion with the concentration of 11 wt% by using water when in use;
(3) the modified polyester is subjected to metering, extrusion, cooling, oiling, stretching, heat setting and winding to prepare the superfine denier polyester drawn yarn, wherein the spinning process parameters of the superfine denier polyester drawn yarn are as follows: spinning temperature: 290 ℃; cooling temperature: 21 ℃; network pressure: 0.24 MPa; a roll speed: 3140 m/min; first roll temperature: 90 ℃; two roll speed: 3960 m/min; temperature of the two rolls: 122 ℃; speed of winding: 3880 m/min; the initial pressure of the spin pack was 120bar and the pressure rise Δ P was 0.57 bar/day.
The filament number of the finally prepared superfine denier polyester drawn yarn is 0.24dtex, the filament number is 58dtex, the breaking strength is 4.8cN/dtex, the elongation at break is 37.0%, the CV value of the breaking strength is 4.8%, the CV value of the elongation at break is 9.5%, the shrinkage rate in boiling water is 7.5%, the oil content is 0.90%, and the number of the broken filaments in one spinning cake is 1.
Example 6
A method for preparing superfine denier polyester drawn yarns comprises the following steps:
(1) preparing modified polyester;
(a) preparing 4, 4-di (1-methylethyl) -1, 7-heptanediol; reacting 4, 4-di (1-methylethyl) -butyraldehyde, propionaldehyde and triethylamine for 20min at 92 ℃ in a nitrogen atmosphere, then adding the concentrated solution into a hydrogenation reactor with a Raney nickel catalyst, reacting at the hydrogen pressure of 2.914MPa and the temperature of 100 ℃, and cooling to separate out the catalyst after the reaction. After the solution is treated by ion exchange resin, water is evaporated under reduced pressure, and the 4, 4-di (1-methylethyl) -1, 7-heptanediol is separated and purified, wherein the structural formula of the 4, 4-di (1-methylethyl) -1, 7-heptanediol is as follows:
Figure GDA0001605145150000171
(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 weight2(s) 126N, which is a high oil film strength of the oil agent, 25.4cN/cm, which is a surface tension of the oil agent, and 1.6X 10 of a specific resistance8Omega 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 20 wt% by using water when in use;
(3) the modified polyester is subjected to metering, extrusion, cooling, oiling, stretching, heat setting and winding to prepare the superfine denier polyester drawn yarn, wherein the spinning process parameters of the superfine denier polyester drawn yarn are as follows: spinning temperature: 290 ℃; cooling temperature: 23 ℃; network pressure: 0.25 MPa; a roll speed: 3150 m/min; first roll temperature: 91 ℃; two roll speed: 3960 m/min; temperature of the two rolls: 125 ℃; speed of winding: 3900 m/min; the initial pressure of the spin pack was 120bar and the pressure rise Δ P was 0.57 bar/day.
The filament number of the finally prepared superfine denier polyester drawn yarn is 0.26dtex, the filament number is 58dtex, the breaking strength is 3.7cN/dtex, the elongation at break is 40.0%, the breaking strength CV value is 4.6%, the elongation at break CV value is 9.9%, the boiling water shrinkage rate is 7.6%, the oil content is 0.95%, and the number of the broken filaments of one spinning cake is 1.
Example 7
A method for preparing superfine denier polyester drawn yarns comprises the following steps:
(1) preparing modified polyester;
(a) preparing 3, 3-dipropyl-1, 5-pentanediol; reacting 3, 3-dipropyl-propionaldehyde, acetaldehyde and triethylamine for 20min at 93 ℃ in a nitrogen atmosphere, then adding the concentrated solution into a hydrogenation reactor with a Raney nickel catalyst, reacting at the hydrogen pressure of 2.914MPa and the temperature of 100 ℃, cooling after the reaction is finished, and separating out the catalyst. After the solution is treated by ion exchange resin, water is evaporated under reduced pressure, and the 3, 3-dipropyl-1, 5-pentanediol is separated and purified, wherein the structural formula of the 3, 3-dipropyl-1, 5-pentanediol is as follows:
Figure GDA0001605145150000181
(b) performing esterification reaction; preparing terephthalic acid, ethylene glycol and 3, 3-dipropyl-1, 5-pentanediol with the molar ratio of 1:1.8:0.03 into slurry, adding antimony trioxide, titanium dioxide and triphenyl phosphate, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.3MPa, the esterification reaction temperature is 250 ℃, and the esterification reaction end point is when the distilled amount of water in the esterification reaction reaches 90% of a theoretical value, wherein the adding amount of the antimony trioxide is 0.03% of the weight of the terephthalic acid, the adding amount of the titanium dioxide is 0.24% of the weight of the terephthalic acid, and the adding amount of the triphenyl phosphate is 0.02% of the weight of the terephthalic acid;
(c) performing polycondensation reaction; after the esterification reaction is finished, the polycondensation reaction in the low vacuum stage is started under the condition of negative pressure, the pressure is smoothly pumped from normal pressure to the absolute pressure of 455Pa within 42min, the reaction temperature is 264 ℃, the reaction time is 45min, then continuously vacuumizing, carrying out polycondensation reaction in a high vacuum stage, further reducing the reaction pressure to 85Pa absolute, the reaction temperature to 285 ℃, the reaction time to 75min, preparing modified polyester, wherein the molecular chain of the modified polyester comprises a terephthalic acid chain segment, an ethylene glycol chain segment and a 3, 3-dipropyl-1, 5-pentanediol chain segment, the content of cyclic oligomers in the modified polyester is 0.45 wt%, the number average molecular weight is 26500, the molecular weight distribution index is 2.2, and the molar content of the 3, 3-dipropyl-1, 5-pentanediol chain segment in the modified polyester is 4.5 percent of the molar content of the terephthalic acid chain segment;
(2) preparing an oiling agent;
uniformly mixing 15-crown ether-5 with dodecyl phosphate potassium salt, trimethylolpropane laurate and sodium hexadecylsulfonate at normal temperature, adding the mixture into 15# mineral oil, and uniformly stirring the mixture for 2 hours at 41 ℃ to obtain an oil agent, wherein the adding amount of each component is as follows in parts by weight: 8 parts of No. 15 mineral oil; 20 parts of trimethylolpropane laurate; 100 portions of 15-crown ether-5; 15 parts of dodecyl phosphate potassium salt; the hexadecyl sodium sulfonate is 2 parts. The content of crown ether in the prepared oil agent is 68.97 wt%, the high temperature resistance of the oil agent is excellent, and the thermal weight loss is 8.5 wt% after the oil agent is heated for 2 hours at 200 ℃; the viscosity of the oil agent is low, and the kinematic viscosity is 28.4mm at the temperature of (50 +/-0.01) ° C2(s) a kinematic viscosity of 0.94mm after preparation with water as an emulsion having a concentration of 10% by weight2(s) the oil film strength of the oil agent was 122N, the surface tension of the oil agent was 26.8cN/cm, and the specific resistance was 1.8X 108Omega cm; coefficient of static friction (. mu.) between fibres (F/F) after oilings) 0.263, coefficient of dynamic friction (. mu.)d) Is 0.268; after oiling, the coefficient of static friction (μ) between the fiber and the metal (F/M)s) 0.210, coefficient of dynamic friction (. mu.)d) 0.320, and the prepared oil agent is prepared into an emulsion with the concentration of 13 wt% by using water when in use;
(3) the modified polyester is subjected to metering, extrusion, cooling, oiling, stretching, heat setting and winding to prepare the superfine denier polyester drawn yarn, wherein the spinning process parameters of the superfine denier polyester drawn yarn are as follows: spinning temperature: 292 deg.C; cooling temperature: 23 ℃; network pressure: 0.26 MPa; a roll speed: 3170 m/min; first roll temperature: 91 ℃; two roll speed: 4050 m/min; temperature of the two rolls: 127 ℃; speed of winding: 3920 m/min; the initial pressure of the spin pack was 120bar and the pressure rise Δ P was 0.55 bar/day.
The filament number of the finally prepared superfine denier polyester drawn yarn is 0.26dtex, the filament number is 62dtex, the breaking strength is 3.9cN/dtex, the elongation at break is 40.0%, the breaking strength CV value is 5.0%, the elongation at break CV value is 10.0%, the boiling water shrinkage rate is 7.5%, the oil content is 1.0%, and the number of the broken filaments of one spinning cake is 1.
Example 8
A method for preparing superfine denier polyester drawn yarns comprises the following steps:
(1) preparing modified polyester;
(a) preparing 4, 4-dipropyl-1, 7-heptanediol; reacting 4, 4-dipropyl-butyraldehyde, acetaldehyde and triethylamine for 20min at 92.5 ℃ in a nitrogen atmosphere, then adding the concentrated solution into a hydrogenation reactor with a Raney nickel catalyst, reacting at the hydrogen pressure of 2.914MPa and the temperature of 100 ℃, cooling after the reaction is finished, and separating out the catalyst. Treating the solution with ion exchange resin, evaporating water under reduced pressure, separating, and purifying to obtain 4, 4-dipropyl-1, 7-heptanediol, wherein the structural formula of the 4, 4-dipropyl-1, 7-heptanediol is as follows:
Figure GDA0001605145150000201
(b) performing esterification reaction; preparing terephthalic acid, ethylene glycol and 4, 4-dipropyl-1, 7-heptanediol with a molar ratio of 1:1.9:0.04 into slurry, adding ethylene glycol antimony, titanium dioxide and trimethyl phosphate, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.3MPa, the esterification reaction temperature is 260 ℃, and the esterification reaction endpoint is determined when the water distillation amount in the esterification reaction reaches 93% of a theoretical value, wherein the adding amount of the ethylene glycol antimony is 0.04% of the weight of the terephthalic acid, the adding amount of the titanium dioxide is 0.21% of the weight of the terephthalic acid, and the adding amount of the trimethyl phosphate is 0.03% of the weight of the terephthalic acid;
(c) performing polycondensation reaction; after the esterification reaction is finished, the polycondensation reaction in the low vacuum stage is started under the condition of negative pressure, the pressure is stably pumped from 0.3MPa to 475Pa in absolute pressure within 45min, the reaction temperature is 265 ℃, the reaction time is 48min, then continuously vacuumizing, carrying out polycondensation reaction in a high vacuum stage, further reducing the reaction pressure to 88Pa absolute, 283 ℃ reaction temperature, and 80min reaction time to obtain modified polyester, wherein the molecular chain of the modified polyester comprises a terephthalic acid chain segment, a glycol chain segment and a 4, 4-dipropyl-1, 7-heptanediol chain segment, the content of cyclic oligomer in the modified polyester is 0.6 wt%, 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 a high oil film strength of 127N, a surface tension of 23.5cN/cm, and a specific resistance of 1.5X 108Omega cm; coefficient of static friction (. mu.) between fibres (F/F) after oilings) 0.262, coefficient of dynamic friction (. mu.)d) Is 0.273; after oiling, the coefficient of static friction (μ) between the fiber and the metal (F/M)s) 0.208, coefficient of dynamic friction (. mu.)d) 0.328, and the prepared oil agent is prepared into emulsion with the concentration of 18 wt% by using water when in use;
(3) the modified polyester is subjected to metering, extrusion, cooling, oiling, stretching, heat setting and winding to prepare the superfine denier polyester drawn yarn, wherein the spinning process parameters of the superfine denier polyester drawn yarn are as follows: spinning temperature: 292 deg.C; cooling temperature: 23 ℃; network pressure: 0.27 MPa; a roll speed: 3180 m/min; first roll temperature: 92 ℃; two roll speed: 4060 m/min; temperature of the two rolls: 128 ℃; speed of winding: 3900 m/min; the initial pressure of the spin pack was 120bar and the pressure rise Δ P was 0.56 bar/day.
The filament number of the finally prepared superfine denier polyester drawn yarn is 0.28dtex, the filament number is 68dtex, the breaking strength is 3.6cN/dtex, the elongation at break is 37.0%, the breaking strength CV value is 4.0%, the elongation at break CV value is 9.6%, the boiling water shrinkage rate is 8.0%, the oil content is 1.05%, and the number of the broken filaments in one spinning cake is 1.
Example 9
A method for preparing superfine denier polyester drawn yarns comprises the following steps:
(1) preparing modified polyester;
(a) preparing 4-methyl-4- (1, 1-dimethylethyl) -1, 7-heptanediol; reacting 4-methyl-4- (1, 1-dimethylethyl) -butyraldehyde, propionaldehyde and triethylamine for 20min at 91 ℃ under the nitrogen atmosphere, then adding the concentrated solution into a hydrogenation reactor with a Raney nickel catalyst, reacting at the hydrogen pressure of 2.914MPa and the temperature of 100 ℃, cooling after the reaction is finished, separating the catalyst out, treating the solution with ion exchange resin, evaporating water under reduced pressure, separating and purifying to obtain 4-methyl-4- (1, 1-dimethylethyl) -1, 7-heptanediol, wherein the structural formula of the 4-methyl-4- (1, 1-dimethylethyl) -1, 7-heptanediol is as follows:
Figure GDA0001605145150000211
(b) performing esterification reaction; preparing terephthalic acid, ethylene glycol and 4-methyl-4- (1, 1-dimethylethyl) -1, 7-heptanediol with the molar ratio of 1:2.0:0.05 into slurry, adding antimony acetate, titanium dioxide and trimethyl phosphate, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is normal pressure, the temperature of the esterification reaction is 251 ℃, and the end point of the esterification reaction is determined when the distilled amount of water in the esterification reaction reaches 96% of a theoretical value, wherein the adding amount of the antimony acetate is 0.05% of the weight of the terephthalic acid, the adding amount of the titanium dioxide is 0.22% of the weight of the terephthalic acid, and the adding amount of the trimethyl phosphate is 0.04% of the weight of the terephthalic acid;
(c) performing polycondensation reaction; after the esterification reaction is finished, starting the polycondensation reaction in the low vacuum stage under the condition of negative pressure, smoothly pumping the pressure from normal pressure to the absolute pressure of 420Pa within 30min, the reaction temperature is 267 ℃, the reaction time is 50min, then continuing to pump the vacuum, carrying out the polycondensation reaction in the high vacuum stage, further reducing the reaction pressure to the absolute pressure of 80Pa, the reaction temperature is 280 ℃, and the reaction time is 90min, thus obtaining the modified polyester, wherein the molecular chain of the modified polyester comprises a terephthalic acid chain segment, a glycol chain segment and a 4-methyl-4- (1, 1-dimethylethyl) -1, 7-heptanediol chain segment, the content of cyclic oligomer in the modified polyester is 0.25 wt%, the number average molecular weight is 24000, the molecular weight distribution index is 2.2, and the 4-methyl-4- (1, 1-dimethylethyl) -1 in the modified polyester, the molar content of the 7-heptanediol chain segment is 4 percent of the molar content of the terephthalic acid chain segment;
(2) preparing an oiling agent;
uniformly mixing 2-hydroxymethyl-15-crown-5 with dodecyl phosphate potassium salt, trimethylolpropane laurate and sodium dodecyl sulfate at normal temperature, and uniformly stirring at 55 ℃ for 3 hours to obtain an oil agent, wherein the adding amount of each component is as follows in parts by weight: 15 parts of trimethylolpropane laurate; 90 portions of 2-hydroxymethyl-15-crown-5; 8 parts of dodecyl phosphate potassium salt; 7 parts of sodium dodecyl sulfate. The content of crown ether in the prepared oil agent is 81.81 wt%, the high temperature resistance of the oil agent is excellent, and the thermal weight loss is 10 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 29.7mm at the temperature of (50 +/-0.01) ° C2(s) a kinematic viscosity of 0.94mm after preparation with water as an emulsion having a concentration of 10% by weight2(s) 126N, which is a high oil film strength of the oil agent, 24.8cN/cm, which is a surface tension of the oil agent, and 1.8X 10 which is a specific resistance8Omega 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, fiberCoefficient of static friction (μ) between dimension and metal (F/M)s) 0.210, coefficient of dynamic friction (. mu.)d) 0.321, when the prepared oil agent is used, water is used for preparing emulsion with the concentration of 10 wt%;
(3) the modified polyester is subjected to metering, extrusion, cooling, oiling, stretching, heat setting and winding to prepare the superfine denier polyester drawn yarn, wherein the spinning process parameters of the superfine denier polyester drawn yarn are as follows: spinning temperature: 294 ℃; cooling temperature: 24 ℃; network pressure: 0.29 MPa; a roll speed: 3190 m/min; first roll temperature: 92 ℃; two roll speed: 4060 m/min; temperature of the two rolls: 129 ℃; speed of winding: 3960 m/min; the initial pressure of the spin pack was 120bar and the pressure rise Δ P was 0.56 bar/day.
The filament number of the finally prepared superfine denier polyester drawn yarn is 0.28dtex, the filament number is 72dtex, the breaking strength is 4.0cN/dtex, the elongation at break is 43.0%, the breaking strength CV value is 4.7%, the elongation at break CV value is 9.1%, the boiling water shrinkage rate is 7.0%, the oil content is 1.06%, and the number of the broken filaments of one spinning cake is 1.
Example 10
A method for preparing superfine denier polyester drawn yarns comprises the following steps:
(1) preparing modified polyester;
(a) preparing 3-methyl-3-pentyl-1, 6-hexanediol; reacting 3-methyl-3-pentyl-propionaldehyde, propionaldehyde and triethylamine for 20min at 94 ℃ in a nitrogen atmosphere, then adding the concentrated solution into a hydrogenation reactor with a Raney nickel catalyst, reacting at the hydrogen pressure of 2.914MPa and the temperature of 100 ℃, cooling after the reaction is finished, and separating out the catalyst. After the solution is treated by ion exchange resin, water is evaporated under reduced pressure, and the 3-methyl-3-pentyl-1, 6-hexanediol is obtained through separation and purification, wherein the structural formula of the 3-methyl-3-pentyl-1, 6-hexanediol is as follows:
Figure GDA0001605145150000231
(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 film strength of the oil agent is high and is 125N,the surface tension of the oil agent was 24.8cN/cm, and the specific resistance was 1.3X 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 15 wt% by using water when in use;
(3) the modified polyester is subjected to metering, extrusion, cooling, oiling, stretching, heat setting and winding to prepare the superfine denier polyester drawn yarn, wherein the spinning process parameters of the superfine denier polyester drawn yarn are as follows: spinning temperature: 294 ℃; cooling temperature: 24 ℃; network pressure: 0.26 MPa; a roll speed: 3180 m/min; first roll temperature: 93 ℃; two roll speed: 4100 m/min; temperature of the two rolls: 130 ℃; speed of winding: 4000 m/min; the initial pressure of the spin pack was 120bar and the pressure rise Δ P was 0.6 bar/day.
The filament number of the finally prepared superfine denier polyester drawn yarn is 0.3dtex, the filament number is 50dtex, the breaking strength is 4.4cN/dtex, the elongation at break is 38.0%, the breaking strength CV value is 4.6%, the elongation at break CV value is 9.5%, the boiling water shrinkage rate is 7.1%, the oil content is 1.08%, and the number of broken filaments of one spinning cake is 0.
Example 11
A method for preparing superfine denier polyester drawn yarns comprises the following steps:
(1) preparing modified polyester;
(a) preparing 3, 3-diamyl-1, 5-pentanediol; reacting 3, 3-diamyl-propionaldehyde, acetaldehyde and triethylamine for 20min at 95 ℃ in a nitrogen atmosphere, then adding the concentrated solution into a hydrogenation reactor with a Raney nickel catalyst, reacting at the hydrogen pressure of 2.914MPa and the temperature of 100 ℃, and cooling to separate out the catalyst after the reaction is finished. After the solution is treated by ion exchange resin, water is evaporated under reduced pressure, and the 3, 3-diamyl-1, 5-pentanediol is obtained by separation and purification, wherein the structural formula of the 3, 3-diamyl-1, 5-pentanediol is as follows:
Figure GDA0001605145150000251
(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 85.58 wt%, 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 1.0X 108Omega cm; coefficient of static friction (. mu.) between fibres (F/F) after oilings) 0.260, coefficient of dynamic friction (. mu.)d) Is 0.263; after oiling, the coefficient of static friction (μ) between the fiber and the metal (F/M)s) 0.202, coefficient of dynamic friction (. mu.)d) 0.330, and the prepared oil agent is prepared into an emulsion with the concentration of 19 wt% by using water when in use;
(3) the modified polyester is subjected to metering, extrusion, cooling, oiling, stretching, heat setting and winding to prepare the superfine denier polyester drawn yarn, wherein the spinning process parameters of the superfine denier polyester drawn yarn are as follows: spinning temperature: 287 deg.C; cooling temperature: 24 ℃; network pressure: 0.30 MPa; a roll speed: 3150 m/min; first roll temperature: 93 ℃; two roll speed: 4100 m/min; temperature of the two rolls: 130 ℃; speed of winding: 4000 m/min; the initial pressure of the spin pack was 120bar and the pressure rise Δ P was 0.57 bar/day.
The filament number of the finally prepared superfine denier polyester drawn yarn is 0.29dtex, the filament number is 74dtex, the breaking strength is 4.5cN/dtex, the elongation at break is 43.0%, the breaking strength CV value is 5.0%, the elongation at break CV value is 9.5%, the boiling water shrinkage rate is 8.0%, the oil content is 1.09%, and the number of broken filaments of one spinning cake is 0.

Claims (7)

1. The preparation method of the superfine denier polyester drawn yarn is characterized by comprising the following steps: the modified polyester is subjected to metering, extrusion, cooling, oiling, stretching, heat setting and winding to prepare superfine denier polyester drawn yarns;
the molecular chain of the modified polyester comprises a terephthalic acid chain segment, an ethylene glycol chain segment and a dihydric alcohol chain segment with a branched chain, wherein the structural formula of the dihydric alcohol with the branched chain is as follows:
Figure FDA0002354401670000011
in the formula, R1And R2Each independently selected fromA linear alkylene group having 1 to 3 carbon atoms, R3Selected from alkyl with 1-5 carbon atoms, R4Selected from alkyl with 2-5 carbon atoms;
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;
the filament number of the superfine denier polyester drawn yarns is 0.2-0.3 dtex;
the fineness of the superfine denier polyester drawn yarns is 50-75 dtex, the breaking strength is more than or equal to 3.6cN/dtex, the elongation at break is 40.0 +/-3.0%, the breaking strength CV value is less than or equal to 5.0%, the elongation at break CV value is less than or equal to 10.0%, the boiling water shrinkage rate is 7.5 +/-0.5%, the oil content is 0.90 +/-0.20%, and the number of broken filaments of one spinning cake is less than or equal to 2;
the content of cyclic oligomer in the modified polyester is less than or equal to 0.6 wt%;
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;
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.
2. The method for preparing the drawn superfine denier polyester yarn as claimed in claim 1, wherein the thermal weight loss of the oil agent after heat treatment at 200 ℃ for 2h is less than 15 wt%;
the kinematic viscosity of the oil agent is 27.5-30.1 mm at the temperature of (50 +/-0.01) ° C2The kinematic viscosity of the oil agent prepared from water into 10 wt% 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 x 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.
3. The method for preparing drawn yarn of extra fine denier polyester as claimed in claim 2, wherein the oil solution further contains mineral oil, potassium phosphate, trimethylolpropane laurate and sodium alkyl 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;
when the oil agent is used, preparing an emulsion with the concentration of 10-20 wt% by using water;
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 FDA0002354401670000021
the mixing is carried out at normal temperature, the stirring temperature is 40-55 ℃, and the stirring time is 1-3 h.
4. The method for preparing the drawn superfine denier polyester yarn according to any one of claims 1 to 3, wherein the parameters of the spinning process of the drawn superfine denier polyester yarn are as follows:
spinning temperature: 287-295 ℃;
cooling temperature: 20-25 ℃;
network pressure: 0.20 to 0.30 MPa;
a roll speed: 3100 to 3200m/min
First roll temperature: 88 to 93 ℃;
two roll speed: 3900 to 4100 m/min;
temperature of the two rolls: 120-130 ℃;
speed of winding: 3800-4000 m/min;
the initial pressure of the spinning assembly is 120bar, and the pressure rise delta P is less than or equal to 0.6 bar/day.
5. The method for preparing drawn superfine denier polyester yarn as claimed in claim 1, wherein the branched diol 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-bis (1, -methylethyl) -1, 7-heptanediol, 3-dipropyl-1, 5-pentanediol, 4-dipropyl-1, 7-heptanediol, 4-methyl-4- (1, 1-dimethylethyl) -1, 7-heptanediol, 3-methyl-3-pentyl-1, 6-hexanediol or 3, 3-diamyl-1, 5-pentanediol.
6. The method for preparing the drawn superfine denier polyester yarn as claimed in claim 5, wherein the modified polyester is prepared by 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 method comprises the following specific steps:
(1) performing esterification reaction;
preparing terephthalic acid, ethylene glycol and the dihydric alcohol with the branched chain into slurry, adding a catalyst, a delustering agent 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.
7. The method for preparing the drawn superfine denier polyester yarn as claimed in claim 6, wherein in the step (1), the molar ratio of terephthalic acid, 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 terephthalic acid, the addition amount of the delustering agent is 0.20-0.25% of the weight of terephthalic acid, and the addition amount of the stabilizer is 0.01-0.05% of the weight of terephthalic acid;
the catalyst is antimony trioxide, ethylene glycol antimony or antimony acetate, the flatting agent is titanium dioxide, and the stabilizer is triphenyl phosphate, trimethyl phosphate or trimethyl phosphite.
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