CN108035007A - Superfine denier polyester drafting silk and preparation method thereof - Google Patents

Superfine denier polyester drafting silk and preparation method thereof Download PDF

Info

Publication number
CN108035007A
CN108035007A CN201711340289.1A CN201711340289A CN108035007A CN 108035007 A CN108035007 A CN 108035007A CN 201711340289 A CN201711340289 A CN 201711340289A CN 108035007 A CN108035007 A CN 108035007A
Authority
CN
China
Prior art keywords
finish
denier polyester
superfine denier
pressure
modified poly
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201711340289.1A
Other languages
Chinese (zh)
Other versions
CN108035007B (en
Inventor
王山水
魏德新
丁竹君
卓怀智
晏金龙
张建光
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Hengli Chemical Fiber Co Ltd
Original Assignee
Jiangsu Hengli Chemical Fiber Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Hengli Chemical Fiber Co Ltd filed Critical Jiangsu Hengli Chemical Fiber Co Ltd
Priority to CN201711340289.1A priority Critical patent/CN108035007B/en
Publication of CN108035007A publication Critical patent/CN108035007A/en
Application granted granted Critical
Publication of CN108035007B publication Critical patent/CN108035007B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—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

Abstract

The present invention relates to a kind of superfine denier polyester drafting silk and preparation method thereof, by modified poly ester through measuring, extruding, cooling down, oiling, stretching, thermal finalization and winding superfine denier polyester drafting silk is made, contain crown ether in the finish wherein to oil, and the content of crown ether is 67.30~85.58wt%, it is as follows that modified poly ester strand includes terephthalic acid (TPA) segment, ethylene glycol segment and branched dihydric alcohol segment, the structural formula of branched dihydric alcohol：In formula, R1And R2It is each independently selected from the straight-chain alkyl-sub that carbon number is 1~3, R3Selected from the alkyl that carbon number is 1~5, R4Selected from the alkyl that carbon number is 2~5, the filament number of obtained superfine denier polyester drafting silk is 0.2~0.3dtex.The method of the present invention advantages of simple, obtained superfine denier polyester drafting silk is soft fine and smooth, and quality is high.

Description

Superfine denier polyester drafting silk and preparation method thereof
Technical field
The invention belongs to fiber preparation field, is related to a kind of superfine denier polyester drafting silk and preparation method thereof.
Background technology
Polyethylene terephthalate (PET) fiber since the advent of the world, obtains fast because of the excellent performance that it has Suddenly develop, its yield has become the hat of world's synthetic fibers.Polyester fiber has high fracture strength, elasticity modulus height, returns Moderate, the thermal finalization excellent performance of elasticity, heat-resisting light resistance be good and a series of Optimality such as acid-fast alkali-proof good corrosion resistance Can, and fabric prepared therefrom has the advantages that crease-resistant and stiffness is good, so, polyester fiber is standby to be widely used in clothes With the field such as home textile.
But during the polycondensation reaction of synthesis ethylene terephthalate, particularly when generating linear polymer, Since high-temperature oxydation is degraded, also association is linear and cyclic oligomer, cyclic oligomer are due to macromolecular chain in polycondensation phase Hold back what is stung cyclisation and formed, about 70% above is cyclic trimer in cyclic oligomer, cyclic trimer have easily aggregation, The easily characteristic such as crystallization, chemistry and heat-resistant stability height, generation cyclic trimer can there are following influence on polyester processing：(1) meeting The blocking of filament spinning component is caused, influences the service life of fondant filter and component；(2) can be separated out in fiber heat-setting process, It is deposited on heating roller, causes frictional force to increase and heat irregular；(3) dyeing course can be made centered on cyclic trimer Dye aggregation is simultaneously adhered to fiber surface, and phenomena such as dyestuff color dot, spot and dyeing defect occurs in fiber surface, influences to be weaved by it The feel and coloured light of the fabric formed, the normal flow velocity of melt can be limited by being simultaneously filled with the cyclic oligomer of pipeline and valve Degree, causes stock-dye irregular, poor reproducibility；(4) fiber surface is adhered to, causes, around yarn difficulty, broken yarn and thickness occur Phenomena such as uneven, influence the mechanical properties such as fracture strength and the elongation at break of fiber, seriously affect product quality.
In order to reduce the generation of the cyclic oligomer during polyester polycondensation reaction, domestic and international researcher has carried out largely Research.The main method for reducing the cyclic oligomer in polyester at this stage has：(1) add pentavalent phosphorous compound or etherificate is closed Thing, makes it be combined with the metallic catalyst in process of polyester synthesizing, or the amount of increase heat stabilizer, so as to be produced to polyester Raw stabilization, thus the generation of cyclic trimer can be suppressed under high-temperature fusion；(2) polyester fondant is reduced at high temperature Residence time.But the above method can cause molecular weight of polyesters reduction and distribution to widen, the product of final obtained fiber are influenced Matter, while the reduction effect to cyclic trimer oligomer and unobvious.
Growing with polyester fiber yield, people also increasingly improve the quality requirement of fiber, in particular with The fast development of microdenier polyester fibers, market propose the quality of fiber the requirement of higher.Flexibility is one for fiber The critically important performance of item, the good fiber of flexibility has fineness thin and uniform, intensity high resilience, soft texture and hand greatly The advantages that sense is sliding glutinous fine and smooth, and the fabric being spun into by it has characteristic soft and that dress is graceful, yet with existing There is the oligomer in technology fiber higher so that fiber is difficult to spin thin, and the finish used in spinning process is often difficult To meet the condition needed for production superfine Denier fibre, obtained fiber quality is not high, and flexibility is often nor very good.
Therefore, preparing the PET fiber that a kind of flexibility is good and quality is high becomes current urgent problem to be solved.
The content of the invention
The purpose of the invention is to overcome prior art fiber flexibility difference and the not high problem of quality, there is provided Yi Zhongrou Soft good and high quality fused mass directly spinning washs ultra-soft composite filament and preparation method thereof.Band side chain in modified poly ester of the present invention Dihydric alcohol introducing, reduce the cyclic oligomer produced in polyester side reaction, improve the level-dyeing property of fiber, make fiber It can spin thinner, and then improve the flexibility of fiber；The use of the finish containing crown ether, improves the heat resistance and profit of finish Slip, so as to improve the spinnability of fiber, reduce causes showing for broken fiber filaments in spinning process because of electrostatic problem As improving the quality of obtained fiber so that final obtained superfine denier polyester drafting silk has soft fine and smooth superiority Energy.
In order to achieve the above object, the technical solution adopted by the present invention is：
Superfine denier polyester drafting silk, the material of superfine denier polyester drafting silk is modified poly ester；
The strand of modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment and branched dihydric alcohol segment, band The structural formula of the dihydric alcohol of side chain is as follows：
In formula, R1And R2It is each independently selected from the straight-chain alkyl-sub that carbon number is 1~3, R3It is 1 selected from carbon number ~5 alkyl, R4Selected from the alkyl that carbon number is 2~5, the purpose that carbon atom number limits：Due to introducing branch in dihydric alcohol Chain structure and backbone, can weaken the electronegativity of alkoxy portion, and the carbon atom number of branched structure is too small, to alcoxyl The electronegativity influence of base section is small, has little significance to the generation for reducing cyclic oligomer；The carbon atom number mistake of branched structure Greatly, intermolecular entanglement can be produced, the distribution to molecular weight has an impact；
The filament number of superfine denier polyester drafting silk is 0.2~0.3dtex.
As preferable technical solution：
Superfine denier polyester drafting silk as described above, the fiber number of the superfine denier polyester drafting silk is 50~75dtex, is broken Resistance to spalling >=3.6cN/dtex, elongation at break are 40.0 ± 3.0%, fracture strength CV value≤5.0%, extension at break CV values ≤ 10.0%, boiling water shrinkage is 7.5 ± 0.5%, and oil content is 0.90 ± 0.20%, lousiness≤2 of a spinning cake.
Superfine denier polyester drafting silk as described above, content≤0.6wt% of cyclic oligomer in the modified poly ester, The amount of cyclic oligomer is 1.5~2.1wt% in polyester made from the prior art, and the present invention is significantly dropped relative to the prior art The low growing amount of cyclic oligomer；
The number-average molecular weight 20000~27000 of the modified poly ester, molecular weight distributing index are 1.8~2.2, modified poly- The molecular weight of ester is higher, and molecular weight distribution is relatively narrow, disclosure satisfy that the demand of spinning processing, and it is excellent to be conducive to processability Fiber；
The molar content of branched dihydric alcohol segment is terephthalic acid (TPA) segment molar content in the modified poly ester 3~5%, the molar content of branched dihydric alcohol segment is relatively low in modified poly ester, is conducive to keep the Optimality of polyester itself Energy.
Superfine denier polyester drafting silk as described above, the branched dihydric alcohol is 2- Ethyl-2-Methyls -1,3- third Glycol, 2,2- diethyl -1,3- propane diols, 2-butyl-2-ethyl-1,3-propanediol, 3,3- diethyl -1,5- pentanediols, 4, 4- diethyl -1,7- heptandiols, 4,4- bis- (1,-Methylethyl) -1,7- heptandiols, 3,3- dipropyl -1,5- pentanediols, 4, 4- dipropyl -1,7- heptandiols, 4- methyl -4- (1,1- dimethyl ethyls) -1,7- heptandiols, 3- methyl -3- amyl groups -1,6- Hexylene glycol or 3,3- diamyl -1,5- pentanediols.
Superfine denier polyester drafting silk as described above, the preparation method of the modified poly ester are：By terephthalic acid (TPA), second Successively progress esterification and polycondensation reaction obtain modified poly ester after mixing for glycol and the branched dihydric alcohol；Tool Body step is as follows：
(1) esterification；
Terephthalic acid (TPA), ethylene glycol and the branched dihydric alcohol are made into slurry, add catalyst, delustering agent and After mixing, the pressurization progress esterification in nitrogen atmosphere, moulding pressure is normal pressure~0.3MPa to stabilizer, and esterification is anti- The temperature answered is 250~260 DEG C, is esterification when the water quantity of distillate in esterification reaches more than the 90% of theoretical value Terminal；
(2) polycondensation reaction；
After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, the staged pressure 30~ Steadily is evacuated to by normal pressure below absolute pressure 500Pa in 50min, reaction temperature is 260~270 DEG C, the reaction time for 30~ 50min, then proceedes to vacuumize, and carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is further reduced to absolute pressure Below 100Pa, reaction temperature are 275~285 DEG C, and the reaction time is 50~90min, and modified poly ester is made.
Superfine denier polyester drafting silk as described above, in step (1), terephthalic acid (TPA), ethylene glycol and described branched The molar ratio of dihydric alcohol is 1:1.2~2.0:0.03~0.06, the addition of the catalyst is terephthalic acid (TPA) weight 0.01~0.05%, the addition of the delustering agent is the 0.20~0.25% of terephthalic acid (TPA) weight, and the stabilizer adds Enter 0.01~0.05% that amount is terephthalic acid (TPA) weight；
The catalyst is antimony oxide, antimony glycol or antimony acetate, and the delustering agent is titanium dioxide, described steady It is triphenyl phosphate, trimethyl phosphate or Trimethyl phosphite to determine agent.
The present invention also provides one kind to prepare as described above prepare as claim 1~6 any one of them super fine denier is washed The method of synthetic fibre drafting silk, by the modified poly ester through measuring, extruding, cooling down, oiling, stretching, thermal finalization and winding be made ultra-fine Denier polyester drawn yarns；
Contain crown ether in the finish to oil, and the content of crown ether is 67.30~85.58wt%, finish of the present invention The content of middle crown ether need to be kept within the specific limits, and the addition of crown ether is too low, can not be made that viscosity is low, heat resistance is good and The higher finish of film strength, the addition of crown ether is excessive, other performance indicators of finish can be affected.
Crown ether is a kind of heterocyclic organic compounds, includes multiple ether groups.The wettability of crown ether-like surfactant Bigger than corresponding open chain compound, crown ether has preferable solubilising, and salt compounds are relatively low in the solubility of organic compound, but As the solubility of the organic matter of the addition salt compounds of crown ether is improved.Conventional polyester class compound or poly- in finish Ethers, since molecular weight is larger and the effect of hydrogen bond, intermolecular effect is larger, and it is larger to show as kinematic viscosity, adds crown ether Afterwards, crown ether can be preferably compatible in polyesters compound or polyethers finish system, into polyesters compound or polyethers Between strand, the active force between strand is shielded, so as to cause the viscosity of finish system to reduce.While preparation medium Antistatic additive is broadly divided into anionic, cationic and amphoteric surfactant, mostly containing metal ion or with salt Form exists, this all makes antistatic additive and polyesters compound in finish or the phase tolerance of polyethers, the addition of crown ether, due to Salting in effect, improves antistatic additive and polyesters compound or the compatibility of polyethers, and then improves the strong of finish oil film Degree, this stability and the product amount of holding to spinning have larger meaning.The index of finish is the embodiment of a composite factor, because And certain restriction is proposed to the addition of crown ether, too low heat resistance, the advantage of film strength to finish embodies not enough, Other excessive indexs can be restricted.
As preferable technical solution：
Method as described above, thermal weight loss is less than 15wt% after the finish heats 2h at 200 DEG C, and crown ether has The volatilization point of higher and excellent heat-resistant stability, the heat resistance of the finish introduced after crown ether are also obviously improved；
For the finish at (50 ± 0.01) DEG C, kinematic viscosity is 27.5~30.1mm2/ s, the finish are configured with water The kinematic viscosity after lotion for being 10wt% into concentration is 0.93~0.95mm2/ s, the viscosity that crown ether can reduce finish are main It is due to that crown ether oneself viscosity is relatively low and be pearl small molecule, after introducing crown ether in finish system, crown ether can be preferably compatible In polyesters compound or polyether compound finish system, while enter polyesters compound or polyether compound point Between subchain, the active force between strand is shielded, so as to reduce the viscosity of finish system；
The film strength of the finish is 121~127N, and the film strength of finish is relatively low in the prior art, generally exists 110N or so, this mostly exists containing metal ion or in a salt form mainly due to the antistatic additive of preparation medium, leads Antistatic additive and polyesters compound or the poor compatibility of polyether compound in finish are caused, crown ether can improve film strength Salting in effect can be produced after being added mainly due to crown ether, improves antistatic additive and polyesters compound or polyethers Compatibility, and then improve finish oil film strength；
The surface tension of the finish is 23.2~26.8cN/cm, and ratio resistance is 1.0 × 108~1.8 × 108Ω·cm；
After oiling, confficient of static friction between fiber and fiber is 0.250~0.263, the coefficient of kinetic friction for 0.262~ 0.273；
After oiling, confficient of static friction between fiber and metal is 0.202~0.210, the coefficient of kinetic friction for 0.320~ 0.332。
Method as described above, the crown ether are 2- methylols -12-crown-4,15- crown ethers -5 or 2- methylol -15- crown-s 5；
Also contain mineral oil, phosphate kalium salt, trimethylolpropane laurate and sodium alkyl sulfonate in the finish；
The mineral oil is one kind in the mineral oil of 9#~17#；
The phosphate kalium salt for 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, isomerous tridecanol polyoxyethylene ether phosphate kalium salt or Ten tetracosanol phosphate kalium salts；
The sodium alkyl sulfonate is dodecyl sodium sulfate, pentadecyl sulfonic acid sodium or sodium cetanesulfonate；
The finish is configured to the emulsion that concentration is 10~20wt% when in use, with water；
The preparation method of the finish is：By crown ether and phosphate kalium salt, trimethylolpropane laurate and alkyl sulphur Sour sodium is added in mineral oil after mixing is uniformly mixing to obtain finish；Count in parts by weight, the addition of each component is such as Under：
The mixing carries out at normal temperatures, and the temperature of the stirring is 40~55 DEG C, and the time is 1~3h.
Method as described above, the spinning technology parameter of the superfine denier polyester drafting silk are as follows：
Spinning temperature：287~295 DEG C；
Cooling temperature：20~25 DEG C；
Network pressure：0.20~0.30MPa；
One roller speed：3100~3200m/min
One roll temperature：88~93 DEG C；
Two roller speeds：3900~4100m/min；
Two roll temperatures：120~130 DEG C；
The speed of winding：3800~4000m/min；
The initial pressure of filament spinning component is 120bar, and pressure rises Δ P≤0.6bar/ days.
Invention mechanism：
In organic compound, the angle between two chemical bonds that the same atom of intramolecular is formed is known as bond angle, and bond angle leads to Commonly use the number of degrees to represent, the electronegativity of central atom and coordination atom in organic compound molecule, the bond angle of molecule can be influenced.When During the electronegativity increase for the coordination atom being bonded with central atom, the enhancing of coordination atom electron-withdrawing power, bond electron pair will be to Ligand direction is moved, from central atom farther out, make it is close to each other because repulsion reduces between key pair so that bond angle also subtracts therewith It is small, on the contrary, when the electronegativity for the coordination atom being bonded with central atom reduces, the enhancing of coordination atom electron donation, bonding Electronics to will be moved to central atom direction, from central atom closer to, make to be located remotely from each other because repulsion increases between key pair so that Bond angle also increases therewith.
According to Pauling Electronegativities, the electronegativity of C, H and O atom is respectively 2.55,2.20 and 3.44, and according to Valence electron balancing energy is theoretical, and the calculation formula of Group Electronegativity is shown below：
In formula, XiFor the electronegativity of i atoms neutral atom before bonding, NVe,I be i atoms in valence electron number, niFor The number of i atoms in the molecule.Calculation procedure for more complicated Group Electronegativity is mainly：Simple radical is calculated first The electronegativity of group, then regards simple group as electronegativity that quasiatom calculates more complicated group again, such successive iteration, Finally obtain the electronegativity of Targeting groups.It should be noted that calculate quasiatom electronegativity when, base son (for example, Base of group-OH is O atom) in the valence electron of non-bonding regard the valence electron of quasiatom as.
C atoms can be with the O atom of hydroxyl in dihydric alcohol after the C-O keys fracture of carboxyl in terephthalic acid (TPA) in the present invention Combine to form the new C-O keys in ester group, the key C-C and the change newly formed that the C atoms in ester group are formed with C atoms on phenyl ring The bond angle learned between key C-O is denoted as α, and the change of bond angle α can influence annulation, and when α is less than 109 °, molecule is easy to cyclization, And as the increase of α, the probability of molecule cyclization can decline.Present invention introduces branched dihydric alcohol, structural formula such as following formula institute Show：
In formula, R1And R2It is each independently selected from the straight-chain alkyl-sub that carbon number is 1~3, R3It is 1 selected from carbon number ~5 alkyl, R4Selected from the alkyl that carbon number is 2~5.The diol structure due to introducing branched structure and backbone, Can weaken the electronegativity of its alkoxy portion, by the calculation formula of Group Electronegativity can also draw in the diol structure with The electronegativity for the group that carbonyl is connected is between 2.59~2.79 in diacid, and the base being connected in ethylene glycol with carbonyl in diacid Group-OCH2CH2- electronegativity be 3.04, thus its alkoxy is than-the OCH in ethylene glycol2CH2- there is stronger electron Property, hence in so that the bond electron pair on the chemical bond C-O keys newly formed will be moved to center C atomic orientations, from central atom Closer to making to be located remotely from each other because repulsion increases between key pair, so that bond angle α is more than 109 °, generate the probability of linear polymer Increase, reduces the generation of cyclic oligomer so that fiber can spin especially thin, and then improve the flexibility of fiber.
The present invention has been made that a kind of viscosity is low, heat resistance is good and film strength is higher by introducing crown ether in finish Finish.The viscosity of finish is higher mainly due to containing conventional polyester class compound or polyethers in finish in the prior art Compound, such compound is since molecular weight is larger and the effect of hydrogen bond, and intermolecular effect is larger shows as kinematic viscosity for its It is larger, thus cause the viscosity of finish higher, the viscosity of finish can significantly reduce after addition crown ether, mainly due to crown ether Oneself viscosity is relatively low and is pearl small molecule, and crown ether can be preferably compatible in polyesters compound or polyethers finish system, At the same time between polyesters compound or polyether compound strand, the active force between strand is shielded, so as to reduce The viscosity of finish system.The relatively low antistatic additive mainly due to preparation medium of the film strength of finish is mostly in the prior art Exist containing metal ion or in a salt form, cause antistatic additive and the phase of polyesters compound or polyethers in finish Capacitive is poor, and crown ether, which can be improved after film strength is added mainly due to crown ether, can produce salting in effect, improve antistatic Agent and polyesters compound or the compatibility of polyethers, and then improve finish oil film strength.In addition, crown ether has higher Volatilization point and excellent heat-resistant stability, the heat resistance of finish introduced after crown ether be also obviously improved, due to The oil agent viscosity of the present invention is low and lubricity is good, therefore precursor can pass through spinning, and oil agent can also be in fibre in addition Tie up filament surfaces and form the high protective film of one layer of intensity, prevent damage and fiber precursor surface of the precursor in spinning process to lack The appearance of phenomena such as sunken generation, the reduction of prevention precursor quality and hydraulic performance decline, reduces in spinning process because of electrostatic problem And causing the phenomenon of broken fiber filaments, final obtained superfine denier polyester drafting silk has soft fine and smooth excellent properties.
Beneficial effect：
(1) a kind of superfine denier polyester drafting silk of the invention, preparation flow advantages of simple, obtained drafting silk have soft The characteristics of soft exquisiteness, quality is high；
(2) a kind of superfine denier polyester drafting silk of the invention, the oil agent containing crown ether used during oiling have The characteristics of viscosity is low, heat resistance is good, film strength is high, Lubricity is good and antistatic property is strong, improves the stabilization of spinning The processing performance of property and fiber；
(3) preparation method of a kind of superfine denier polyester drafting silk of the invention, by introducing band side chain in modified poly ester Dihydric alcohol, the bond angle of polyester molecule is changed, so as to significantly reduce the generation of cyclic oligomer in process of polyester synthesizing.
Embodiment
The invention will be further elucidated with reference to specific embodiments.It is to be understood that these embodiments are merely to illustrate this Invent rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, this area Technical staff can make various changes or modifications the present invention, and such equivalent forms equally fall within the application appended claims Book limited range.
Embodiment 1
A kind of preparation method of superfine denier polyester drafting silk, step are as follows：
(1) preparation of modified poly ester；
(a) esterification；It is 1 by molar ratio:1.2:0.03 terephthalic acid (TPA), ethylene glycol and 2- Ethyl-2-Methyls- 1,3-PD is made into slurry, antimony oxide, titanium dioxide and triphenyl phosphate is added after mixing, in nitrogen atmosphere Middle pressurization carries out esterification, and moulding pressure is normal pressure, and the temperature of esterification is 250 DEG C, when the water in esterification distillates Amount is esterification terminal when reaching the 90% of theoretical value, and wherein the addition of antimony oxide is terephthalic acid (TPA) weight 0.01%, the addition of titanium dioxide is the 0.20% of terephthalic acid (TPA) weight, and the addition of triphenyl phosphate is terephthaldehyde The 0.05% of sour weight, wherein 2- ethyls -2- methyl isophthalic acids, the structural formula of ammediol are as follows：
(b) polycondensation reaction；After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, It is 500Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 30min, and reaction temperature is 260 DEG C, reaction time 40min, Then proceed to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, it is 100Pa reaction pressure is further reduced to absolute pressure, Reaction temperature is 275 DEG C, reaction time 70min, and modified poly ester is made, and the wherein strand of modified poly ester is included to benzene two Formic acid segment, ethylene glycol segment and 2- ethyl -2- methyl isophthalic acids, ammediol segment, the content of cyclic oligomer in modified poly ester For 0.6wt%, number-average molecular weight 20000, molecular weight distributing index 2.0,2- Ethyl-2-Methyls -1,3- third in modified poly ester The molar content of glycol segment is the 3% of terephthalic acid (TPA) segment molar content；
(2) preparation to oil with finish；
By 2- methylols -12-crown-4 and 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, trimethylolpropane laurate and dodecane Base sodium sulfonate is added in 9# mineral oil and obtains finish in 40 DEG C of uniform stirring 1h after mixing at normal temperatures, by weight Number meter, the addition of each component are as follows：9# mineral oil is 2 parts；Trimethylolpropane laurate is 10 parts；2- methylols- 12-crown-4 is 90 parts；1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite is 8 parts；Dodecyl sodium sulfate is 3 parts；Crown ether in the finish prepared Content be 79.6wt%, the resistance to elevated temperatures of finish is excellent, 200 DEG C heat 2h after thermal weight loss be 14.5wt%；Oil The viscosity of agent is relatively low, at (50 ± 0.01) DEG C, kinematic viscosity 29.6mm2/ s, the breast that concentration is 10wt% is configured to water Kinematic viscosity after liquid is 0.93mm2/ s, the film strength of finish is higher, film strength 125N, and the surface tension of finish is 24.8cN/cm, ratio resistance are 1.3 × 108Ω·cm；After oiling, the confficient of static friction (μ between fiber and fiber (F/F)s) be 0.255, the coefficient of kinetic friction (μd) it is 0.266；After oiling, the confficient of static friction (μ between fiber and metal (F/M)s) be 0.203, the coefficient of kinetic friction (μd) it is 0.320, the finish of preparation is configured to the emulsification that concentration is 15wt% when in use, with water Liquid；
(3) by modified poly ester through measuring, extruding, cooling down, oiling, stretching, thermal finalization and winding be made superfine denier polyester and lead Silk is stretched, the spinning technology parameter of wherein superfine denier polyester drafting silk is as follows：Spinning temperature：290℃；Cooling temperature：22℃；Net Network pressure：0.25MPa；One roller speed：3150m/min；One roll temperature：90℃；Two roller speeds：4000m/min；Two roll temperatures： 125℃；The speed of winding：3900m/min；The initial pressure of filament spinning component is 120bar, and it is 0.54bar/ days that pressure, which rises Δ P,.
The filament number of final obtained superfine denier polyester drafting silk is 0.25dtex, fiber number 65dtex, fracture strength For 4.5cN/dtex, elongation at break 40.0%, fracture strength CV values are 5.0%, and extension at break CV values are 9.0%, boiling water Shrinking percentage is 7.5%, oil content 1.1%, and the lousiness of a spinning cake is 0.
Embodiment 2
A kind of preparation method of superfine denier polyester drafting silk, step are as follows：
(1) preparation of modified poly ester；
(a) esterification；It is 1 by molar ratio:1.3:0.04 terephthalic acid (TPA), ethylene glycol and 2,2- diethyl -1,3- Propane diols is made into slurry, adds antimony glycol, titanium dioxide and trimethyl phosphate after mixing, pressurizes in nitrogen atmosphere Esterification is carried out, moulding pressure is normal pressure, and the temperature of esterification is 260 DEG C, when the water quantity of distillate in esterification reaches Theoretical value 91% when be esterification terminal, wherein the addition of antimony glycol be terephthalic acid (TPA) weight 0.02%, two The addition of titanium oxide is the 0.21% of terephthalic acid (TPA) weight, and the addition of trimethyl phosphate is terephthalic acid (TPA) weight 0.03%, wherein the structural formula of 2,2- diethyl -1,3- propane diols is as follows：
(b) polycondensation reaction；After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, It is 490Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 35min, and reaction temperature is 261 DEG C, reaction time 30min, Then proceed to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, it is 100Pa reaction pressure is further reduced to absolute pressure, Reaction temperature is 277 DEG C, reaction time 85min, and modified poly ester is made, and the wherein strand of modified poly ester is included to benzene two Formic acid segment, ethylene glycol segment and 2,2- diethyl -1,3-PD segment, the content of cyclic oligomer is in modified poly ester 0.6wt%, number-average molecular weight 27000, molecular weight distributing index 1.8,2,2- diethyl -1,3-PD in modified poly ester The molar content of segment is the 5% of terephthalic acid (TPA) segment molar content；
(2) preparation to oil with finish；
By 15- crown ethers -5 and isomerous tridecanol polyoxyethylene ether phosphate kalium salt, trimethylolpropane laurate and ten Five sodium alkyl sulfonates are added in 10# mineral oil and obtain finish in 43 DEG C of uniform stirring 1.5h after mixing at normal temperatures, Count in parts by weight, the addition of each component is as follows：10# mineral oil is 2 parts；Trimethylolpropane laurate is 15 parts； 15- crown ethers -5 are 70 parts；Isomerous tridecanol polyoxyethylene ether phosphate kalium salt is 10 parts；Pentadecyl sulfonic acid sodium is 7 parts；System Content for crown ether in the finish gone out is 67.30wt%, and the resistance to elevated temperatures of finish is excellent, the heat after 200 DEG C of heating 2h Weightlessness is 13wt%；The viscosity of finish is relatively low, at (50 ± 0.01) DEG C, kinematic viscosity 28.1mm2/ s, is configured to water Kinematic viscosity after the lotion that concentration is 10wt% is 0.93mm2/ s, the film strength of finish is higher, is 123N, the table of finish Face tension force is 25.1cN/cm, and ratio resistance is 1.5 × 108Ω·cm；After oiling, the static friction between fiber and fiber (F/F) Coefficient (μs) it is 0.257, the coefficient of kinetic friction (μd) it is 0.265；After oiling, the confficient of static friction between fiber and metal (F/M) (μs) it is 0.205, the coefficient of kinetic friction (μd) it is 0.323；When in use, it is 14wt%'s to be configured to concentration with water to the finish of preparation Emulsion；
(3) by modified poly ester through measuring, extruding, cooling down, oiling, stretching, thermal finalization and winding be made superfine denier polyester and lead Silk is stretched, the spinning technology parameter of wherein superfine denier polyester drafting silk is as follows：Spinning temperature：287℃；Cooling temperature：20℃；Net Network pressure：0.20MPa；One roller speed：3100m/min；One roll temperature：88℃；Two roller speeds：3900m/min；Two roll temperatures： 120℃；The speed of winding：3800m/min；The initial pressure of filament spinning component is 120bar, and it is 0.6bar/ days that pressure, which rises Δ P,.
The filament number of final obtained superfine denier polyester drafting silk is 0.2dtex, fiber number 50dtex, fracture strength For 4.0cN/dtex, elongation at break 43.0%, fracture strength CV values are 5.0%, and extension at break CV values are 9.2%, boiling water Shrinking percentage is 7.0%, oil content 0.7%, and the lousiness of a spinning cake is 2.
Embodiment 3
A kind of preparation method of superfine denier polyester drafting silk, step are as follows：
(1) preparation of modified poly ester；
(a) esterification；It is 1 by molar ratio:1.4:0.05 terephthalic acid (TPA), ethylene glycol and 2- butyl -2- ethyls - 1,3-PD is made into slurry, antimony acetate, titanium dioxide and Trimethyl phosphite is added after mixing, in nitrogen atmosphere Pressurization carries out esterification, and moulding pressure 0.1MPa, the temperature of esterification is 252 DEG C, when the water in esterification distillates Amount is esterification terminal when reaching the 92% of theoretical value, and wherein the addition of antimony acetate is terephthalic acid (TPA) weight 0.03%, the addition of titanium dioxide is the 0.23% of terephthalic acid (TPA) weight, and the addition of Trimethyl phosphite is to benzene two The 0.01% of formic acid weight, the structural formula of wherein 2- butyl -2- ethyls -1,3-PD are as follows：
(b) polycondensation reaction；After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, It is 495Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 40min, and reaction temperature is 263 DEG C, reaction time 45min, Then proceed to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, it is 95Pa reaction pressure is further reduced to absolute pressure, Reaction temperature is 278 DEG C, reaction time 60min, and modified poly ester is made, and the wherein strand of modified poly ester is included to benzene two Formic acid segment, ethylene glycol segment and 2- butyl -2- ethyls -1,3-PD segment, the content of cyclic oligomer in modified poly ester For 0.5wt%, number-average molecular weight 21000, molecular weight distributing index 2.2,2- butyl -2- ethyls -1,3- third in modified poly ester The molar content of glycol segment is the 4% of terephthalic acid (TPA) segment molar content；
(2) preparation to oil with finish；
By 2- methylol -15- crown-s 5 and ten tetracosanol phosphate kalium salts, trimethylolpropane laurate and 15 Sodium alkyl sulfonate is added in 11# mineral oil and obtains finish in 48 DEG C of uniform stirring 3h after mixing at normal temperatures, by weight Number meter is measured, the addition of each component is as follows：11# mineral oil is 8 parts；Trimethylolpropane laurate is 10 parts；2- hydroxyl first Base -15- crown-s 5 are 85 parts；Ten tetracosanol phosphate kalium salts are 11 parts；Pentadecyl sulfonic acid sodium is 5 parts；The finish prepared The content of middle crown ether is 70.83wt%, and the resistance to elevated temperatures of finish is excellent, and thermal weight loss is after heating 2h at 200 DEG C 11wt%；The viscosity of finish is relatively low, at (50 ± 0.01) DEG C, kinematic viscosity 30.1mm2/ s, being configured to concentration with water is Kinematic viscosity after the lotion of 10wt% is 0.94mm2/ s, the film strength of finish is higher, is 125N, the surface tension of finish For 23.2cN/cm, ratio resistance is 1.8 × 108Ω·cm；After oiling, the confficient of static friction (μ between fiber and fiber (F/F)s) For 0.250, the coefficient of kinetic friction (μd) it is 0.272；After oiling, the confficient of static friction (μ between fiber and metal (F/M)s) be 0.209, the coefficient of kinetic friction (μd) it is 0.329, the finish of preparation is configured to the emulsification that concentration is 10wt% when in use, with water Liquid；
(3) by modified poly ester through measuring, extruding, cooling down, oiling, stretching, thermal finalization and winding be made superfine denier polyester and lead Silk is stretched, the spinning technology parameter of wherein superfine denier polyester drafting silk is as follows：Spinning temperature：295℃；Cooling temperature：25℃；Net Network pressure：0.30MPa；One roller speed：3200m/min；One roll temperature：93℃；Two roller speeds：4100m/min；Two roll temperatures： 130℃；The speed of winding：4000m/min；The initial pressure of filament spinning component is 120bar, and it is 0.59bar/ days that pressure, which rises Δ P,.
The filament number of final obtained superfine denier polyester drafting silk is 0.3dtex, fiber number 75dtex, fracture strength For 3.9cN/dtex, elongation at break 43.0%, fracture strength CV values are 4.5%, and extension at break CV values are 9.5%, boiling water Shrinking percentage is 8.0%, oil content 0.75%, and the lousiness of a spinning cake is 2.
Embodiment 4
A kind of preparation method of superfine denier polyester drafting silk, step are as follows：
(1) preparation of modified poly ester；
(a) 3,3- diethyl -1,5- pentanediols are prepared；At 90 DEG C, under nitrogen atmosphere, by 3,3- diethyl-propionic aldehyde, second Aldehyde and triethylamine react 20min, then adding concentrate has in the hydrogenation reactor of thunder girl's Raney nickel, in 2.914MPa Hydrogen press and 100 DEG C at react, reaction finish, cooling, separate out catalyst, solution spent ion exchange resin processing after, decompression steam Water, separates, and purification, obtains 3,3- diethyl -1,5-PD, wherein the structural formula of 3,3- diethyl -1,5-PD is such as Under：
(b) esterification；It is 1 by molar ratio:1.5:0.06 terephthalic acid (TPA), ethylene glycol and 3,3- diethyl -1,5- Pentanediol is made into slurry, adds antimony oxide, titanium dioxide and triphenyl phosphate after mixing, adds in nitrogen atmosphere Pressure carries out esterification, and moulding pressure 0.3MPa, the temperature of esterification is 255 DEG C, when the water quantity of distillate in esterification It is esterification terminal when reaching the 95% of theoretical value, wherein the addition of antimony oxide is terephthalic acid (TPA) weight 0.04%, the addition of titanium dioxide is the 0.25% of terephthalic acid (TPA) weight, and the addition of triphenyl phosphate is terephthaldehyde The 0.01% of sour weight；
(c) polycondensation reaction；After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, It is 400Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 50min, and reaction temperature is 265 DEG C, reaction time 33min, Then proceed to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, it is 90Pa reaction pressure is further reduced to absolute pressure, Reaction temperature is 280 DEG C, reaction time 50min, and modified poly ester is made, and the wherein strand of modified poly ester is included to benzene two Formic acid segment, ethylene glycol segment and 3,3- diethyl -1,5-PD segment, the content of cyclic oligomer is in modified poly ester 0.2wt%, number-average molecular weight 23000, molecular weight distributing index 1.9,3,3- diethyl -1,5-PD in modified poly ester The molar content of segment is the 3.5% of terephthalic acid (TPA) segment molar content；
(2) preparation to oil with finish；
By 2- methylols -12-crown-4 and 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, trimethylolpropane laurate and hexadecane Base sodium sulfonate is added in 12# mineral oil and obtains finish in 40 DEG C of uniform stirring 2.5h after mixing at normal temperatures, by weight Number meter is measured, the addition of each component is as follows：12# mineral oil is 5 parts；2- methylol -12- crown-s 4 are 95 parts；Dodecyl phosphorus Acid esters sylvite is 9 parts；Sodium cetanesulfonate is 2 parts.The content of crown ether is 85.58wt% in the finish prepared, finish Resistance to elevated temperatures is excellent, and thermal weight loss is 9wt% after heating 2h at 200 DEG C；The viscosity of finish is relatively low, in (50 ± 0.01) DEG C when, kinematic viscosity 29.5mm2/ s, the kinematic viscosity being configured to water after the lotion that concentration is 10wt% is 0.93mm2/ s, The film strength of finish is higher, is 121N, the surface tension of finish is 24.3cN/cm, and ratio resistance is 1.0 × 108Ω·cm； After oiling, the confficient of static friction (μ between fiber and fiber (F/F)s) it is 0.260, the coefficient of kinetic friction (μd) it is 0.263；Oil Afterwards, the confficient of static friction (μ between fiber and metal (F/M)s) it is 0.202, the coefficient of kinetic friction (μd) it is 0.330, the oil of preparation Agent is configured to the emulsion that concentration is 19wt% when in use, with water；
(3) by modified poly ester through measuring, extruding, cooling down, oiling, stretching, thermal finalization and winding be made superfine denier polyester and lead Silk is stretched, the spinning technology parameter of wherein superfine denier polyester drafting silk is as follows：Spinning temperature：288℃；Cooling temperature：21℃；Net Network pressure：0.23MPa；One roller speed：3120m/min；One roll temperature：89℃；Two roller speeds：3920m/min；Two roll temperatures： 122℃；The speed of winding：3830m/min；The initial pressure of filament spinning component is 120bar, and it is 0.58bar/ days that pressure, which rises Δ P,.
The filament number of final obtained superfine denier polyester drafting silk is 0.21dtex, fiber number 55dtex, fracture strength For 3.6cN/dtex, elongation at break 37.0%, fracture strength CV values are 4.0%, and extension at break CV values are 10.0%, boiling Water shrinking percentage is 8.0%, oil content 0.8%, and the lousiness of a spinning cake is 1.
Embodiment 5
A kind of preparation method of superfine denier polyester drafting silk, step are as follows：
(1) preparation of modified poly ester；
(a) 4,4- diethyl -1,7- heptandiols are prepared；At 95 DEG C, under nitrogen atmosphere, by 4,4- diethyl-butyraldehyde, third Aldehyde and triethylamine react 20min, then adding concentrate has in the hydrogenation reactor of thunder girl's Raney nickel, in 2.914MPa Hydrogen press and 100 DEG C at react, reaction finish, cooling, separate out catalyst, solution spent ion exchange resin processing after, decompression steam Water, separates, and purification, obtains 4,4- diethyl -1,7- heptandiols, the structural formula of wherein 44- diethyl -17- heptandiols is as follows：
(b) esterification；It is 1 by molar ratio:1.6:0.03 terephthalic acid (TPA), ethylene glycol and 4,4- diethyl -1,7- Heptandiol is made into slurry, adds antimony glycol, titanium dioxide and trimethyl phosphate after mixing, pressurizes in nitrogen atmosphere Esterification is carried out, moulding pressure is normal pressure, and the temperature of esterification is 257 DEG C, when the water quantity of distillate in esterification reaches Theoretical value 92% when be esterification terminal, wherein the addition of antimony glycol be terephthalic acid (TPA) weight 0.05%, two The addition of titanium oxide is the 0.20% of terephthalic acid (TPA) weight, and the addition of trimethyl phosphate is terephthalic acid (TPA) weight 0.04%；
(c) polycondensation reaction；After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, It is 450Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 33min, and reaction temperature is 270 DEG C, reaction time 30min, Then proceed to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, it is 95Pa reaction pressure is further reduced to absolute pressure, Reaction temperature is 275 DEG C, reaction time 60min, and modified poly ester is made, and the wherein strand of modified poly ester is included to benzene two Formic acid segment, ethylene glycol segment and 4,4- diethyl -1,7- heptandiol segment, the content of cyclic oligomer is in modified poly ester 0.5wt%, number-average molecular weight 25000, molecular weight distributing index 2.1,4,4- diethyl -1,7- heptandiols in modified poly ester The molar content of segment is the 5% of terephthalic acid (TPA) segment molar content；
(2) preparation to oil with finish；
By 15- crown ethers -5 and isomerous tridecanol polyoxyethylene ether phosphate kalium salt, trimethylolpropane laurate and ten Dialkyl sulfonates are added in 13# mineral oil and obtain finish in 52 DEG C of uniform stirring 2h after mixing at normal temperatures, press Parts by weight meter, the addition of each component are as follows：13# mineral oil is 10 parts；Trimethylolpropane laurate is 5 parts；15- Crown ether -5 is 70 parts；Isomerous tridecanol polyoxyethylene ether phosphate kalium salt is 8 parts；Dodecyl sodium sulfate is 6 parts.Prepare Finish in the content of crown ether be 70.70wt%, the resistance to elevated temperatures of finish is excellent, heats thermal weight loss after 2h at 200 DEG C For 13.5wt%；The viscosity of finish is relatively low, at (50 ± 0.01) DEG C, kinematic viscosity 28.6mm2/ s, is configured to dense with water The kinematic viscosity spent after the lotion for 10wt% is 0.95mm2/ s, the film strength of finish is higher, is 126N, the surface of finish Tension force is 24.9cN/cm, and ratio resistance is 1.2 × 108Ω·cm；After oiling, the static friction system between fiber and fiber (F/F) Number (μs) it is 0.251, the coefficient of kinetic friction (μd) it is 0.262；After oiling, the confficient of static friction between fiber and metal (F/M) (μs) it is 0.202, the coefficient of kinetic friction (μd) it is 0.332, when in use, it is 11wt%'s to be configured to concentration with water to the finish of preparation Emulsion；
(3) by modified poly ester through measuring, extruding, cooling down, oiling, stretching, thermal finalization and winding be made superfine denier polyester and lead Silk is stretched, the spinning technology parameter of wherein superfine denier polyester drafting silk is as follows：Spinning temperature：290℃；Cooling temperature：21℃；Net Network pressure：0.24MPa；One roller speed：3140m/min；One roll temperature：90℃；Two roller speeds：3960m/min；Two roll temperatures： 122℃；The speed of winding：3880m/min；The initial pressure of filament spinning component is 120bar, and it is 0.57bar/ days that pressure, which rises Δ P,.
The filament number of final obtained superfine denier polyester drafting silk is 0.24dtex, fiber number 58dtex, fracture strength For 4.8cN/dtex, elongation at break 37.0%, fracture strength CV values are 4.8%, and extension at break CV values are 9.5%, boiling water Shrinking percentage is 7.5%, oil content 0.90%, and the lousiness of a spinning cake is 1.
Embodiment 6
A kind of preparation method of superfine denier polyester drafting silk, step are as follows：
(1) preparation of modified poly ester；
(a) 4,4- bis- (1,-Methylethyl) -1,7- heptandiols are prepared；At 92 DEG C, under nitrogen atmosphere, by 4,4-, bis- (1- Methylethyl)-butyraldehyde, propionic aldehyde and triethylamine react 20min, then adding concentrate has the hydrogenation of thunder girl's Raney nickel anti- Answer in device, reacted at 2.914MPa hydrogen pressure and 100 DEG C, reaction is finished, and cooling, separates out catalyst.Solution amberlite After fat processing, water is steamed in decompression, separates, and purification, obtains 4,4- bis- (1,-Methylethyl) -1,7- heptandiols, wherein 4,4- bis- The structural formula of (1,-Methylethyl) -1,7- heptandiols is as follows：
(b) esterification；It is 1 by molar ratio:1.7:0.05 terephthalic acid (TPA), ethylene glycol and 4,4- bis- (1 ,-methyl Ethyl) -1,7- heptandiols are made into slurry, antimony acetate, titanium dioxide and Trimethyl phosphite are added after mixing, in nitrogen Pressurization carries out esterification in atmosphere, and moulding pressure 0.2MPa, the temperature of esterification is 253 DEG C, when in esterification Water quantity of distillate is esterification terminal when reaching the 96% of theoretical value, and wherein the addition of antimony acetate is terephthalic acid (TPA) weight 0.01%, the addition of titanium dioxide is the 0.20% of terephthalic acid (TPA) weight, and the addition of Trimethyl phosphite is to benzene The 0.05% of dioctyl phthalate weight；
(c) polycondensation reaction；After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, It is 480Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 38min, and reaction temperature is 262 DEG C, reaction time 38min, Then proceed to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, it is 98Pa reaction pressure is further reduced to absolute pressure, Reaction temperature is 279 DEG C, reaction time 80min, and modified poly ester is made, and the wherein strand of modified poly ester is included to benzene two Formic acid segment, ethylene glycol segment and 4,4- bis- (1,-Methylethyl) -1,7- heptandiol segments, cyclic oligomer in modified poly ester Content be 0.55wt%, number-average molecular weight 27000, molecular weight distributing index 2.2,4,4- bis- in modified poly ester (1 ,-first Base ethyl) -1,7- heptandiol segments molar content be terephthalic acid (TPA) segment molar content 4%；
(2) preparation to oil with finish；
By 2- methylol -15- crown-s 5 and ten tetracosanol phosphate kalium salts, trimethylolpropane laurate and 15 Sodium alkyl sulfonate is added in 14# mineral oil and obtains finish in 55 DEG C of uniform stirring 1h after mixing at normal temperatures, by weight Number meter is measured, the addition of each component is as follows：14# mineral oil is 3 parts；Trimethylolpropane laurate is 10 parts；2- hydroxyl first Base -15- crown-s 5 are 75 parts；Ten tetracosanol phosphate kalium salts are 14 parts；Pentadecyl sulfonic acid sodium is 7 parts.The finish prepared The content of middle crown ether is 68.80wt%, and the resistance to elevated temperatures of finish is excellent, and thermal weight loss is after heating 2h at 200 DEG C 12wt%；The viscosity of finish is relatively low, at (50 ± 0.01) DEG C, kinematic viscosity 27.5mm2/ s, being configured to concentration with water is Kinematic viscosity after the lotion of 10wt% is 0.95mm2/ s, the film strength of finish is higher, is 126N, the surface tension of finish For 25.4cN/cm, ratio resistance is 1.6 × 108Ω·cm；After oiling, the confficient of static friction between fiber and fiber (F/F) (μs) it is 0.255, the coefficient of kinetic friction (μd) it is 0.267；After oiling, the confficient of static friction (μ between fiber and metal (F/M)s) For 0.203, the coefficient of kinetic friction (μd) it is 0.330, the finish of preparation is configured to the breast that concentration is 20wt% when in use, with water Change liquid；
(3) by modified poly ester through measuring, extruding, cooling down, oiling, stretching, thermal finalization and winding be made superfine denier polyester and lead Silk is stretched, the spinning technology parameter of wherein superfine denier polyester drafting silk is as follows：Spinning temperature：290℃；Cooling temperature：23℃；Net Network pressure：0.25MPa；One roller speed：3150m/min；One roll temperature：91℃；Two roller speeds：3960m/min；Two roll temperatures： 125℃；The speed of winding：3900m/min；The initial pressure of filament spinning component is 120bar, and it is 0.57bar/ days that pressure, which rises Δ P,.
The filament number of final obtained superfine denier polyester drafting silk is 0.26dtex, fiber number 58dtex, fracture strength For 3.7cN/dtex, elongation at break 40.0%, fracture strength CV values are 4.6%, and extension at break CV values are 9.9%, boiling water Shrinking percentage is 7.6%, oil content 0.95%, and the lousiness of a spinning cake is 1.
Embodiment 7
A kind of preparation method of superfine denier polyester drafting silk, step are as follows：
(1) preparation of modified poly ester；
(a) 3,3- dipropyl -1,5- pentanediols are prepared；At 93 DEG C, under nitrogen atmosphere, by 3,3- dipropyl-propionic aldehyde, second Aldehyde and triethylamine react 20min, then adding concentrate has in the hydrogenation reactor of thunder girl's Raney nickel, in 2.914MPa Hydrogen press and 100 DEG C at react, reaction finish, cooling, separate out catalyst.After the processing of solution spent ion exchange resin, decompression is steamed Water, separates, and purification, obtains 3,3- dipropyl -1,5-PD, wherein the structural formula of 3,3- dipropyl -1,5-PD is such as Under：
(b) esterification；It is 1 by molar ratio:1.8:0.03 terephthalic acid (TPA), ethylene glycol and 3,3- dipropyl -1,5- Pentanediol is made into slurry, adds antimony oxide, titanium dioxide and triphenyl phosphate after mixing, adds in nitrogen atmosphere Pressure carries out esterification, and moulding pressure 0.3MPa, the temperature of esterification is 250 DEG C, when the water quantity of distillate in esterification It is esterification terminal when reaching the 90% of theoretical value, wherein the addition of antimony oxide is terephthalic acid (TPA) weight 0.03%, the addition of titanium dioxide is the 0.24% of terephthalic acid (TPA) weight, and the addition of triphenyl phosphate is terephthaldehyde The 0.02% of sour weight；
(c) polycondensation reaction；After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, It is 455Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 42min, and reaction temperature is 264 DEG C, reaction time 45min, Then proceed to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, it is 85Pa reaction pressure is further reduced to absolute pressure, Reaction temperature is 285 DEG C, reaction time 75min, and modified poly ester is made, and the wherein strand of modified poly ester is included to benzene two Formic acid segment, ethylene glycol segment and 3,3- dipropyl -1,5-PD segment, the content of cyclic oligomer is in modified poly ester 0.45wt%, number-average molecular weight 26500, molecular weight distributing index 2.2,3,3- dipropyl -1,5-PD in modified poly ester The molar content of segment is the 4.5% of terephthalic acid (TPA) segment molar content；
(2) preparation to oil with finish；
By 15- crown ethers -5 and 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, trimethylolpropane laurate and sodium cetanesulfonate It is added to after mixing at normal temperatures in 15# mineral oil and obtains finish in 41 DEG C of uniform stirring 2h, counts in parts by weight, The addition of each component is as follows：15# mineral oil is 8 parts；Trimethylolpropane laurate is 20 parts；15- crown ethers -5 are 100 Part；1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite is 15 parts；Sodium cetanesulfonate is 2 parts.The content of crown ether is in the finish prepared 68.97wt%, the resistance to elevated temperatures of finish is excellent, and thermal weight loss is 8.5wt% after heating 2h at 200 DEG C；The viscosity of finish It is relatively low, at (50 ± 0.01) DEG C, kinematic viscosity 28.4mm2/ s, the fortune being configured to water after the lotion that concentration is 10wt% Kinetic viscosity is 0.94mm2/ s, the film strength of finish is higher, is 122N, the surface tension of finish is 26.8cN/cm, than electricity Hinder for 1.8 × 108Ω·cm；After oiling, the confficient of static friction (μ between fiber and fiber (F/F)s) it is 0.263, dynamic friction system Number (μd) it is 0.268；After oiling, the confficient of static friction (μ between fiber and metal (F/M)s) it is 0.210, the coefficient of kinetic friction (μd) it is 0.320, the finish of preparation is configured to the emulsion that concentration is 13wt% when in use, with water；
(3) by modified poly ester through measuring, extruding, cooling down, oiling, stretching, thermal finalization and winding be made superfine denier polyester and lead Silk is stretched, the spinning technology parameter of wherein superfine denier polyester drafting silk is as follows：Spinning temperature：292℃；Cooling temperature：23℃；Net Network pressure：0.26MPa；One roller speed：3170m/min；One roll temperature：91℃；Two roller speeds：4050m/min；Two roll temperatures： 127℃；The speed of winding：3920m/min；The initial pressure of filament spinning component is 120bar, and it is 0.55bar/ days that pressure, which rises Δ P,.
The filament number of final obtained superfine denier polyester drafting silk is 0.26dtex, fiber number 62dtex, fracture strength For 3.9cN/dtex, elongation at break 40.0%, fracture strength CV values are 5.0%, and extension at break CV values are 10.0%, boiling Water shrinking percentage is 7.5%, oil content 1.0%, and the lousiness of a spinning cake is 1.
Embodiment 8
A kind of preparation method of superfine denier polyester drafting silk, step are as follows：
(1) preparation of modified poly ester；
(a) 4,4- dipropyl -1,7- heptandiols are prepared；At 92.5 DEG C, under nitrogen atmosphere, by 4,4- dipropyl-butyraldehyde, Acetaldehyde and triethylamine react 20min, then adding concentrate has in the hydrogenation reactor of thunder girl's Raney nickel, 2.914MPa hydrogen press and 100 DEG C at react, reaction finish, cooling, separate out catalyst.After the processing of solution spent ion exchange resin, Water is steamed in decompression, separates, and purification, obtains 4,4- dipropyl -1,7- heptandiols, wherein the structure of 4,4- dipropyl -1,7- heptandiols Formula is as follows：
(b) esterification；It is 1 by molar ratio:1.9:0.04 terephthalic acid (TPA), ethylene glycol and 4,4- dipropyl -1,7- Heptandiol is made into slurry, adds antimony glycol, titanium dioxide and trimethyl phosphate after mixing, pressurizes in nitrogen atmosphere Esterification is carried out, moulding pressure 0.3MPa, the temperature of esterification is 260 DEG C, when the water quantity of distillate in esterification reaches To theoretical value 93% when be esterification terminal, wherein the addition of antimony glycol be terephthalic acid (TPA) weight 0.04%, The addition of titanium dioxide is the 0.21% of terephthalic acid (TPA) weight, and the addition of trimethyl phosphate is terephthalic acid (TPA) weight 0.03%；
(c) polycondensation reaction；After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, It is 475Pa that pressure is steadily evacuated to absolute pressure by 0.3MPa in 45min, and reaction temperature is 265 DEG C, and the reaction time is 48min, then proceedes to vacuumize, and carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is further reduced to absolute pressure and is 88Pa, reaction temperature be 283 DEG C, reaction time 80min, be made modified poly ester, wherein the strand of modified poly ester include pair Phthalic acid segment, ethylene glycol segment and 4,4- dipropyl -1,7- heptandiol segment, cyclic oligomer contains in modified poly ester Measure as 0.6wt%, number-average molecular weight 23000, molecular weight distributing index 2.0,4,4- dipropyl -1,7- heptan in modified poly ester The molar content of glycol segment is the 3% of terephthalic acid (TPA) segment molar content；
(2) preparation to oil with finish；
By 2- methylols -12-crown-4 and ten tetracosanol phosphate kalium salts, trimethylolpropane laurate and 15 Sodium alkyl sulfonate is added in 16# mineral oil and obtains finish in 45 DEG C of uniform stirring 3h after mixing at normal temperatures, by weight Number meter is measured, the addition of each component is as follows：16# mineral oil is 9 parts；2- methylol -12- crown-s 4 are 80 parts；Ten tetracosanols Phosphate kalium salt is 12 parts；Pentadecyl sulfonic acid sodium is 5 parts.The content of crown ether is 83.33wt% in the finish prepared, oil The resistance to elevated temperatures of agent is excellent, and thermal weight loss is 14wt% after heating 2h at 200 DEG C；The viscosity of finish is relatively low, (50 ± DEG C 0.01) when, kinematic viscosity 30.0mm2/ s, the kinematic viscosity after the lotion that concentration is 10wt% is configured to water is 0.93mm2/ s, the film strength of finish is higher, is 127N, and the surface tension of finish is 23.5cN/cm, ratio resistance for 1.5 × 108Ω·cm；After oiling, the confficient of static friction (μ between fiber and fiber (F/F)s) it is 0.262, the coefficient of kinetic friction (μd) be 0.273；After oiling, the confficient of static friction (μ between fiber and metal (F/M)s) it is 0.208, the coefficient of kinetic friction (μd) be 0.328, the finish of preparation is configured to the emulsion that concentration is 18wt% when in use, with water；
(3) by modified poly ester through measuring, extruding, cooling down, oiling, stretching, thermal finalization and winding be made superfine denier polyester and lead Silk is stretched, the spinning technology parameter of wherein superfine denier polyester drafting silk is as follows：Spinning temperature：292℃；Cooling temperature：23℃；Net Network pressure：0.27MPa；One roller speed：3180m/min；One roll temperature：92℃；Two roller speeds：4060m/min；Two roll temperatures： 128℃；The speed of winding：3900m/min；The initial pressure of filament spinning component is 120bar, and it is 0.56bar/ days that pressure, which rises Δ P,.
The filament number of final obtained superfine denier polyester drafting silk is 0.28dtex, fiber number 68dtex, fracture strength For 3.6cN/dtex, elongation at break 37.0%, fracture strength CV values are 4.0%, and extension at break CV values are 9.6%, boiling water Shrinking percentage is 8.0%, oil content 1.05%, and the lousiness of a spinning cake is 1.
Embodiment 9
A kind of preparation method of superfine denier polyester drafting silk, step are as follows：
(1) preparation of modified poly ester；
(a) 4- methyl -4- (1,1- dimethyl ethyls) -1,7- heptandiols are prepared；At 91 DEG C, under nitrogen atmosphere, by 4- first Base -4- (1,1- dimethyl ethyl)-butyraldehyde, propionic aldehyde and triethylamine react 20min, then adding concentrate has thunder girl's nickel to urge In the hydrogenation reactor of agent, reacted at 2.914MPa hydrogen pressure and 100 DEG C, reaction is finished, and cooling, separates out catalyst, solution After spent ion exchange resin processing, water is steamed in decompression, separates, and purification, obtains 4- methyl -4- (1,1- dimethyl ethyl) -1,7- heptan The structural formula of glycol, wherein 4- methyl -4- (1,1- dimethyl ethyl) -1,7- heptandiols is as follows：
(b) esterification；It is 1 by molar ratio:2.0:0.05 terephthalic acid (TPA), ethylene glycol and 4- methyl -4- (1,1- Dimethyl ethyl) -1,7- heptandiols are made into slurry, add antimony acetate, titanium dioxide and trimethyl phosphate after mixing, Pressurization carries out esterification in nitrogen atmosphere, and moulding pressure is normal pressure, and the temperature of esterification is 251 DEG C, when in esterification Water quantity of distillate be esterification terminal when reaching the 96% of theoretical value, wherein the addition of antimony acetate is terephthalic acid (TPA) weight The 0.05% of amount, the addition of titanium dioxide are the 0.22% of terephthalic acid (TPA) weight, and the addition of trimethyl phosphate is to benzene The 0.04% of dioctyl phthalate weight；
(c) polycondensation reaction；After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, It is 420Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 30min, and reaction temperature is 267 DEG C, reaction time 50min, Then proceed to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, it is 80Pa reaction pressure is further reduced to absolute pressure, Reaction temperature is 280 DEG C, reaction time 90min, and modified poly ester is made, and the wherein strand of modified poly ester is included to benzene two Formic acid segment, ethylene glycol segment and 4- methyl -4- (1,1- dimethyl ethyl) -1,7- heptandiol segments, ring-type in modified poly ester The content of oligomer is 0.25wt%, number-average molecular weight 24000, molecular weight distributing index 2.2,4- methyl in modified poly ester- The molar content of 4- (1,1- dimethyl ethyls) -1,7- heptandiol segments is the 4% of terephthalic acid (TPA) segment molar content；
(2) preparation to oil with finish；
By 2- methylol -15- crown-s 5 and 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, trimethylolpropane laurate and dodecane Base sodium sulfonate after mixing and obtains finish in 55 DEG C of uniform stirring 3h at normal temperatures, counts in parts by weight, and each component adds It is as follows to enter amount：Trimethylolpropane laurate is 15 parts；2- methylol -15- crown-s 5 are 90 parts；1-isobutyl-3,5-dimethylhexylphosphoric acid potassium Salt is 8 parts；Dodecyl sodium sulfate is 7 parts.The content of crown ether is 81.81wt% in the finish prepared, the high temperature resistant of finish Function admirable, thermal weight loss is 10wt% after heating 2h at 200 DEG C；The viscosity of finish is relatively low, at (50 ± 0.01) DEG C, Kinematic viscosity is 29.7mm2/ s, the kinematic viscosity being configured to water after the lotion that concentration is 10wt% is 0.94mm2/ s, finish Film strength it is higher, be 126N, the surface tension of finish is 24.8cN/cm, and ratio resistance is 1.8 × 108Ω·cm；Oil Afterwards, the confficient of static friction (μ between fiber and fiber (F/F)s) it is 0.250, the coefficient of kinetic friction (μd) it is 0.264；It is fine after oiling Confficient of static friction (μ between dimension and metal (F/M)s) it is 0.210, the coefficient of kinetic friction (μd) it is 0.321, the finish of preparation exists In use, it is configured to the emulsion that concentration is 10wt% with water；
(3) by modified poly ester through measuring, extruding, cooling down, oiling, stretching, thermal finalization and winding be made superfine denier polyester and lead Silk is stretched, the spinning technology parameter of wherein superfine denier polyester drafting silk is as follows：Spinning temperature：294℃；Cooling temperature：24℃；Net Network pressure：0.29MPa；One roller speed：3190m/min；One roll temperature：92℃；Two roller speeds：4060m/min；Two roll temperatures： 129℃；The speed of winding：3960m/min；The initial pressure of filament spinning component is 120bar, and it is 0.56bar/ days that pressure, which rises Δ P,.
The filament number of final obtained superfine denier polyester drafting silk is 0.28dtex, fiber number 72dtex, fracture strength For 4.0cN/dtex, elongation at break 43.0%, fracture strength CV values are 4.7%, and extension at break CV values are 9.1%, boiling water Shrinking percentage is 7.0%, oil content 1.06%, and the lousiness of a spinning cake is 1.
Embodiment 10
A kind of preparation method of superfine denier polyester drafting silk, step are as follows：
(1) preparation of modified poly ester；
(a) 3- methyl -3- amyl groups -1,6-HD is prepared；At 94 DEG C, under nitrogen atmosphere, by 3- methyl -3- amyl groups-the third Aldehyde, propionic aldehyde and triethylamine react 20min, then adding concentrate has in the hydrogenation reactor of thunder girl's Raney nickel, 2.914MPa hydrogen press and 100 DEG C at react, reaction finish, cooling, separate out catalyst.After the processing of solution spent ion exchange resin, Water is steamed in decompression, separates, and purification, obtains 3- methyl -3- amyl group -1,6- hexylene glycols, wherein 3- methyl -3- amyl group -1,6- hexylene glycols Structural formula it is as follows：
(b) esterification；It is 1 by molar ratio:1.2:0.06 terephthalic acid (TPA), ethylene glycol and 3- methyl -3- amyl groups - 1,6- hexylene glycol is made into slurry, antimony glycol, titanium dioxide and Trimethyl phosphite is added after mixing, in nitrogen atmosphere Middle pressurization carries out esterification, and moulding pressure 0.1MPa, the temperature of esterification is 255 DEG C, when the water in esterification evaporates Output is esterification terminal when reaching the 92% of theoretical value, and wherein the addition of antimony glycol is terephthalic acid (TPA) weight 0.01%, the addition of titanium dioxide is the 0.20% of terephthalic acid (TPA) weight, and the addition of Trimethyl phosphite is to benzene two The 0.01% of formic acid weight；
(c) polycondensation reaction；After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, It is 490Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 50min, and reaction temperature is 269 DEG C, reaction time 30min, Then proceed to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, it is 100Pa reaction pressure is further reduced to absolute pressure, Reaction temperature is 281 DEG C, reaction time 55min, and modified poly ester is made, and the wherein strand of modified poly ester is included to benzene two Formic acid segment, ethylene glycol segment and 3- methyl -3- amyl group -1,6- hexylene glycol segments, the content of cyclic oligomer in modified poly ester For 0.1wt%, number-average molecular weight 20000, molecular weight distributing index 1.9, in modified poly ester 3- methyl -3- amyl groups -1,6- oneself The molar content of glycol segment is the 3.5% of terephthalic acid (TPA) segment molar content；
(2) preparation to oil with finish；
By 2- methylols -12-crown-4 and 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, trimethylolpropane laurate and dodecane Base sodium sulfonate is added in 9# mineral oil and obtains finish in 40 DEG C of uniform stirring 1h after mixing at normal temperatures, by weight Number meter, the addition of each component are as follows：9# mineral oil is 2 parts；Trimethylolpropane laurate is 10 parts；2- methylols- 12-crown-4 is 90 parts；1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite is 8 parts；Dodecyl sodium sulfate is 3 parts；Crown ether in the finish prepared Content be 79.6wt%, the resistance to elevated temperatures of finish is excellent, 200 DEG C heat 2h after thermal weight loss be 14.5wt%；Oil The viscosity of agent is relatively low, at (50 ± 0.01) DEG C, kinematic viscosity 29.6mm2/ s, the breast that concentration is 10wt% is configured to water Kinematic viscosity after liquid is 0.93mm2/ s, the film strength of finish is higher, film strength 125N, and the surface tension of finish is 24.8cN/cm, ratio resistance are 1.3 × 108Ω·cm；After oiling, the confficient of static friction (μ between fiber and fiber (F/F)s) be 0.255, the coefficient of kinetic friction (μd) it is 0.266；After oiling, the confficient of static friction (μ between fiber and metal (F/M)s) be 0.203, the coefficient of kinetic friction (μd) it is 0.320, the finish of preparation is configured to the emulsification that concentration is 15wt% when in use, with water Liquid；
(3) by modified poly ester through measuring, extruding, cooling down, oiling, stretching, thermal finalization and winding be made superfine denier polyester and lead Silk is stretched, the spinning technology parameter of wherein superfine denier polyester drafting silk is as follows：Spinning temperature：294℃；Cooling temperature：24℃；Net Network pressure：0.26MPa；One roller speed：3180m/min；One roll temperature：93℃；Two roller speeds：4100m/min；Two roll temperatures： 130℃；The speed of winding：4000m/min；The initial pressure of filament spinning component is 120bar, and it is 0.6bar/ days that pressure, which rises Δ P,.
The filament number of final obtained superfine denier polyester drafting silk is 0.3dtex, fiber number 50dtex, fracture strength For 4.4cN/dtex, elongation at break 38.0%, fracture strength CV values are 4.6%, and extension at break CV values are 9.5%, boiling water Shrinking percentage is 7.1%, oil content 1.08%, and the lousiness of a spinning cake is 0.
Embodiment 11
A kind of preparation method of superfine denier polyester drafting silk, step are as follows：
(1) preparation of modified poly ester；
(a) 3,3- diamyl -1,5- pentanediols are prepared；At 95 DEG C, under nitrogen atmosphere, by 3,3- diamyl-propionic aldehyde, second Aldehyde and triethylamine react 20min, then adding concentrate has in the hydrogenation reactor of thunder girl's Raney nickel, in 2.914MPa Hydrogen press and 100 DEG C at react, reaction finish, cooling, separate out catalyst.After the processing of solution spent ion exchange resin, decompression is steamed Water, separates, and purification, obtains 3,3- diamyl -1,5-PD, wherein the structural formula of 3,3- diamyl -1,5-PD is such as Under：
(b) esterification；It is 1 by molar ratio:2.0:0.03 terephthalic acid (TPA), ethylene glycol and 3,3- diamyl -1,5- Pentanediol is made into slurry, adds antimony acetate, titanium dioxide and Trimethyl phosphite after mixing, pressurizes in nitrogen atmosphere Esterification is carried out, moulding pressure 0.2MPa, the temperature of esterification is 250 DEG C, when the water quantity of distillate in esterification reaches To theoretical value 97% when be esterification terminal, wherein the addition of antimony acetate be terephthalic acid (TPA) weight 0.01%, two The addition of titanium oxide is the 0.23% of terephthalic acid (TPA) weight, and the addition of Trimethyl phosphite is terephthalic acid (TPA) weight 0.05%；
(c) polycondensation reaction；After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, It is 500Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 45min, and reaction temperature is 260 DEG C, reaction time 40min, Then proceed to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, it is 92Pa reaction pressure is further reduced to absolute pressure, Reaction temperature is 277 DEG C, reaction time 80min, and modified poly ester is made, and the wherein strand of modified poly ester is included to benzene two Formic acid segment, ethylene glycol segment and 3,3- diamyl -1,5-PD segment, the content of cyclic oligomer is in modified poly ester 0.35wt%, number-average molecular weight 25500, molecular weight distributing index 1.8,3,3- diamyl -1,5-PD in modified poly ester The molar content of segment is the 5% of terephthalic acid (TPA) segment molar content；
(2) preparation to oil with finish；
By 2- methylols -12-crown-4 and 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, trimethylolpropane laurate and hexadecane Base sodium sulfonate is added in 12# mineral oil and obtains finish in 40 DEG C of uniform stirring 2.5h after mixing at normal temperatures, by weight Number meter is measured, the addition of each component is as follows：12# mineral oil is 5 parts；2- methylol -12- crown-s 4 are 95 parts；Dodecyl phosphorus Acid esters sylvite is 9 parts；Sodium cetanesulfonate is 2 parts.The content of crown ether is 85.58wt% in the finish prepared, finish Resistance to elevated temperatures is excellent, and thermal weight loss is 9wt% after heating 2h at 200 DEG C；The viscosity of finish is relatively low, in (50 ± 0.01) DEG C when, kinematic viscosity 29.5mm2/ s, the kinematic viscosity being configured to water after the lotion that concentration is 10wt% is 0.93mm2/ s, The film strength of finish is higher, is 121N, the surface tension of finish is 24.3cN/cm, and ratio resistance is 1.0 × 108Ω·cm； After oiling, the confficient of static friction (μ between fiber and fiber (F/F)s) it is 0.260, the coefficient of kinetic friction (μd) it is 0.263；Oil Afterwards, the confficient of static friction (μ between fiber and metal (F/M)s) it is 0.202, the coefficient of kinetic friction (μd) it is 0.330, the oil of preparation Agent is configured to the emulsion that concentration is 19wt% when in use, with water；
(3) by modified poly ester through measuring, extruding, cooling down, oiling, stretching, thermal finalization and winding be made superfine denier polyester and lead Silk is stretched, the spinning technology parameter of wherein superfine denier polyester drafting silk is as follows：Spinning temperature：287℃；Cooling temperature：24℃；Net Network pressure：0.30MPa；One roller speed：3150m/min；One roll temperature：93℃；Two roller speeds：4100m/min；Two roll temperatures： 130℃；The speed of winding：4000m/min；The initial pressure of filament spinning component is 120bar, and it is 0.57bar/ days that pressure, which rises Δ P,.
The filament number of final obtained superfine denier polyester drafting silk is 0.29dtex, fiber number 74dtex, fracture strength For 4.5cN/dtex, elongation at break 43.0%, fracture strength CV values are 5.0%, and extension at break CV values are 9.5%, boiling water Shrinking percentage is 8.0%, oil content 1.09%, and the lousiness of a spinning cake is 0.

Claims (10)

1. superfine denier polyester drafting silk, it is characterized in that：The material of superfine denier polyester drafting silk is modified poly ester；
The strand of modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment and branched dihydric alcohol segment, band side chain Dihydric alcohol structural formula it is as follows：
In formula, R1And R2It is each independently selected from the straight-chain alkyl-sub that carbon number is 1~3, R3It is 1~5 selected from carbon number Alkyl, R4Selected from the alkyl that carbon number is 2~5；
The filament number of superfine denier polyester drafting silk is 0.2~0.3dtex.
2. superfine denier polyester drafting silk according to claim 1, it is characterised in that the fibre of the superfine denier polyester drafting silk It is 40.0 ± 3.0% to spend for 50~75dtex, fracture strength >=3.6cN/dtex, elongation at break, fracture strength CV values≤ 5.0%, extension at break CV value≤10.0%, boiling water shrinkage is 7.5 ± 0.5%, and oil content is 0.90 ± 0.20%, a silk Lousiness≤2 of cake.
3. superfine denier polyester drafting silk according to claim 1 or 2, it is characterised in that ring-type is low in the modified poly ester Content≤0.6wt% of polymers；
The number-average molecular weight 20000~27000 of the modified poly ester, molecular weight distributing index are 1.8~2.2；
In the modified poly ester molar content of branched dihydric alcohol segment for terephthalic acid (TPA) segment molar content 3~ 5%.
4. superfine denier polyester drafting silk according to claim 3, it is characterised in that the branched dihydric alcohol is 2- second Base -2- methyl-1,3-propanediols, 2,2- diethyl -1,3- propane diols, 2-butyl-2-ethyl-1,3-propanediol, 3,3- diethyls Base -1,5- pentanediols, 4,4- diethyl -1,7- heptandiols, 4,4- bis- (1,-Methylethyl) -1,7- heptandiols, 3,3- dipropyls Base -1,5- pentanediols, 4,4- dipropyl -1,7- heptandiols, 4- methyl -4- (1,1- dimethyl ethyls) -1,7- heptandiols, 3- first Base -3- amyl groups -1,6-HD or 3,3- diamyl -1,5- pentanediols.
5. superfine denier polyester drafting silk according to claim 4, it is characterised in that the preparation method of the modified poly ester For：Terephthalic acid (TPA), ethylene glycol and the branched dihydric alcohol are successively subjected to esterification after mixing and polycondensation is anti- It should obtain modified poly ester；Comprise the following steps that：
(1) esterification；
Terephthalic acid (TPA), ethylene glycol and the branched dihydric alcohol are made into slurry, add catalyst, delustering agent and stabilizer After mixing, pressurization carries out esterification in nitrogen atmosphere, and moulding pressure is normal pressure~0.3MPa, the temperature of esterification It is esterification terminal when the water quantity of distillate in esterification reaches more than the 90% of theoretical value for 250~260 DEG C；
(2) polycondensation reaction；
After esterification, start the polycondensation reaction in low vacuum stage under condition of negative pressure, the staged pressure is in 30~50min Interior to be steadily evacuated to by normal pressure below absolute pressure 500Pa, reaction temperature is 260~270 DEG C, and the reaction time is 30~50min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is further reduced to below absolute pressure 100Pa, Reaction temperature is 275~285 DEG C, and the reaction time is 50~90min, and modified poly ester is made.
6. superfine denier polyester drafting silk according to claim 5, it is characterised in that in step (1), terephthalic acid (TPA), second The molar ratio of glycol and the branched dihydric alcohol is 1:1.2~2.0:0.03~0.06, the addition of the catalyst is The 0.01~0.05% of terephthalic acid (TPA) weight, the addition of the delustering agent for terephthalic acid (TPA) weight 0.20~ 0.25%, the addition of the stabilizer is the 0.01~0.05% of terephthalic acid (TPA) weight；
The catalyst is antimony oxide, antimony glycol or antimony acetate, and the delustering agent is titanium dioxide, and the stabilizer is Triphenyl phosphate, trimethyl phosphate or Trimethyl phosphite.
7. the method such as claim 1~6 any one of them superfine denier polyester drafting silk is prepared, it is characterized in that：Change described Property polyester through measuring, extruding, cooling down, oiling, stretching, thermal finalization and winding superfine denier polyester drafting silk is made；
Contain crown ether in the finish to oil, and the content of crown ether is 67.30~85.58wt%.
8. the method according to the description of claim 7 is characterized in that thermal weight loss is small after the finish heats 2h at 200 DEG C In 15wt%；
For the finish at (50 ± 0.01) DEG C, kinematic viscosity is 27.5~30.1mm2/ s, the finish are configured to concentration with water It is 0.93~0.95mm for the kinematic viscosity after the lotion of 10wt%2/s；
The film strength of the finish is 121~127N；
The surface tension of the finish is 23.2~26.8cN/cm, and ratio resistance is 1.0 × 108~1.8 × 108Ω·cm；
After oiling, the confficient of static friction between fiber and fiber is 0.250~0.263, and the coefficient of kinetic friction is 0.262~0.273；
After oiling, the confficient of static friction between fiber and metal is 0.202~0.210, and the coefficient of kinetic friction is 0.320~0.332.
9. according to the method described in claim 8, it is characterized in that, the crown ether is 2- methylols -12-crown-4,15- crown ethers -5 Or 2- methylol -15- crown-s 5；
Also contain mineral oil, phosphate kalium salt, trimethylolpropane laurate and sodium alkyl sulfonate in the finish；
The mineral oil is one kind in the mineral oil of 9#~17#；
The phosphate kalium salt is 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, isomerous tridecanol polyoxyethylene ether phosphate kalium salt or 12 Tetrol phosphate kalium salt；
The sodium alkyl sulfonate is dodecyl sodium sulfate, pentadecyl sulfonic acid sodium or sodium cetanesulfonate；
The finish is configured to the emulsion that concentration is 10~20wt% when in use, with water；
The preparation method of the finish is：By crown ether and phosphate kalium salt, trimethylolpropane laurate and sodium alkyl sulfonate It is added to after mixing in mineral oil and is uniformly mixing to obtain finish；Count in parts by weight, the addition of each component is as follows：
The mixing carries out at normal temperatures, and the temperature of the stirring is 40~55 DEG C, and the time is 1~3h.
10. according to claim 7~9 any one of them method, it is characterised in that the spinning of the superfine denier polyester drafting silk Technological parameter is as follows：
Spinning temperature：287~295 DEG C；
Cooling temperature：20~25 DEG C；
Network pressure：0.20~0.30MPa；
One roller speed：3100~3200m/min
One roll temperature：88~93 DEG C；
Two roller speeds：3900~4100m/min；
Two roll temperatures：120~130 DEG C；
The speed of winding：3800~4000m/min；
The initial pressure of filament spinning component is 120bar, and pressure rises Δ P≤0.6bar/ days.
CN201711340289.1A 2017-12-14 2017-12-14 Superfine denier polyester drawn yarn and preparation method thereof Active CN108035007B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711340289.1A CN108035007B (en) 2017-12-14 2017-12-14 Superfine denier polyester drawn yarn and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711340289.1A CN108035007B (en) 2017-12-14 2017-12-14 Superfine denier polyester drawn yarn and preparation method thereof

Publications (2)

Publication Number Publication Date
CN108035007A true CN108035007A (en) 2018-05-15
CN108035007B CN108035007B (en) 2020-05-05

Family

ID=62103415

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711340289.1A Active CN108035007B (en) 2017-12-14 2017-12-14 Superfine denier polyester drawn yarn and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108035007B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109666989A (en) * 2018-12-27 2019-04-23 江苏恒力化纤股份有限公司 Superfine denier polyester low stretch yarn and preparation method thereof
CN109735924A (en) * 2018-12-27 2019-05-10 江苏恒力化纤股份有限公司 Superfine denier polyester drafting silk and preparation method thereof
CN112746349A (en) * 2020-12-29 2021-05-04 江苏恒力化纤股份有限公司 High-strength creep-resistant polyester industrial yarn and preparation method thereof
CN114182385A (en) * 2021-12-20 2022-03-15 扬州富威尔复合材料有限公司 Preparation method of fine denier polyester staple fiber
CN117684290A (en) * 2023-11-30 2024-03-12 江苏恒科新材料有限公司 Preparation method of superfine polyester filament yarn for chenille yarn

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101139735A (en) * 2007-08-16 2008-03-12 江苏恒力化纤有限公司 Method for preparing ultra-fine denier polyester filament yarn
CN105002603A (en) * 2015-07-31 2015-10-28 江苏恒科新材料有限公司 Super-fine-denier polyester fiber and manufacturing method thereof
CN105019059A (en) * 2015-07-31 2015-11-04 江苏恒科新材料有限公司 Super-soft superfine polyester fiber and preparation method thereof
CN106400167A (en) * 2016-08-31 2017-02-15 江苏恒力化纤股份有限公司 Porous superfine denier flat yarn and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101139735A (en) * 2007-08-16 2008-03-12 江苏恒力化纤有限公司 Method for preparing ultra-fine denier polyester filament yarn
CN105002603A (en) * 2015-07-31 2015-10-28 江苏恒科新材料有限公司 Super-fine-denier polyester fiber and manufacturing method thereof
CN105019059A (en) * 2015-07-31 2015-11-04 江苏恒科新材料有限公司 Super-soft superfine polyester fiber and preparation method thereof
CN106400167A (en) * 2016-08-31 2017-02-15 江苏恒力化纤股份有限公司 Porous superfine denier flat yarn and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张俊彦等: "一种冠醚化合物作为新型润滑油添加剂的抗磨减摩性能研究", 《摩擦学学报》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109666989A (en) * 2018-12-27 2019-04-23 江苏恒力化纤股份有限公司 Superfine denier polyester low stretch yarn and preparation method thereof
CN109735924A (en) * 2018-12-27 2019-05-10 江苏恒力化纤股份有限公司 Superfine denier polyester drafting silk and preparation method thereof
CN112746349A (en) * 2020-12-29 2021-05-04 江苏恒力化纤股份有限公司 High-strength creep-resistant polyester industrial yarn and preparation method thereof
WO2022142399A1 (en) * 2020-12-29 2022-07-07 江苏恒力化纤股份有限公司 High-strength creep-resistant polyester industrial fiber and preparation method therefor
CN114182385A (en) * 2021-12-20 2022-03-15 扬州富威尔复合材料有限公司 Preparation method of fine denier polyester staple fiber
CN114182385B (en) * 2021-12-20 2023-08-29 扬州富威尔复合材料有限公司 Preparation method of fine denier polyester staple fiber
CN117684290A (en) * 2023-11-30 2024-03-12 江苏恒科新材料有限公司 Preparation method of superfine polyester filament yarn for chenille yarn

Also Published As

Publication number Publication date
CN108035007B (en) 2020-05-05

Similar Documents

Publication Publication Date Title
CN108071009A (en) A kind of method for reducing spun polyester thread filoplume
CN108035007A (en) Superfine denier polyester drafting silk and preparation method thereof
CN108035011A (en) Fused mass directly spinning colored polyester fiber and preparation method thereof
CN108130624B (en) Polyester linen-like different-shrinkage composite yarn and preparation method thereof
CN108130611A (en) It is a kind of high to stretch low-shrinkage type polyester industrial fiber and preparation method thereof
CN108130605B (en) A kind of polyester Wool-Like abnormal contraction composite filament and preparation method thereof
CN108048939B (en) One step spins elastic force composite filament and preparation method thereof
CN108130609A (en) A kind of lower shrinkage type polyester industrial fiber and preparation method thereof
CN108385194A (en) A kind of metachromia polyester FDY fiber and preparation method thereof
CN108385189A (en) A kind of low-shrinkage high-strength polyester industrial fiber and preparation method thereof
CN108130610A (en) A kind of superelevation strong type polyester industrial fiber and preparation method thereof
CN107988649A (en) Superfine draw texturing yarn and preparation method thereof
CN108385195A (en) A kind of polyester DTY fiber and preparation method thereof
CN108385226A (en) A kind of polyester imitates cotton abnormal contraction composite filament and preparation method thereof
CN107604464A (en) A kind of preparation method of double odd-shaped cross section moisture absorbing and sweat releasing fiber types
CN104532392B (en) Porous super-bright polyester fiber and preparation method thereof
CN107987260A (en) Modified poly ester and preparation method thereof
CN107868997A (en) Fused mass directly spinning washs ultra-soft composite filament and preparation method thereof
CN101545151A (en) Polypropylene fiber with dyeability and good fastness to washing
CN108385196A (en) A kind of high-strength coloured polyester industrial yarn and preparation method thereof
CN108385418A (en) A kind of high mode and low mode type rigid line rope and preparation method thereof
CN105648594B (en) A kind of low aberration polyester imitates linen look abnormal contraction composite filament and preparation method thereof
CN108130743A (en) Ultralow shrinkage type puggaree and preparation method thereof
CN108385187A (en) High-strength aircraft safety band and preparation method thereof
CN108130613A (en) A kind of double heterotypic fibres and preparation method thereof

Legal Events

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