CN108385187A - High-strength aircraft safety band and preparation method thereof - Google Patents

High-strength aircraft safety band and preparation method thereof Download PDF

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Publication number
CN108385187A
CN108385187A CN201711342800.1A CN201711342800A CN108385187A CN 108385187 A CN108385187 A CN 108385187A CN 201711342800 A CN201711342800 A CN 201711342800A CN 108385187 A CN108385187 A CN 108385187A
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strength
finish
modified poly
poly ester
aircraft safety
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CN108385187B (en
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王丽丽
邵义伟
李晓林
赵艳丽
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Jiangsu Hengli Chemical Fiber Co Ltd
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Jiangsu Hengli Chemical Fiber Co Ltd
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • 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
    • C08G63/78—Preparation processes
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The present invention relates to a kind of high-strength aircraft safety bands and preparation method thereof, modified poly ester is viscosified through solid phase polycondensation, melts, measure, squeezing out, cooling down, oiling, stretching, high-strength polyester industrial silk is made in thermal finalization and winding, high-strength aircraft safety band is made by weaving, contain the crown ether that content is 67.30~85.58wt% in the finish to oil, finish when in use, the emulsion of a concentration of 10~20wt% is configured to water.Preparation method of the present invention is simple, and the material of high-strength polyester industrial silk obtained is the modified poly ester that strand includes terephthalic acid (TPA) segment, ethylene glycol segment and branched dihydric alcohol segment, and branched dihydric alcohol chain structure formula is：In formula, R1And R2It is each independently selected from the straight-chain alkyl-sub that carbon atom number is 1~3, R3The alkyl for being 1~5 selected from carbon atom number, R4The alkyl for being 2~5 selected from carbon atom number, tensile load value >=14700N of final high-strength aircraft safety band obtained.

Description

High-strength aircraft safety band and preparation method thereof
Technical field
The invention belongs to fiber preparation field, it is related to a kind of high-strength aircraft safety band and preparation method thereof.
Background technology
Polyethylene terephthalate (PET) is a kind of polymer of function admirable, and PET is high with modulus, strong because of it The advantages that degree is high, conformality is good and barrier property is good is widely used in the fields such as fiber, bottle packaging, film and sheet material, yield Cumulative year after year, position in industry are obviously improved.
But during synthesizing the polycondensation reaction of ethylene terephthalate, especially when generating linear polymer, Since high-temperature oxydation degradation also association linear and cyclic oligomer, cyclic oligomer are in polycondensation phase due to the macromolecular end of the chain Return sting cyclisation and formed, about 70% or more is cyclic trimer in cyclic oligomer, cyclic trimer have easily aggregation, Yi Jie The characteristics such as brilliant, chemistry and heat-resistant stability height, generation cyclic trimer can there are following influences on polyester processing：(1) it can cause The blocking of filament spinning component influences the service life of fondant filter and component；(2) it can be precipitated, deposit in fiber heat-setting process On heating roller, frictional force is caused to increase and heat irregular；(3) dyeing course can make dyestuff centered on cyclic trimer Assemble and be adhered to fiber surface, phenomena such as dyestuff color dot, spot and dyeing defect occurs in fiber surface, influences made of its weaving The feel and coloured light of fabric, the normal flow stream velocity of melt can be limited by being simultaneously filled with the cyclic oligomer of pipeline and valve, be caused Stock-dye is irregular, poor reproducibility；(4) it is adhered to fiber surface, causes, around yarn difficulty, broken yarn occur and thickness is unequal existing As influencing the mechanical properties such as fracture strength and the elongation at break of fiber, seriously affecting product quality.With polyester fiber yield It is growing, polyester quality requirement is also increasingly improved, thus caused by cyclic oligomer the problem of polyester post-processing by Gradually people is caused to pay close attention to, in particular with the fast development of microdenier polyester fibers, market proposes more the dyeing of polyester fiber High requirement.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) pentavalent phosphorous compound is added or etherificate is closed Object makes it be combined with the metallic catalyst in process of polyester synthesizing, or increases the amount of heat stabilizer, to be generated to polyester Stabilization, thus the generation of cyclic trimer can be inhibited under high-temperature fusion；(2) polyester fondant stopping at high temperature is reduced Stay the time.But the above method can cause molecular weight of polyesters reduction and distribution to widen, and influence the quality of final fiber obtained, simultaneously The reduction effect of cyclic trimer oligomer is not obvious.
It, must in spinning process since the dielectric constant of most of PET fiber is smaller, regain is relatively low and friction coefficient is higher Spinning oil must be used.The main component of finish is surfactant, can form oriented attachment layer on chemical fibre surface, i.e., oily Film, on the one hand, the hydrophilic radical of oil film can adsorb the moisture in air towards space, form continuous water on the fiber surface Film makes charged ion that migration occur on it, reduces the accumulation because of electrostatic charge caused by friction between fiber, to reduce The sheet resistance of fiber increases the electric conductivity of fiber, and on the other hand, fiber, which is isolated, in oil film again can generate centainly fiber Affinity makes it be not at random there are certain convergence, and in addition to this, oil film also imparts certain smooth of fiber Property, so that fiber is not damaged in friction process, and have good feel, can be passed through in spinning winding, stretching, The operational sequences such as dry, eliminate the electrostatic interaction during textile process, will not occur bad around apron, roller, cylinder etc. Phenomenon reduces the generation of lousiness and broken end, ensures the quality of fiber product.Since the oil film of fiber surface is in high temperature, high speed After being ruptured under certain pressure, the friction behavior of fiber can be changed, frictional force is caused to increase, fiber is caused lousiness, broken end occur Equal other problems, film strength is higher, is more not easily broken, and is more conducive to the spinnability of fiber, when finish is equably adsorbed on fibre When on dimension table face, surface forms the oil film of distribution uniform, and oil film is rapid after fiber is stretched and uniformly extends, if finish Viscosity it is excessively high, be unfavorable for the dispersion of finish, form uniform oil film.And with the high speed of polyester filament, ultrahigh speed and more The development of function fiber type, develops that a kind of heat resistance is good, viscosity is low, film strength is high, Lubricity is good and antistatic property The great realistic meaning of strong finish.
High-strength polyester industrial yarn is widely used, can be used for the fields such as safety belt, conveyer belt.But high intensity is prepared at this stage The main problem that polyester industrial fiber faces has two, first, finish volatilization is very fast and is easily bonded in fiber surface so that be made Fiber unevenness rate it is higher, performance is poor；Second is that the volatilization of oligomer remains in the surface of spinneret in fiber, fiber hair is caused Silk, influences the quality of fiber.
Therefore, how to provide the high strength fibre that a kind of spinning is uniform and oligomer is few becomes current urgently to be resolved hurrily Problem.
Invention content
The purpose of the invention is to overcome finish volatilization in the prior art fast easily caused by fiber surface bonds The problem of residual oligomer excessively influences fiber quality during fiber is uneven and spinneret provides a kind of spinning uniformly and oligomer contains Measure few high intensity aircraft safety band and preparation method thereof.The introducing of branched dihydric alcohol in modified poly ester of the present invention is reduced The cyclic oligomer generated in polyester side reaction, improves the quality of fiber；The use of the finish containing crown ether, improves finish Heat resistance and lubricity improve the quality of fiber, since the more conventional smooth agent of crown ether has lower viscosity, higher volatilization Point, makes the friction coefficient smaller of finish containing crown ether and with more excellent heat-resistant stability, to improve the processing of fiber Performance reduces the appearance of lousiness phenomenon；
In order to achieve the above object, the technical solution adopted by the present invention is：
High-strength aircraft safety band, high-strength aircraft safety band are made by high-strength polyester industrial silk weaving, high-strength polyester industrial silk Material be modified poly ester, the strand of modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment and branched binary The structural formula of alcohol segment, branched dihydric alcohol is as follows：
In formula, R1And R2It is each independently selected from the straight-chain alkyl-sub that carbon atom number is 1~3, R3It is 1 selected from carbon atom number ~5 alkyl, R4The alkyl for being 2~5 selected from carbon atom number, the purpose that carbon atom number limits：Due to introducing branch in dihydric alcohol Chain structure and backbone can be such that the electronegativity of alkoxy portion weakens, and the carbon atom number of branched structure is too small, to alkoxy Partial electronegativity influence is small, and the generation to reducing cyclic oligomer has little significance；The carbon atom number of branched structure is excessive, meeting Intermolecular entanglement is generated, the distribution of molecular weight is had an impact；
Tensile load value >=14700N of high-strength aircraft safety band.
As preferred technical solution：
The fiber number of high-strength aircraft safety band as described above, the high-strength polyester industrial silk is 1100~1670dtex, line Density variation rate is -1.2~1.5%, fracture strength >=8.1cN/dtex, fracture strength CV value≤2.0%, in elongation at break Center value is 14.0%, and elongation at break deviation ratio is ± 1.0%, and extension at break CV value≤6.0%, 4.0cN/dtex loads are stretched The central value of long rate is that the deviation ratio of the elongation of 5.5~6.2%, 4.0cN/dtex loads is ± 0.8%, 177 DEG C, Dry-hot shrinkage under the conditions of 10min and 0.05cN/dtex is 6.0~9.5%, and network is 3~9/m, oil content 0.35 ~0.8%.It can be seen that the polyester industrial fiber fracture strength prepared by the present invention is high, uniformity is good.
High-strength aircraft safety band as described above, content≤0.6wt% of cyclic oligomer, existing in the modified poly ester The amount of cyclic oligomer is 1.5~2.1wt% in polyester made from technology, and the present invention significantly reduces ring compared with the existing technology The production quantity of shape oligomer；
The number-average molecular weight 20000~27000 of the modified poly ester, molecular weight distributing index are 1.8~2.2, modified poly- The molecular weight of ester is higher, and molecular weight distribution is relatively narrow, disclosure satisfy that the demand of spinning processing, and it is excellent to be conducive to processability Fiber；
The molar content of branched dihydric alcohol segment is the 3 of terephthalic acid (TPA) segment molar content in the modified poly ester ~5%, the molar content of branched dihydric alcohol segment is relatively low in modified poly ester, is conducive to the Optimality for keeping polyester itself Energy；
The branched dihydric alcohol is 2- Ethyl-2-Methyl -1,3- propylene glycol, 2,2- diethyl -1,3- propylene glycol, 2- Butyl -2- ethyl -1,3- propylene glycol, 3,3- diethyl -1,5- pentanediols, 4,4- diethyl -1,7- heptandiols, 4,4- bis- (1, - Methylethyl) -1,7- heptandiols, 3,3- dipropyl -1,5- pentanediols, 4,4- dipropyl -1,7- heptandiols, 4- methyl -4- (1,1- dimethyl ethyls) -1,7- heptandiols, 3- methyl -3- amyls -1,6-HD or 3,3- diamyl -1,5- pentanediols.
High-strength aircraft safety band as described above, the preparation method of the modified poly ester are：By terephthalic acid (TPA), ethylene glycol Successively esterification is carried out with the branched dihydric alcohol after mixing and polycondensation reaction obtains modified poly ester.
High-strength aircraft safety band as described above, the specific preparation process of the modified poly ester are as follows：
(1) esterification；
Terephthalic acid (TPA), ethylene glycol and the branched dihydric alcohol are made into slurry, catalyst is added and stabilizer is mixed After closing uniformly, pressurization progress esterification, moulding pressure are normal pressure~0.3MPa in nitrogen atmosphere, and the temperature of esterification is 250~260 DEG C, be esterification terminal when the water quantity of distillate in esterification reaches 90% or more of theoretical value；
(2) polycondensation reaction；
After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure 30~ Absolute pressure 500Pa being steadily evacuated to by normal pressure in 50min hereinafter, reaction temperature is 260~270 DEG C, the reaction time is 30~ 50min then proceedes to vacuumize, and carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be further reduced to absolute pressure For 100Pa hereinafter, reaction temperature is 275~285 DEG C, the reaction time is 50~90min, and modified poly ester is made.
High-strength aircraft safety band as described above, in step (1), terephthalic acid (TPA), ethylene glycol and described branched two The molar ratio of first alcohol is 1:1.2~2.0:0.03~0.06, the addition of the catalyst is the 0.01 of terephthalic acid (TPA) weight ~0.05%, 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 stabilizer is triphenyl phosphate, tricresyl phosphate Methyl esters or Trimethyl phosphite.
The present invention also provides a kind of methods preparing high-strength aircraft safety band as described above, by the modified poly ester through solid Phase condensation viscosity enhancing, melting, metering, extrusion, cooling, oil, stretch, high-strength polyester industrial silk is made in thermal finalization and winding, high-strength High-strength aircraft safety band is made through weaving in polyester industrial fiber；
Contain crown ether in the finish to oil, and the content of crown ether is 67.30~85.58wt%, finish of the present invention The content of middle crown ether need to be kept in a certain range, and the addition of crown ether is too low, can not be made that viscosity is low, heat resistance is good and The higher finish of film strength, the addition of crown ether is excessively high, other performance indicators of finish can be affected.
Crown ether is a kind of heterocyclic organic compounds, includes multiple ether groups.The wetting ability of crown ether-like surfactant Bigger than corresponding open chain compound, crown ether has preferable solubilising, and salt compounds are relatively low in the solubility of organic compound, but with The solubility for the organic matter of the addition salt compounds of crown ether is improved.Conventional polyester class compound or polyethers in finish Class, since molecular weight is larger and the effect of hydrogen bond, intermolecular effect is larger, and it is larger to show as kinematic viscosity, after crown ether is added, Crown ether can be preferably compatible in polyesters compound or polyethers finish system, into polyesters compound or polyethers molecule Between chain, the active force between strand is shielded, is reduced so as to cause the viscosity of finish system.Preparation medium is antistatic simultaneously Agent is broadly divided into anionic, cationic and amphoteric surfactant, mostly contains metal ion or deposits in a salt form This all makes antistatic agent and polyesters compound in finish or the phase tolerance of polyethers, the addition of crown ether, due to the molten effect of salt It answers, improves antistatic agent and polyesters compound or the compatibility of polyethers, and then improve finish oil film strength, this is right The stability and the product amount of holding of spinning have larger meaning.The index of finish is the embodiment of a composite factor, thus to crown ether Addition propose certain restriction, too low heat resistance, the advantage of film strength to finish embodies inadequate, and excessive other refer to Rotating savings is restricted；
The finish when in use, the emulsion of a concentration of 10~20wt% is configured to water.
As preferred technical solution：
The inherent viscosity of method as described above, the solid phase polycondensation thickening post-modification polyester is 1.0~1.2dL/g；It is special Property viscosity be molecular weight a kind of characteristic manner, inherent viscosity is excessively high, and following process temperature increases, and thermal degradation easily occurs for product； Inherent viscosity is too low, then is difficult to intensity and performance required for reaching；
The finish heats thermal weight loss after 2h at 200 DEG C and is less than 15wt%, and crown ether has higher volatilization point and excellent The heat resistance of good heat-resistant stability, the finish introduced after crown ether is also obviously improved；
For the finish at (50 ± 0.01) DEG C, kinematic viscosity is 27.5~30.1mm2/ s, the finish are configured to water Kinematic viscosity after the lotion of a concentration of 10wt% is 0.93~0.95mm2/ s, the viscosity that crown ether can reduce finish are mainly Since crown ether oneself viscosity is relatively low and is pearl small molecule, after introducing crown ether in finish system, crown ether can be preferably compatible to In polyesters compound or polyether compound finish system, while entering polyesters compound or polyether compound strand Between, the active force between strand is shielded, to reduce the viscosity of finish system；
The film strength of the finish is 121~127N, and the film strength of finish is relatively low in the prior art, generally in 110N Left and right is mostly contained metal ion this is mainly due to the antistatic agent of preparation medium or is existed in a salt form, causes to resist Electrostatic agent can improve film strength and be mainly with polyesters compound or the poor compatibility of polyether compound in finish, crown ether Salting in effect can be generated after being added due to crown ether, improves antistatic agent and polyesters compound or the compatibility of polyethers, And then improve finish oil film strength；
The surface tension of the finish is 23.2~26.8cN/cm, and specific resistance is 1.0 × 108~1.8 × 108Ω·cm；
After oiling, confficient of static friction between fiber and fiber is 0.250~0.263, the coefficient of kinetic friction is 0.262~ 0.273；
After oiling, confficient of static friction between fiber and metal is 0.202~0.210, the coefficient of kinetic friction is 0.320~ 0.332。
The crown ether is 2- methylols -12-crown-4,15- crown ethers -5 or 2- methylol -15- crown-s 5；
Also contain mineral oil, phosphate kalium salt, trimethylolpropane laurate and sodium alkyl sulfonate in the finish；
The mineral oil is one kind in the mineral oil of 9#~17#；
The phosphate kalium salt is 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, isomerous tridecanol polyoxyethylene ether phosphate kalium salt or ten Tetracosanol phosphate kalium salt；
The sodium alkyl sulfonate is dodecyl sodium sulfate, pentadecyl sulfonic acid sodium or sodium cetanesulfonate；
The preparation method of method as described above, the finish is：By crown ether and phosphate kalium salt, the trimethylolpropane moon Cinnamic acid ester and sodium alkyl sulfonate are added in mineral oil after mixing is uniformly mixing to obtain finish；It counts in parts by weight, each group The addition divided is as follows：
The mixing carries out at normal temperatures, and the temperature of the stirring is 40~55 DEG C, and the time is 1~3h.
The spinning technology parameter of method as described above, the high-strength polyester industrial silk is as follows：
295 DEG C of spinning temperature；
The technological parameter of post-heater is：
300~400mm of length；310~330 DEG C of temperature；
The technological parameter of cooling wind is：
700~850Pa of pressure；20~25 DEG C of temperature；
Humidity 75~85%；0.4~0.6m/s of wind speed；
It stretches, the technological parameter of thermal finalization is：
Invention mechanism：
The method comprises the steps of firstly, preparing include changing for terephthalic acid (TPA) segment, ethylene glycol segment and branched dihydric alcohol segment Property polyester, then by modified poly ester through viscosifying, melting through solid phase polycondensation, measure, squeeze out, cool down, oil, stretch, thermal finalization and High-strength polyester industrial silk is made in winding, and high-strength aircraft safety band is made through weaving in high-strength polyester industrial silk, in the finish to oil Containing crown ether, and the content of crown ether is 67.30~85.58wt%, wherein modified poly ester and finish and its mutual association Same-action influences the performance of final high-strength aircraft safety band obtained specific as follows：
The addition of modified poly ester in the present invention, reduces the generation of cyclic oligomer, on the one hand improves the use of component On the other hand service life improves the stability of spinning, improve the uniformity of fiber.In addition the present invention, which also uses, contains crown ether Finish increases the stability of spinning, is mutually cooperateed with modified poly ester, improves the stability of spinning, and then improve fiber Quality.
In organic compound, the angle between two chemical bonds that the same atom of intramolecular is formed is known as bond angle, and bond angle is logical The common number of degrees indicate that the electronegativity of central atom and coordination atom, can influence the bond angle of molecule in organic compound molecule.When with Central atom bonding coordination atom electronegativity increase when, coordination atom electron-withdrawing ability enhancing, bond electron pair will to The movement of position body direction farther out from central atom makes between key pair because that repulsion reduces is close to each other, so that bond angle also reduces therewith, On the contrary, when the electronegativity for the coordination atom being bonded with central atom reduces, the enhancing of coordination atom electron donation, bonding electrons To will be moved to central atom direction, from central atom closer to making to be located remotely from each other because repulsion increases between key pair, to bond angle Increase therewith.
According to Pauling Electronegativities, the electronegativity of C, H and O atom is respectively 2.55,2.20 and 3.44, and according to Valence electron balancing energy is theoretical, and the calculation formula of Group Electronegativity is shown below：
In formula, xiFor the electronegativity of i atoms neutral atom before bonding, Nve,iFor valence electron number in i atoms, niFor i The number of atom in the molecule.Calculating step for more complex Group Electronegativity is mainly：Simple group is calculated first Electronegativity, then regard simple group as electronegativity that quasiatom calculates more complex group again, such successive iteration, finally Obtain the electronegativity of Targeting groups.It should be noted that when calculating the electronegativity of quasiatom, base (for example, group- Base of OH is O atom) in the valence electron of non-bonding regard the valence electron of quasiatom as.
C atoms can be with the O atom knot of hydroxyl in dihydric alcohol after the C-O keys fracture of carboxyl in terephthalic acid (TPA) in the present invention The new C-O keys formed in ester group are closed, the C atoms key C-C formed with C atoms on phenyl ring in ester group and the chemical bond newly formed Bond angle between C-O is denoted as α, and the change of bond angle α can influence annulation, and when α is less than 109 °, molecule is easy to cyclic, and with The increase of α, the probability of molecule cyclization can decline.Present invention introduces branched dihydric alcohol, structural formula is shown below：
In formula, R1And R2It is each independently selected from the straight-chain alkyl-sub that carbon atom number is 1~3, R3It is 1 selected from carbon atom number ~5 alkyl, R4The alkyl for being 2~5 selected from carbon atom number.The diol structure due to introducing branched structure and backbone, The electronegativity of its alkoxy portion can be made to weaken, can also be obtained in the diol structure with two by the calculation formula of Group Electronegativity The electronegativity of the connected group of carbonyl is between 2.59~2.79 in acid, and the group-being connected with carbonyl in diacid in ethylene glycol OCH2CH2Electronegativity be 3.04, thus its alkoxy is than-the OCH in ethylene glycol2CH2There is stronger electron, because This makes the bond electron pair on the chemical bond C-O keys newly formed that will be moved to center C atomic orientations, from central atom closer to, Make to be located remotely from each other because repulsion increases between key pair, so that bond angle α is more than 109 °, the probability for generating linear polymer increases, The generation of phenomena such as to reduce the generation of cyclic oligomer, advantageously reduce fracture of wire and uneven thickness, advantageously reduces pair The influence that the mechanical properties such as the fracture strength of fiber and elongation at break generate, to improve product quality.
The present invention has been made that a kind of viscosity is low, heat resistance is good and film strength is higher by introducing crown ether in finish Finish.The viscosity of finish is higher mainly due to containing conventional polyester class compound or polyethers chemical combination in finish in the prior art Object, for such compound since molecular weight is larger and the effect of hydrogen bond, the intermolecular larger kinematic viscosity that shows as of effect is larger, Thus cause the viscosity of finish higher, the viscosity of finish can significantly reduce after addition crown ether, mainly since crown ether itself is viscous It spends relatively low and is pearl small molecule, crown ether can be preferably compatible in polyesters compound or polyethers finish system, while into Enter between polyesters compound or polyether compound strand, the active force between strand is shielded, to reduce finish body The viscosity of system.The film strength of finish is relatively low mainly since the antistatic agent of preparation medium mostly contains metal in the prior art Ion exists in a salt form, leads to antistatic agent and the poor compatibility of polyesters compound or polyethers in finish, hat Ether, which can improve after film strength is mainly added due to crown ether, can generate salting in effect, improve antistatic agent and polyesters The compatibility of compound or polyethers, and then improve finish oil film strength.In addition, crown ether has higher volatilization point and excellent The heat resistance of good heat-resistant stability, the finish introduced after crown ether is also obviously improved, since crown ether is with relatively low Viscosity, higher volatilization point, smaller friction coefficient and excellent heat-resistant stability, improve the processing performance of fiber.
Advantageous effect：
(1) high-strength aircraft safety band and preparation method thereof of the invention, preparation flow advantages of simple, by high-strength polyester industrial High-strength aircraft safety band made from silk has high tensile property and high fracture strength；
(2) preparation method of high-strength aircraft safety band of the invention, by introducing branched binary in modified poly ester Alcohol changes the bond angle of polyester molecule, to significantly reduce the generation of cyclic oligomer in process of polyester synthesizing；
(3) preparation method of high-strength aircraft safety band of the invention, oil the oil agent containing crown ether used in the process Have the characteristics that viscosity is low, heat resistance is good, film strength is high, Lubricity is good and antistatic property is strong, improves spinning The processing performance of stability and fiber.
Specific implementation mode
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Fixed range.
Embodiment 1
The preparation method of high-strength aircraft safety band, is as follows：
(1) modified poly ester is prepared：
(a) esterification；It is 1 by molar ratio:1.2:0.03 terephthalic acid (TPA), ethylene glycol and Ethyl-2-Methyl -1 2-, 3- propylene glycol is made into slurry, and antimony oxide and triphenyl phosphate is added after mixing, the pressurization progress ester in nitrogen atmosphere Change reaction, moulding pressure is normal pressure, and the temperature of esterification is 250 DEG C, when the water quantity of distillate in esterification reaches theoretical value 90% when be esterification terminal, wherein the addition of antimony oxide be terephthalic acid (TPA) weight 0.01%, tricresyl phosphate The addition of phenyl ester is the 0.05% of terephthalic acid (TPA) weight, and the structural formula of wherein 2- Ethyl-2-Methyls -1,3-PD is such as Under：
(b) polycondensation reaction；After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, It is 500Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 30min, and reaction temperature is 260 DEG C, reaction time 40min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be further reduced to absolute pressure be 100Pa, instead It is 275 DEG C, reaction time 70min to answer temperature, and modified poly ester is made.The strand of wherein modified poly ester includes terephthalic acid (TPA) Segment, ethylene glycol segment and 2- Ethyl-2-Methyls -1,3-PD segment, the content of cyclic oligomer is in modified poly ester 0.6wt%, number-average molecular weight 20000, molecular weight distributing index 2.0,2- Ethyl-2-Methyls -1,3- the third two in modified poly ester The molar content of alcohol segment is the 3% of terephthalic acid (TPA) segment molar content；
(2) it oils and is prepared with finish；By 2- methylols -12-crown-4 and 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, trimethylolpropane Laurate and dodecyl sodium sulfate are added to after mixing at normal temperatures in 9# mineral oil and in 40 DEG C of uniform stirring 1h Obtain finish；It counts in parts by weight, the addition of each component is as follows：2 parts of 9# mineral oil；Trimethylolpropane laurate 10 Part；2- methylols -90 parts of 12-crown-4；8 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite；3 parts of dodecyl sodium sulfate.The oil prepared The content of crown ether is 79.6wt% in agent, and the high temperature resistance of finish is excellent, and thermal weight loss is after heating 2h at 200 DEG C 14.5wt%；The viscosity of finish is relatively low, at (50 ± 0.01) DEG C, kinematic viscosity 29.6mm2/ s is configured to a concentration of with water Kinematic viscosity after the lotion of 10wt% is 0.93mm2/s；The film strength of finish is higher, film strength 125N, finish Surface tension is 24.8cN/cm, and specific resistance is 1.3 × 108Ω cm, after oiling, quiet between fiber and fiber (F/F) rubs Wipe coefficient (μs) it is 0.255, the coefficient of kinetic friction (μd) it is 0.266, the confficient of static friction (μ between fiber and metal (F/M)s) be 0.203, the coefficient of kinetic friction (μd) it is 0.320, the finish of preparation when in use, the emulsification of a concentration of 15wt% is configured to water Liquid；
(3) modified poly ester viscosified through solid phase polycondensation, melted, measured, squeezed out, cooled down, oiled, stretched, thermal finalization and volume Around obtained high-strength polyester industrial silk, high-strength aircraft safety band is made through weaving in high-strength polyester industrial silk.Wherein, when doubling twisting most Big plying fiber number is 32000dtex, and the inherent viscosity that solid phase polycondensation viscosifies post-modification polyester is 1.0dL/g, and filament spinning component is more It is 40 days to change the period.
The spinning technology parameter of high-strength polyester industrial silk is shown in Table 1.
High-strength polyester industrial silk and final high-strength aircraft safety band various performance parameters obtained are shown in Table 2.
Embodiment 2
The preparation method of high-strength aircraft safety band, is as follows：
(1) modified poly ester is prepared：
(a) esterification；It is 1 by molar ratio:1.3:0.04 terephthalic acid (TPA), ethylene glycol and 2,2- diethyl -1,3- Propylene glycol is made into slurry, and antimony glycol and trimethyl phosphate is added after mixing, and pressurizeing in nitrogen atmosphere, it is anti-be esterified It answers, 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 It is esterification terminal when 91%, the wherein addition of antimony glycol is the 0.02% of terephthalic acid (TPA) weight, trimethyl phosphate Addition be terephthalic acid (TPA) weight 0.03%, wherein the structural formula of 2,2- diethyl -1,3-PD is as follows：
(b) polycondensation reaction；After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, It is 490Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 35min, and reaction temperature is 261 DEG C, reaction time 30min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be further reduced to absolute pressure be 100Pa, instead It is 277 DEG C, reaction time 85min to answer temperature, and modified poly ester is made.The strand of wherein modified poly ester includes terephthalic acid (TPA) Segment, ethylene glycol segment and 2,2- diethyl -1,3-PD segment, the content of cyclic oligomer is in modified poly ester 0.6wt%, number-average molecular weight 27000, molecular weight distributing index 1.8,2,2- diethyl -1,3-PD chain in modified poly ester The molar content of section is the 5% of terephthalic acid (TPA) segment molar content；
(2) it oils and is prepared with finish；By 15- crown ethers -5 and isomerous tridecanol polyoxyethylene ether phosphate kalium salt, three hydroxyl first Base propane laurate and pentadecyl sulfonic acid sodium be added to after mixing at normal temperatures in 10# mineral oil and 43 DEG C uniformly Stirring 1.5h obtains finish；It counts in parts by weight, the addition of each component is as follows：2 parts of 10# mineral oil；The trimethylolpropane moon 15 parts of cinnamic acid ester；- 5 70 parts of 15- crown ethers；10 parts of isomerous tridecanol polyoxyethylene ether phosphate kalium salt；Pentadecyl sulfonic acid sodium 7 Part.The content of crown ether is 67.30wt% in the finish prepared, and the high temperature resistance of finish is excellent, heats 2h at 200 DEG C Thermal weight loss is 13wt% afterwards, and the viscosity of finish is relatively low, at (50 ± 0.01) DEG C, kinematic viscosity 28.1mm2/ s, is configured with water It is 0.93mm at the kinematic viscosity after the lotion of a concentration of 10wt%2The film strength of/s, finish are higher, are 123N, finish Surface tension is 25.1cN/cm, and specific resistance is 1.5 × 108Ω cm, after oiling, the static friction between fiber and fiber (F/F) Coefficient (μs) it is 0.257, the coefficient of kinetic friction (μd) it is 0.265, after oiling, the confficient of static friction between fiber and metal (F/M) (μs) it is 0.205, the coefficient of kinetic friction (μd) it is 0.323, the finish of preparation is configured to a concentration of 10wt%'s when in use, with water Emulsion；
(3) modified poly ester viscosified through solid phase polycondensation, melted, measured, squeezed out, cooled down, oiled, stretched, thermal finalization and volume Around obtained high-strength polyester industrial silk, high-strength aircraft safety band is made through weaving in high-strength polyester industrial silk.Wherein, when doubling twisting most Big plying fiber number is 38000dtex, and the inherent viscosity that solid phase polycondensation viscosifies post-modification polyester is 1.08dL/g, and filament spinning component is more It is 42 days to change the period.
The spinning technology parameter of high-strength polyester industrial silk is shown in Table 1.
High-strength polyester industrial silk and final high-strength aircraft safety band various performance parameters obtained are shown in Table 2.
Embodiment 3
The preparation method of high-strength aircraft safety band, is as follows：
(1) modified poly ester is prepared：
(a) esterification；It is 1 by molar ratio:1.4:0.05 terephthalic acid (TPA), ethylene glycol and ethyl -1 2- butyl -2-, 3- propylene glycol is made into slurry, and antimony acetate and Trimethyl phosphite is added after mixing, pressurizes and is esterified in nitrogen atmosphere The temperature of reaction, moulding pressure 0.1MPa, esterification is 252 DEG C, when the water quantity of distillate in esterification reaches theoretical value 92% when be esterification terminal, wherein the addition of antimony acetate be terephthalic acid (TPA) weight 0.03%, phosphorous acid front three The addition of ester is the 0.01% of terephthalic acid (TPA) weight, and the structural formula of wherein 2- butyl -2- ethyls -1,3-PD is as follows：
(b) polycondensation reaction；After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, It is 495Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 40min, and reaction temperature is 263 DEG C, reaction time 45min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be further reduced to absolute pressure be 95Pa, reaction Temperature is 278 DEG C, reaction time 60min, modified poly ester is made, the strand of wherein modified poly ester includes terephthalic acid (TPA) chain Section, ethylene glycol segment and 2- butyl -2- ethyls -1,3-PD segment, the content of cyclic oligomer is in modified poly ester 0.5wt%, number-average molecular weight 21000, molecular weight distributing index 2.2,2- butyl -2- ethyls -1,3- the third two in modified poly ester The molar content of alcohol segment is the 4% of terephthalic acid (TPA) segment molar content；
(2) it oils and is prepared with finish；By 2- methylol -15- crown-s 5 and ten tetracosanol phosphate kalium salts, trihydroxy methyl third Alkane laurate and pentadecyl sulfonic acid sodium are added to after mixing at normal temperatures in 11# mineral oil and in 48 DEG C of uniform stirrings 3h obtains finish；It counts in parts by weight, the addition of each component is as follows：8 parts of 11# mineral oil；Trimethylolpropane laurate 10 parts；585 parts of 2- methylol -15- crown-s；Ten 11 parts of tetracosanol phosphate kalium salts；5 parts of pentadecyl sulfonic acid sodium.It prepares Finish in crown ether content be 70.83wt%, the high temperature resistance of finish is excellent, at 200 DEG C heat 2h after thermal weight loss Viscosity for 11wt%, finish is relatively low, at (50 ± 0.01) DEG C, kinematic viscosity 30.1mm2/ s is configured to a concentration of with water Kinematic viscosity after the lotion of 10wt% is 0.94mm2The film strength of/s, finish are higher, are 125N.The surface tension of finish For 23.2cN/cm, specific resistance is 1.8 × 108Ω cm, after oiling, 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 0.272, after oiling, the confficient of static friction (μ between fiber and metal (F/M)s) be 0.209, the coefficient of kinetic friction (μd) it is 0.329, the finish of preparation when in use, the emulsification of a concentration of 15wt% is configured to water Liquid；
(3) modified poly ester viscosified through solid phase polycondensation, melted, measured, squeezed out, cooled down, oiled, stretched, thermal finalization and volume Around obtained high-strength polyester industrial silk, high-strength aircraft safety band is made through weaving in high-strength polyester industrial silk.Wherein, when doubling twisting most Big plying fiber number is 30000dtex, and the inherent viscosity that solid phase polycondensation viscosifies post-modification polyester is 1.10dL/g, and filament spinning component is more It is 48 days to change the period.
The spinning technology parameter of high-strength polyester industrial silk is shown in Table 1.
High-strength polyester industrial silk and final high-strength aircraft safety band various performance parameters obtained are shown in Table 2.
Embodiment 4
The preparation method of high-strength aircraft safety band, is as follows：
(1) modified poly ester is prepared：
(a) 3,3- diethyl -1,5- pentanediols are prepared；At 90 DEG C, under nitrogen atmosphere, by 3,3- diethyl-propionic aldehyde, acetaldehyde and Triethylamine react 20min, then by concentrate addition have in the hydrogenation reactor of thunder girl's Raney nickel, 2.914MPa hydrogen pressure and It is reacted at 100 DEG C, reaction is finished, cooling, and catalyst is made to be precipitated, and after the processing of solution spent ion exchange resin, is depressurized and is steamed water, separation, Purification, obtains 3,3- diethyl -1,5-PD, wherein the structural formula of 3,3- diethyl -1,5-PD is as follows：
(b) esterification；It is 1 by molar ratio:1.5:0.06 terephthalic acid (TPA), ethylene glycol and 3,3- diethyl -1,5- Pentanediol is made into slurry, and antimony oxide and triphenyl phosphate is added after mixing, pressurizes and is esterified in nitrogen atmosphere The temperature of reaction, moulding pressure 0.3MPa, esterification is 255 DEG C, when the water quantity of distillate in esterification reaches theoretical value 95% when be esterification terminal, wherein the addition of antimony oxide be terephthalic acid (TPA) weight 0.04%, tricresyl phosphate The addition of phenyl ester is the 0.01% of terephthalic acid (TPA) weight；
(c) polycondensation reaction；After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, It is 400Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 50min, and reaction temperature is 265 DEG C, reaction time 33min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be further reduced to absolute pressure be 90Pa, reaction Temperature is 280 DEG C, reaction time 50min, modified poly ester is made, the strand of wherein modified poly ester includes terephthalic acid (TPA) chain Section, ethylene glycol segment and 3,3- diethyl -1,5-PD segment, the content of cyclic oligomer is 0.2wt% in modified poly ester, Number-average molecular weight 23000, molecular weight distributing index 1.9, mole of 3,3- diethyl -1,5-PD segment in modified poly ester Content is the 3.5% of terephthalic acid (TPA) segment molar content；
(2) it oils and is prepared with finish；By 2- methylols -12-crown-4 and 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, trimethylolpropane Laurate and sodium cetanesulfonate are added to after mixing at normal temperatures in 12# mineral oil and in 40 DEG C of uniform stirrings 2.5h obtains finish；It counts in parts by weight, the addition of each component is as follows：5 parts of 12# mineral oil；2- methylols -12-crown-4 95 Part；9 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite；2 parts of sodium cetanesulfonate.The content of crown ether is in the finish prepared The high temperature resistance of 85.58wt%, finish are excellent, and it is 9wt% to heat thermal weight loss after 2h at 200 DEG C, the viscosity of finish compared with It is low, at (50 ± 0.01) DEG C, kinematic viscosity 29.5mm2/ s, the movement being configured to water after the lotion of a concentration of 10wt% Viscosity is 0.93mm2The film strength of/s, finish are higher, are 121N, the surface tension of finish is 24.3cN/cm, and specific resistance is 1.0×108Ω cm, after oiling, the confficient of static friction (μ between fiber and fiber (F/F)s) it is 0.260, the coefficient of kinetic friction (μd) it is 0.263, after oiling, the confficient of static friction (μ between fiber and metal (F/M)s) it is 0.202, the coefficient of kinetic friction (μd) be 0.330, the finish of preparation when in use, the emulsion of a concentration of 18wt% is configured to water；
(3) modified poly ester viscosified through solid phase polycondensation, melted, measured, squeezed out, cooled down, oiled, stretched, thermal finalization and volume Around obtained high-strength polyester industrial silk, high-strength aircraft safety band is made through weaving in high-strength polyester industrial silk.Wherein, when doubling twisting most Big plying fiber number is 33000dtex, and the inherent viscosity that solid phase polycondensation viscosifies post-modification polyester is 1.13dL/g, and filament spinning component is more It is 44 days to change the period.
The spinning technology parameter of high-strength polyester industrial silk is shown in Table 1.
High-strength polyester industrial silk and final high-strength aircraft safety band various performance parameters obtained are shown in Table 2.
Embodiment 5
The preparation method of high-strength aircraft safety band, is as follows：
(1) modified poly ester is prepared：
(a) 4,4- diethyl -1,7- heptandiols are prepared；At 92 DEG C, under nitrogen atmosphere, by 4,4- diethyl-butyraldehyde, propionic aldehyde and Triethylamine react 20min, then by concentrate addition have in the hydrogenation reactor of thunder girl's Raney nickel, 2.914MPa hydrogen pressure and It is reacted at 100 DEG C, reaction is finished, cooling, and catalyst is made to be precipitated, and after the processing of solution spent ion exchange resin, is depressurized and is steamed water, separation, Purification, obtains 4,4- diethyl -1,7- heptandiols, wherein the structural formula of 4,4- diethyl -1,7- heptandiols is as follows：
(b) esterification；It is 1 by molar ratio:1.6:0.03 terephthalic acid (TPA), ethylene glycol and 4,4- diethyl -1,7- Heptandiol is made into slurry, and antimony glycol and trimethyl phosphate is added after mixing, and pressurizeing in nitrogen atmosphere, it is anti-be esterified It answers, 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 It is esterification terminal when 92%, the wherein addition of antimony glycol is the 0.05% of terephthalic acid (TPA) weight, trimethyl phosphate Addition be terephthalic acid (TPA) weight 0.04%；
(c) polycondensation reaction；After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, It is 450Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 33min, and reaction temperature is 270 DEG C, reaction time 30min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be further reduced to absolute pressure be 95Pa, reaction Temperature is 275 DEG C, reaction time 60min, modified poly ester is made, the strand of wherein modified poly ester includes terephthalic acid (TPA) chain Section, ethylene glycol segment and 4,4- diethyl -1,7- heptandiol segments, the content of cyclic oligomer is 0.5wt% in modified poly ester, Number-average molecular weight 25000, molecular weight distributing index 2.1, mole of 4,4- diethyl -1,7- heptandiol segments in modified poly ester Content is the 5% of terephthalic acid (TPA) segment molar content.
(2) it oils and is prepared with finish；By 15- crown ethers -5 and isomerous tridecanol polyoxyethylene ether phosphate kalium salt, three hydroxyl first Base propane laurate and dodecyl sodium sulfate be added to after mixing at normal temperatures in 13# mineral oil and 52 DEG C uniformly Stirring 2h obtains finish；It counts in parts by weight, the addition of each component is as follows：10 parts of 13# mineral oil；The trimethylolpropane moon 5 parts of cinnamic acid ester；- 5 70 parts of 15- crown ethers；8 parts of isomerous tridecanol polyoxyethylene ether phosphate kalium salt；Dodecyl sodium sulfate 6 Part.The content of crown ether is 70.70wt% in the finish prepared, and the high temperature resistance of finish is excellent, heats 2h at 200 DEG C Thermal weight loss is 13.5wt% afterwards, and the viscosity of finish is relatively low, at (50 ± 0.01) DEG C, kinematic viscosity 28.6mm2/ s, is matched with water It is 0.95mm to be set to the kinematic viscosity after the lotion of a concentration of 10wt%2The film strength of/s, finish are higher, are 126N, finish Surface tension be 24.9cN/cm, specific resistance be 1.2 × 108Ω cm, after oiling, quiet between fiber and fiber (F/F) rubs Wipe coefficient (μs) it is 0.251, the coefficient of kinetic friction (μd) it is 0.262, after oiling, the static friction system between fiber and metal (F/M) Number (μs) it is 0.202, the coefficient of kinetic friction (μd) it is 0.332, the finish of preparation is configured to a concentration of 20wt% when in use, with water Emulsion；
(3) modified poly ester viscosified through solid phase polycondensation, melted, measured, squeezed out, cooled down, oiled, stretched, thermal finalization and volume Around obtained high-strength polyester industrial silk, high-strength aircraft safety band is made through weaving in high-strength polyester industrial silk.Wherein, when doubling twisting most Big plying fiber number is 35000dtex, and the inherent viscosity that solid phase polycondensation viscosifies post-modification polyester is 1.07dL/g, and filament spinning component is more It is 49 days to change the period.
The spinning technology parameter of high-strength polyester industrial silk is shown in Table 1.
High-strength polyester industrial silk and final high-strength aircraft safety band various performance parameters obtained are shown in Table 2.
Embodiment 6
The preparation method of high-strength aircraft safety band, is as follows：
(1) modified poly ester is prepared：
(a) 4,4- bis- (1,-Methylethyl) -1,7- heptandiols are prepared；At 95 DEG C, under nitrogen atmosphere, by (the 1- methyl of 4,4- bis- Ethyl)-butyraldehyde, propionic aldehyde and triethylamine react 20min, then concentrate is added to the hydrogenation reactor for having thunder girl's Raney nickel In, it is reacted at 2.914MPa hydrogen pressure and 100 DEG C, reaction is finished, cooling, and catalyst is made to be precipitated.At solution spent ion exchange resin After reason, water is steamed in decompression, detaches, and purification obtains 4,4- bis- (1,-Methylethyl) -1,7- heptandiols, wherein 4,4- bis- (1,-methyl Ethyl) -1,7- heptandiols structural formula it is as follows：
(b) esterification；It is 1 by molar ratio:1.7:0.05 terephthalic acid (TPA), ethylene glycol and 4,4- bis- (1 ,-methyl second Base) -1,7- heptandiols are made into slurry, and antimony acetate and Trimethyl phosphite is added after mixing, pressurize in nitrogen atmosphere into The temperature of row esterification, moulding pressure 0.2MPa, esterification is 253 DEG C, when the water quantity of distillate in esterification reaches Theoretical value 96% when be esterification terminal, wherein the addition of antimony acetate be terephthalic acid (TPA) weight 0.01%, phosphorous The addition of sour trimethyl is the 0.05% of terephthalic acid (TPA) weight；
(c) polycondensation reaction；After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, It is 480Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 38min, and reaction temperature is 262 DEG C, reaction time 38min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be further reduced to absolute pressure be 98Pa, reaction Temperature is 279 DEG C, reaction time 80min, modified poly ester is made, the strand of wherein modified poly ester includes terephthalic acid (TPA) chain Section, ethylene glycol segment and 4,4- bis- (1,-Methylethyl) -1,7- heptandiol segments, the content of cyclic oligomer in modified poly ester For 0.55wt%, number-average molecular weight 27000, molecular weight distributing index 2.2,4,4- bis- (1 ,-Methylethyl) in modified poly ester The molar content of -1,7- heptandiol segments is the 4% of terephthalic acid (TPA) segment molar content；
(2) it oils and is prepared with finish；By 2- methylol -15- crown-s 5 and ten tetracosanol phosphate kalium salts, trihydroxy methyl third Alkane laurate and pentadecyl sulfonic acid sodium are added to after mixing at normal temperatures in 14# mineral oil and in 55 DEG C of uniform stirrings 1h obtains finish；It counts in parts by weight, the addition of each component is as follows：3 parts of 14# mineral oil；Trimethylolpropane laurate 10 parts；5 75 parts of 2- methylol -15- crown-s；Ten 14 parts of tetracosanol phosphate kalium salts；7 parts of pentadecyl sulfonic acid sodium.It prepares Finish in crown ether content be 68.80wt%, the high temperature resistance of finish is excellent, at 200 DEG C heat 2h after thermal weight loss Viscosity for 12wt%, finish is relatively low, at (50 ± 0.01) DEG C, kinematic viscosity 27.5mm2/ s is configured to a concentration of with water Kinematic viscosity after the lotion of 10wt% is 0.95mm2The film strength of/s, finish are higher, are 126N.The surface tension of finish For 25.4cN/cm, specific resistance is 1.6 × 108Ω cm, after oiling, the confficient of static friction (μ between fiber and fiber (F/F)s) 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) be 0.203, the coefficient of kinetic friction (μd) it is 0.330, the finish of preparation when in use, the emulsification of a concentration of 16wt% is configured to water Liquid；
(3) modified poly ester viscosified through solid phase polycondensation, melted, measured, squeezed out, cooled down, oiled, stretched, thermal finalization and volume Around obtained high-strength polyester industrial silk, high-strength aircraft safety band is made through weaving in high-strength polyester industrial silk.Wherein, when doubling twisting most Big plying fiber number is 31000dtex, and the inherent viscosity that solid phase polycondensation viscosifies post-modification polyester is 1.08dL/g, and filament spinning component is more It is 40 days to change the period.
The spinning technology parameter of high-strength polyester industrial silk is shown in Table 1.
High-strength polyester industrial silk and final high-strength aircraft safety band various performance parameters obtained are shown in Table 2.
Embodiment 7
The preparation method of high-strength aircraft safety band, is as follows：
(1) modified poly ester is prepared：
(a) 3,3- dipropyl -1,5- pentanediols are prepared；At 94 DEG C, under nitrogen atmosphere, by 3,3- dipropyl-propionic aldehyde, acetaldehyde and Triethylamine react 20min, then by concentrate addition have in the hydrogenation reactor of thunder girl's Raney nickel, 2.914MPa hydrogen pressure and It is reacted at 100 DEG C, reaction is finished, cooling, and catalyst is made to be precipitated.After the processing of solution spent ion exchange resin, water is steamed in decompression, detaches, Purification, obtains 3,3- dipropyl -1,5-PD, wherein the structural formula of 3,3- dipropyl -1,5-PD is as follows：
(b) esterification；It is 1 by molar ratio:1.8:0.03 terephthalic acid (TPA), ethylene glycol and 3,3- dipropyl -1,5- Pentanediol is made into slurry, and antimony oxide and triphenyl phosphate is added after mixing, pressurizes and is esterified in nitrogen atmosphere The temperature of reaction, moulding pressure 0.3MPa, esterification is 250 DEG C, when the water quantity of distillate in esterification reaches theoretical value 90% when be esterification terminal, wherein the addition of antimony oxide be terephthalic acid (TPA) weight 0.03%, tricresyl phosphate The addition of phenyl ester is the 0.02% of terephthalic acid (TPA) weight；
(c) polycondensation reaction；After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, It is 455Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 42min, and reaction temperature is 264 DEG C, reaction time 45min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be further reduced to absolute pressure be 85Pa, reaction Temperature is 285 DEG C, reaction time 75min, modified poly ester is made, the strand of wherein modified poly ester includes terephthalic acid (TPA) chain Section, ethylene glycol segment and 3,3- dipropyl -1,5-PD segment, the content of cyclic oligomer is in modified poly ester 0.45wt%, number-average molecular weight 26500, molecular weight distributing index 2.2,3,3- dipropyl -1,5-PD in modified poly ester The molar content of segment is the 4.5% of terephthalic acid (TPA) segment molar content.
(2) it oils and is prepared with finish；By 15- crown ethers -5 and 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, trimethylolpropane lauric acid Ester and sodium cetanesulfonate are added in 15# mineral oil and obtain oil in 41 DEG C of uniform stirring 2h after mixing at normal temperatures Agent；It counts in parts by weight, the addition of each component is as follows：8 parts of 15# mineral oil；20 parts of trimethylolpropane laurate；15- 100 parts of crown ether -5；15 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite；2 parts of sodium cetanesulfonate.Crown ether contains in the finish prepared Amount is 68.97wt%, and the high temperature resistance of finish is excellent, and thermal weight loss is 8.5wt% after heating 2h at 200 DEG C, finish Viscosity is relatively low, at (50 ± 0.01) DEG C, kinematic viscosity 28.4mm2/ s, after the lotion of a concentration of 10wt% is configured to water Kinematic viscosity be 0.94mm2The film strength of/s, finish are higher, are 122N.The surface tension of finish is 26.8cN/cm, than Resistance is 1.8 × 108Ω cm, after oiling, the confficient of static friction (μ between fiber and fiber (F/F)s) it is 0.263, dynamic friction Coefficient (μd) it is 0.268, after oiling, the confficient of static friction (μ between fiber and metal (F/M)s) it is 0.210, the coefficient of kinetic friction (μd) it is 0.320, the finish of preparation when in use, the emulsion of a concentration of 17wt% is configured to water；
(3) modified poly ester viscosified through solid phase polycondensation, melted, measured, squeezed out, cooled down, oiled, stretched, thermal finalization and volume Around obtained high-strength polyester industrial silk, high-strength aircraft safety band is made through weaving in high-strength polyester industrial silk.Wherein, when doubling twisting most Big plying fiber number is 35000dtex, and the inherent viscosity that solid phase polycondensation viscosifies post-modification polyester is 1.2dL/g, and filament spinning component is more It is 41 days to change the period.
The spinning technology parameter of high-strength polyester industrial silk is shown in Table 1.
High-strength polyester industrial silk and final high-strength aircraft safety band various performance parameters obtained are shown in Table 2.
Embodiment 8
The preparation method of high-strength aircraft safety band, is as follows：
(1) modified poly ester is prepared：
(a) 4,4- dipropyl -1,7- heptandiols are prepared；At 92 DEG C, under nitrogen atmosphere, by 4,4- dipropyl-butyraldehyde, acetaldehyde and Triethylamine react 20min, then by concentrate addition have in the hydrogenation reactor of thunder girl's Raney nickel, 2.914MPa hydrogen pressure and It is reacted at 100 DEG C, reaction is finished, cooling, and catalyst is made to be precipitated.After the processing of solution spent ion exchange resin, water is steamed in decompression, detaches, Purification, obtains 4,4- dipropyl -1,7- heptandiols, wherein the structural formula of 4,4- dipropyl -1,7- heptandiols is as follows：
(b) esterification；It is 1 by molar ratio:1.9:0.04 terephthalic acid (TPA), ethylene glycol and 4,4- dipropyl -1,7- Heptandiol is made into slurry, and antimony glycol and trimethyl phosphate is added after mixing, and pressurizeing in nitrogen atmosphere, it is anti-be esterified It answers, moulding pressure 0.3MPa, the temperature of esterification is 260 DEG C, when the water quantity of distillate in esterification reaches theoretical value It is esterification terminal when 93%, the wherein addition of antimony glycol is the 0.04% of terephthalic acid (TPA) weight, trimethyl phosphate Addition be terephthalic acid (TPA) weight 0.03%；
(c) polycondensation reaction；After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, It is 475Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 45min, and reaction temperature is 265 DEG C, reaction time 48min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be further reduced to absolute pressure be 88Pa, reaction Temperature is 283 DEG C, reaction time 80min, modified poly ester is made, the strand of wherein modified poly ester includes terephthalic acid (TPA) chain Section, ethylene glycol segment and 4,4- dipropyl -1,7- heptandiol segments, the content of cyclic oligomer is 0.6wt% in modified poly ester, Number-average molecular weight 23000, molecular weight distributing index 2.0, mole of 4,4- dipropyl -1,7- heptandiol segments in modified poly ester Content is the 3% of terephthalic acid (TPA) segment molar content；
(2) it oils and is prepared with finish；By 2- methylols -12-crown-4 and ten tetracosanol phosphate kalium salts, trihydroxy methyl third Alkane laurate and pentadecyl sulfonic acid sodium are added to after mixing at normal temperatures in 16# mineral oil and in 45 DEG C of uniform stirrings 3h obtains finish；It counts in parts by weight, the addition of each component is as follows：9 parts of 16# mineral oil；2- methylols -12-crown-4 80 Part；Ten 12 parts of tetracosanol phosphate kalium salts；5 parts of pentadecyl sulfonic acid sodium.The content of crown ether is in the finish prepared The high temperature resistance of 83.33wt%, finish are excellent, and it is 14wt% to heat thermal weight loss after 2h at 200 DEG C, the viscosity of finish compared with It is low, at (50 ± 0.01) DEG C, kinematic viscosity 30.0mm2/ s, the movement being configured to water after the lotion of a concentration of 10wt% Viscosity is 0.93mm2The film strength of/s, finish are higher, are 127N.The surface tension of finish is 23.5cN/cm, and specific resistance is 1.5×108Ω cm, after oiling, the confficient of static friction (μ between fiber and fiber (F/F)s) it is 0.262, the coefficient of kinetic friction (μd) it is 0.273, after oiling, the confficient of static friction (μ between fiber and metal (F/M)s) it is 0.208, the coefficient of kinetic friction (μd) It is 0.328, the finish of preparation when in use, the emulsion of a concentration of 18wt% is configured to water；
(3) modified poly ester viscosified through solid phase polycondensation, melted, measured, squeezed out, cooled down, oiled, stretched, thermal finalization and volume Around obtained high-strength polyester industrial silk, high-strength aircraft safety band is made through weaving in high-strength polyester industrial silk.Wherein, when doubling twisting most Big plying fiber number is 30000dtex, and the inherent viscosity that solid phase polycondensation viscosifies post-modification polyester is 1.15dL/g, and filament spinning component is more It is 44 days to change the period.
The spinning technology parameter of high-strength polyester industrial silk is shown in Table 1.
High-strength polyester industrial silk and final high-strength aircraft safety band various performance parameters obtained are shown in Table 2.
Embodiment 9
The preparation method of high-strength aircraft safety band, is as follows：
(1) modified poly ester is prepared：
(a) 4- methyl -4- (1,1- dimethyl ethyls) -1,7- heptandiols are prepared；At 92 DEG C, under nitrogen atmosphere, by 4- methyl Then concentrate addition is had thunder girl's Raney nickel by -4- (1,1- dimethyl ethyl)-butyraldehyde, propionic aldehyde and triethylamine react 20min Hydrogenation reactor in, reacted at 2.914MPa hydrogen pressure and 100 DEG C, reaction is finished, cooling, and catalyst is made to be precipitated, solution with from After sub-exchange resin processing, water is steamed in decompression, detaches, and purification obtains 4- methyl -4- (1,1- dimethyl ethyl) -1,7- heptandiols, The structural formula of wherein 4- methyl -4- (1,1- dimethyl ethyls) -1,7- heptandiols is as follows：
(b) esterification；It is 1 by molar ratio:2.0:0.05 terephthalic acid (TPA), ethylene glycol and 4- methyl -4- (1,1- bis- Methylethyl) -1,7- heptandiols are made into slurry, antimony acetate and trimethyl phosphate is added after mixing, in nitrogen atmosphere plus Pressure carries out esterification, and moulding pressure is normal pressure MPa, and the temperature of esterification is 251 DEG C, when the water quantity of distillate in esterification It is esterification terminal when reaching the 96% of theoretical value, wherein the addition of antimony acetate is the 0.05% of terephthalic acid (TPA) weight, The addition of trimethyl phosphate is the 0.04% of terephthalic acid (TPA) weight；
(c) polycondensation reaction；After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, It is 420Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 30min, and reaction temperature is 267 DEG C, reaction time 50min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be further reduced to absolute pressure be 80Pa, reaction Temperature is 280 DEG C, reaction time 90min, modified poly ester is made, the strand of wherein modified poly ester includes terephthalic acid (TPA) chain Section, ethylene glycol segment and 4- methyl -4- (1,1- dimethyl ethyl) -1,7- heptandiol segments, cyclic oligomer in modified poly ester Content be 0.25wt%, number-average molecular weight 24000, molecular weight distributing index 2.2,4- methyl -4- (1,1- in modified poly ester Dimethyl ethyl) -1,7- heptandiol segments molar content be terephthalic acid (TPA) segment molar content 4%；
(2) it oils and is prepared with finish；By 2- methylol -15- crown-s 5 and 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, trimethylolpropane Laurate and dodecyl sodium sulfate obtain finish after mixing and in 55 DEG C of uniform stirring 3h at normal temperatures；By weight Number meter, the addition of each component are as follows：15 parts of trimethylolpropane laurate；5 90 parts of 2- methylol -15- crown-s；Dodecane 8 parts of base phosphate kalium salt；7 parts of dodecyl sodium sulfate.The content of crown ether is 81.81wt% in the finish prepared, finish High temperature resistance is excellent, and thermal weight loss is 10wt% after heating 2h at 200 DEG C, and the viscosity of finish is relatively low, in (50 ± 0.01) DEG C when, kinematic viscosity 29.7mm2/ s, it is 0.94mm that the kinematic viscosity after the lotion of a concentration of 10wt% is configured to water2/ s, The film strength of finish is higher, is 126N.The surface tension of finish is 24.8cN/cm, and specific resistance is 1.8 × 108Ω cm, on After oil, the confficient of static friction (μ between fiber and fiber (F/F)s) it is 0.250, the coefficient of kinetic friction (μd) it is 0.264, after oiling, Confficient of static friction (μ between fiber and metal (F/M)s) it is 0.210, the coefficient of kinetic friction (μd) it is 0.321, the finish of preparation exists In use, being configured to the emulsion of a concentration of 11wt% with water；
(3) modified poly ester viscosified through solid phase polycondensation, melted, measured, squeezed out, cooled down, oiled, stretched, thermal finalization and volume Around obtained high-strength polyester industrial silk, high-strength aircraft safety band is made through weaving in high-strength polyester industrial silk.Wherein, when doubling twisting most Big plying fiber number is 30000dtex, and the inherent viscosity that solid phase polycondensation viscosifies post-modification polyester is 1.0dL/g, and filament spinning component is more It is 45 days to change the period.
The spinning technology parameter of high-strength polyester industrial silk is shown in Table 1.
High-strength polyester industrial silk and final high-strength aircraft safety band various performance parameters obtained are shown in Table 2.
Embodiment 10
The preparation method of high-strength aircraft safety band, is as follows：
(1) modified poly ester is prepared：
(a) 3- methyl -3- amyls -1,6-HD is prepared；At 90 DEG C, under nitrogen atmosphere, by 3- methyl -3- amyls-propionic aldehyde, Then propionic aldehyde and triethylamine react 20min have concentrate addition in the hydrogenation reactor of thunder girl's Raney nickel, in 2.914MPa Hydrogen press and 100 DEG C at react, reaction is finished, cooling, and catalyst is made to be precipitated.After the processing of solution spent ion exchange resin, water is steamed in decompression, Separation, purification, obtains 3- methyl -3- amyl -1,6- hexylene glycols, the wherein structural formula of 3- methyl -3- amyl -1,6- hexylene glycols such as Under：
(b) esterification；It is 1 by molar ratio:1.2:0.06 terephthalic acid (TPA), ethylene glycol and amyl -1 3- methyl -3-, 6- hexylene glycols are made into slurry, and antimony glycol and Trimethyl phosphite is added after mixing, the pressurization progress ester in nitrogen atmosphere Change reaction, the temperature of moulding pressure 0.1MPa, esterification are 255 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 0.01%, phosphorous acid The addition of trimethyl is the 0.01% of terephthalic acid (TPA) weight；
(c) polycondensation reaction；After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, It is 490Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 50min, and reaction temperature is 269 DEG C, reaction time 30min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be further reduced to absolute pressure be 100Pa, instead It is 281 DEG C, reaction time 55min to answer temperature, modified poly ester is made, the strand of wherein modified poly ester includes terephthalic acid (TPA) Segment, ethylene glycol segment and 3- methyl -3- amyl -1,6- hexylene glycol segments, the content of cyclic oligomer is in modified poly ester 0.1wt%, number-average molecular weight 20000, molecular weight distributing index 1.9, in modified poly ester 3- methyl -3- amyls -1,6- oneself two The molar content of alcohol segment is the 3.5% of terephthalic acid (TPA) segment molar content；
(2) it oils and is prepared with finish；By 2- methylol -15- crown-s 5 and 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, trimethylolpropane Laurate and dodecyl sodium sulfate obtain finish after mixing and in 55 DEG C of uniform stirring 3h at normal temperatures；By weight Number meter, the addition of each component are as follows：15 parts of trimethylolpropane laurate；5 90 parts of 2- methylol -15- crown-s；Dodecane 8 parts of base phosphate kalium salt；7 parts of dodecyl sodium sulfate.The content of crown ether is 81.81wt% in the finish prepared, finish High temperature resistance is excellent, and thermal weight loss is 10wt% after heating 2h at 200 DEG C, and the viscosity of finish is relatively low, in (50 ± 0.01) DEG C when, kinematic viscosity 29.7mm2/ s, it is 0.94mm that the kinematic viscosity after the lotion of a concentration of 10wt% is configured to water2/ s, The film strength of finish is higher, is 126N, the surface tension of finish is 24.8cN/cm, and specific resistance is 1.8 × 108Ω cm, on After oil, the confficient of static friction (μ between fiber and fiber (F/F)s) it is 0.250, the coefficient of kinetic friction (μd) it is 0.264, after oiling, Confficient of static friction (μ between fiber and metal (F/M)s) it is 0.210, the coefficient of kinetic friction (μd) it is 0.321, the finish of preparation exists In use, being configured to the emulsion of a concentration of 12wt% with water；
(3) modified poly ester viscosified through solid phase polycondensation, melted, measured, squeezed out, cooled down, oiled, stretched, thermal finalization and volume Around obtained high-strength polyester industrial silk, high-strength aircraft safety band is made through weaving in high-strength polyester industrial silk.Wherein, when doubling twisting most Big plying fiber number is 33000dtex, and the inherent viscosity that solid phase polycondensation viscosifies post-modification polyester is 1.1dL/g, and filament spinning component is more It is 42 days to change the period.
The spinning technology parameter of high-strength polyester industrial silk is shown in Table 1.
High-strength polyester industrial silk and final high-strength aircraft safety band various performance parameters obtained are shown in Table 2.
Embodiment 11
The preparation method of high-strength aircraft safety band, is as follows：
(1) modified poly ester is prepared：
(a) 3,3- diamyl -1,5- pentanediols are prepared；At 95 DEG C, under nitrogen atmosphere, by 3,3- diamyl-propionic aldehyde, acetaldehyde and Triethylamine react 20min, then by concentrate addition have in the hydrogenation reactor of thunder girl's Raney nickel, 2.914MPa hydrogen pressure and It is reacted at 100 DEG C, reaction is finished, cooling, and catalyst is made to be precipitated.After the processing of solution spent ion exchange resin, water is steamed in decompression, detaches, Purification, obtains 3,3- diamyl -1,5-PD, wherein the structural formula of 3,3- diamyl -1,5-PD is as follows：
(b) esterification；It is 1 by molar ratio:2.0:0.03 terephthalic acid (TPA), ethylene glycol and 3,3- diamyl -1,5- Pentanediol is made into slurry, and antimony acetate and Trimethyl phosphite is added after mixing, and pressurizeing in nitrogen atmosphere, it is anti-be esterified It answers, moulding pressure 0.2MPa, the temperature of esterification is 250 DEG C, when the water quantity of distillate in esterification reaches theoretical value It is esterification terminal when 97%, the wherein addition of antimony acetate is the 0.01% of terephthalic acid (TPA) weight, Trimethyl phosphite Addition be terephthalic acid (TPA) weight 0.05%；
(c) polycondensation reaction；After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, It is 500Pa that pressure is steadily evacuated to absolute pressure by normal pressure in 45min, and reaction temperature is 260 DEG C, reaction time 40min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, make reaction pressure be further reduced to absolute pressure be 92Pa, reaction Temperature is 277 DEG C, reaction time 80min, modified poly ester is made, the strand of wherein modified poly ester includes terephthalic acid (TPA) chain Section, ethylene glycol segment and 3,3- diamyl -1,5-PD segment, the content of cyclic oligomer is in modified poly ester 0.35wt%, number-average molecular weight 25500, molecular weight distributing index 1.8,3,3- diamyl -1,5-PD in modified poly ester The molar content of segment is the 5% of terephthalic acid (TPA) segment molar content；
(2) it oils and is prepared with finish；By 2- methylols -12-crown-4 and 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, trimethylolpropane Laurate and dodecyl sodium sulfate are added to after mixing at normal temperatures in 9# mineral oil and in 40 DEG C of uniform stirring 1h Obtain finish；It counts in parts by weight, the addition of each component is as follows：2 parts of 9# mineral oil；Trimethylolpropane laurate 10 Part；2- methylols -90 parts of 12-crown-4；8 parts of 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite；3 parts of dodecyl sodium sulfate.The oil prepared The content of crown ether is 79.6wt% in agent, and the high temperature resistance of finish is excellent, and thermal weight loss is after heating 2h at 200 DEG C The viscosity of 14.5wt%, finish are relatively low, at (50 ± 0.01) DEG C, kinematic viscosity 29.6mm2/ s is configured to a concentration of with water Kinematic viscosity after the lotion of 10wt% is 0.93mm2The film strength of/s, finish are higher, film strength 125N, finish Surface tension is 24.8cN/cm, and specific resistance is 1.3 × 108Ω cm, after oiling, quiet between fiber and fiber (F/F) rubs Wipe coefficient (μs) it is 0.255, the coefficient of kinetic friction (μd) it is 0.266, after oiling, the confficient of static friction between fiber and metal (F/M) (μs) it is 0.203, the coefficient of kinetic friction (μd) it is 0.320, the finish of preparation is configured to a concentration of 15wt%'s when in use, with water Emulsion；
(3) modified poly ester viscosified through solid phase polycondensation, melted, measured, squeezed out, cooled down, oiled, stretched, thermal finalization and volume Around obtained high-strength polyester industrial silk, high-strength aircraft safety band is made through weaving in high-strength polyester industrial silk.Wherein, when doubling twisting most Big plying fiber number is 37000dtex, and the inherent viscosity that solid phase polycondensation viscosifies post-modification polyester is 1.2dL/g, and filament spinning component is more Change the period 47 days.
The spinning technology parameter of high-strength polyester industrial silk is shown in Table 1.
High-strength polyester industrial silk and final high-strength aircraft safety band various performance parameters obtained are shown in Table 2.
Table 1
Table 2
Note：It is (%) that A, which is the central value of the elongation of high-strength polyester industrial silk 4.0cN/dtex loads, in table 2, and B is high-strength The deviation ratio (%) of the elongation of polyester industrial fiber 4.0cN/dtex loads, C are high-strength polyester industrial silk 10min and 0.05cN/ Dry-hot shrinkage (%) under the conditions of dtex.

Claims (10)

1. high-strength aircraft safety band, it is characterized in that：High-strength aircraft safety band is made by high-strength polyester industrial silk weaving, high-strength polyester The material of industrial yarn is modified poly ester, and the strand of modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment and with branch Dihydric alcohol segment, the structural formula of branched dihydric alcohol is as follows：
In formula, R1And R2It is each independently selected from the straight-chain alkyl-sub that carbon atom number is 1~3, R3It is 1~5 selected from carbon atom number Alkyl, R4The alkyl for being 2~5 selected from carbon atom number；
Tensile load value >=14700N of high-strength aircraft safety band.
2. high-strength aircraft safety band according to claim 1, which is characterized in that the fiber number of the high-strength polyester industrial silk is 1100~1670dtex, line density deviation ratio are -1.2~1.5%, fracture strength >=8.1cN/dtex, fracture strength CV values≤ 2.0%, elongation at break central value is 14.0%, and elongation at break deviation ratio is ± 1.0%, extension at break CV value≤6.0%, The central value of the elongation of 4.0cN/dtex loads be the elongation of 5.5~6.2%, 4.0cN/dtex loads deviation ratio be ± 0.8%, dry-hot shrinkage under the conditions of 177 DEG C, 10min and 0.05cN/dtex is 6.0~9.5%, network is 3~9/ M, oil content are 0.35~0.8%.
3. high-strength aircraft safety band according to claim 1 or 2, which is characterized in that cyclic oligomer in the modified poly ester Content≤0.6wt% of object；
The number-average molecular weight 20000~27000 of the modified poly ester, molecular weight distributing index are 1.8~2.2；
In the modified poly ester molar content of branched dihydric alcohol segment be terephthalic acid (TPA) segment molar content 3~ 5%；
The branched dihydric alcohol is 2- Ethyl-2-Methyl -1,3- propylene glycol, 2,2- diethyl -1,3- propylene glycol, 2- fourths Base -2- ethyl -1,3- propylene glycol, 3,3- diethyl -1,5- pentanediols, 4,4- diethyl -1,7- heptandiols, 4,4- bis- (1,-first Base ethyl) -1,7- heptandiols, 3,3- dipropyl -1,5- pentanediols, 4,4- dipropyl -1,7- heptandiols, 4- methyl -4- (1,1- Dimethyl ethyl) -1,7- heptandiols, 3- methyl -3- amyls -1,6-HD or 3,3- diamyl -1,5- pentanediols.
4. high-strength aircraft safety band according to claim 3, which is characterized in that the preparation method of the modified poly ester is： Terephthalic acid (TPA), ethylene glycol and the branched dihydric alcohol are successively subjected to esterification after mixing and polycondensation reaction obtains To modified poly ester.
5. high-strength aircraft safety band according to claim 4, which is characterized in that the specific preparation process of the modified poly ester It is as follows：
(1) esterification；
Terephthalic acid (TPA), ethylene glycol and the branched dihydric alcohol are made into slurry, catalyst is added and stabilizer mixing is equal After even, the pressurization progress esterification in nitrogen atmosphere, moulding pressure is normal pressure~0.3MPa, and the temperature of esterification is 250 ~260 DEG C, be esterification terminal when the water quantity of distillate in esterification reaches 90% or more of theoretical value；
(2) polycondensation reaction；
After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 30~50min Interior to be steadily evacuated to absolute pressure 500Pa hereinafter, reaction temperature is 260~270 DEG C by normal pressure, the reaction time is 30~50min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, so that reaction pressure is further reduced to absolute pressure 100Pa hereinafter, Reaction temperature is 275~285 DEG C, and the reaction time is 50~90min, and modified poly ester is made.
6. high-strength aircraft safety band according to claim 5, which is characterized in that in step (1), terephthalic acid (TPA), second two The molar ratio of alcohol and the branched dihydric alcohol is 1:1.2~2.0:0.03~0.06, the addition of the catalyst is pair The 0.01~0.05% of phthalic acid weight, the addition of the stabilizer are the 0.01~0.05% of terephthalic acid (TPA) weight；
The catalyst is antimony oxide, antimony glycol or antimony acetate, and the stabilizer is triphenyl phosphate, trimethyl phosphate Or Trimethyl phosphite.
7. preparing the method such as the high-strength aircraft safety band of claim 1~6 any one of them, which is characterized in that change described Property polyester is viscosified through solid phase polycondensation, is melted, measuring, squeezing out, cooling down, oiling, stretching, high-strength polyester work is made in thermal finalization and winding High-strength aircraft safety band is made through weaving in industry silk, high-strength polyester industrial silk；
Contain crown ether in the finish to oil, and the content of crown ether is 67.30~85.58wt%；
The finish when in use, the emulsion of a concentration of 10~20wt% is configured to water.
8. the method according to the description of claim 7 is characterized in that the inherent viscosity of solid phase polycondensation thickening post-modification polyester For 1.0~1.2dL/g；
Thermal weight loss is less than 15wt% after the finish heats 2h at 200 DEG C；
For the finish at (50 ± 0.01) DEG C, kinematic viscosity is 27.5~30.1mm2/ s, the finish are configured to concentration with water It is 0.93~0.95mm for the kinematic viscosity after the lotion of 10wt%2/s；
The film strength of the finish is 121~127N；
The surface tension of the finish is 23.2~26.8cN/cm, and specific resistance is 1.0 × 108~1.8 × 108Ω·cm；
After oiling, the confficient of static friction between fiber and fiber is 0.250~0.263, and the coefficient of kinetic friction is 0.262~0.273；
After oiling, the confficient of static friction between fiber and metal is 0.202~0.210, and the coefficient of kinetic friction is 0.320~0.332；
The crown ether is 2- methylols -12-crown-4,15- crown ethers -5 or 2- methylol -15- crown-s 5；
Also contain mineral oil, phosphate kalium salt, trimethylolpropane laurate and sodium alkyl sulfonate in the finish；
The mineral oil is one kind in the mineral oil of 9#~17#；
The phosphate kalium salt is 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, isomerous tridecanol polyoxyethylene ether phosphate kalium salt or 12 Tetrol phosphate kalium salt；
The sodium alkyl sulfonate is dodecyl sodium sulfate, pentadecyl sulfonic acid sodium or sodium cetanesulfonate.
9. according to the method described in claim 8, it is characterized in that, the preparation method of the finish is：By crown ether and phosphate Sylvite, trimethylolpropane laurate and sodium alkyl sulfonate are added in mineral oil are uniformly mixing to obtain oil after mixing Agent；It counts in parts by weight, the addition of each component is as follows：
The mixing carries out at normal temperatures, and the temperature of the stirring is 40~55 DEG C, and the time is 1~3h.
10. according to the method described in claim 9, it is characterized in that, the spinning technology parameter of the high-strength polyester industrial silk such as Under：
295 DEG C of spinning temperature；
The technological parameter of post-heater is：
300~400mm of length；310~330 DEG C of temperature；
The technological parameter of cooling wind is：
700~850Pa of pressure；20~25 DEG C of temperature；
Humidity 75~85%；0.4~0.6m/s of wind speed；
It stretches, the technological parameter of thermal finalization is：
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