WO2020134490A1 - 高模低缩活化型涤纶工业丝及其制备方法 - Google Patents

高模低缩活化型涤纶工业丝及其制备方法 Download PDF

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Publication number
WO2020134490A1
WO2020134490A1 PCT/CN2019/113658 CN2019113658W WO2020134490A1 WO 2020134490 A1 WO2020134490 A1 WO 2020134490A1 CN 2019113658 W CN2019113658 W CN 2019113658W WO 2020134490 A1 WO2020134490 A1 WO 2020134490A1
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Prior art keywords
industrial yarn
reaction
polyester industrial
polyester
activated
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PCT/CN2019/113658
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English (en)
French (fr)
Inventor
汤方明
王山水
杨大矛
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江苏恒力化纤股份有限公司
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Priority to JP2021533197A priority Critical patent/JP7059446B2/ja
Priority to US17/051,442 priority patent/US11174575B2/en
Publication of WO2020134490A1 publication Critical patent/WO2020134490A1/zh

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • 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
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C08G63/86—Germanium, antimony, or compounds thereof
    • C08G63/866—Antimony or compounds thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/096—Humidity control, or oiling, of filaments, threads or the like, leaving the spinnerettes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
    • D01D5/16—Stretch-spinning methods using rollers, or like mechanical devices, e.g. snubbing pins
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
    • D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
    • D02J1/229—Relaxing
    • 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
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/06—Load-responsive characteristics
    • D10B2401/062—Load-responsive characteristics stiff, shape retention
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/06—Load-responsive characteristics
    • D10B2401/063—Load-responsive characteristics high strength

Definitions

  • the invention belongs to the technical field of polyester fibers, and relates to a high-modulus low-shrink activated polyester industrial yarn and a preparation method thereof.
  • Polyester is the trade name of polyester fiber in China, and it is an important variety of synthetic fiber. It is based on terephthalic acid (PAT) or dimethyl terephthalate (DMT) and ethylene glycol (EG) as raw materials. Fiber or polyethylene terephthalate (PET), a fiber-forming polymer obtained by chemical conversion or transesterification and polycondensation, after spinning and post-treatment. Since its inception, PET fiber has a series of excellent properties such as high breaking strength and elastic modulus, moderate resilience, excellent heat setting, good heat and light resistance, acid and alkali resistance, corrosion resistance, etc. It is widely used in industrial and automotive fields .
  • PAT terephthalic acid
  • DMT dimethyl terephthalate
  • EG ethylene glycol
  • PET polyethylene terephthalate
  • PET fiber-forming polymer obtained by chemical conversion or transesterification and polycondensation, after spinning and post-treatment. Since its inception, PET fiber has a series of excellent properties such as high breaking strength and elastic
  • Activated polyester industrial filaments have the advantages of high breaking strength, low elongation at break, and stable dry heat shrinkage; however, compared with viscose and nylon, its bonding performance is relatively poor. Therefore, in the production process, it is generally necessary to perform pretreatment to activate the polyester industrial yarn. The activation and aging process can improve the adhesion between it and rubber products.
  • PET is a symmetrical straight-chain macromolecule
  • its crystalline part of the molecular chains are parallel to each other, and the molecular chain does not contain side chain groups.
  • the regularity is very good.
  • Its main chain contains rigid benzene rings and flexible hydrocarbon groups.
  • the ester group directly connected to the benzene ring and the benzene ring form a rigid conjugated system. All the aromatic rings are almost on the same plane, so the macromolecular structure is dense, easy to crystallize and the crystallinity is large, resulting in fiber orientation.
  • the activator molecules are not easy to enter into the fiber. In the process of industrial yarn activation, it needs to be treated at a higher temperature and a longer time, which causes stress relaxation during the process and affects the mechanical properties of the activated polyester fiber.
  • Shrinkage is an important performance index of industrial yarns. Unlike the reversible thermal expansion and contraction of general solid materials, irreversible thermal shrinkage often occurs after chemical fibers are heated. The shrinkage performance is more pronounced in hot water washing and ironing obvious. Industrial yarns (such as cords, conveyor belts, conveyor belts, etc.) are used at high temperatures for a long time, and their shrinkage performance becomes an important evaluation index. The low-shrinkage polyester industrial yarn has the characteristics of small shrinkage after heating.
  • the purpose of the present invention is to provide a preparation method of high-modulus low-shrink activated polyester industrial yarn with good activation effect and small heat shrinkage in view of the shortcomings of the prior art.
  • the present invention adopts the following technical solutions:
  • the preparation method of high-modulus low-shrinkage activated polyester industrial yarn is to thicken, melt, meter, extrude, cool, oil, stretch, heat-set, relax and heat-treat the activated polyester by solid-phase polycondensation.
  • High-modulus low-shrink activated polyester industrial yarn made by oil, winding and pre-activation treatment;
  • the preparation method of the modified polyester before solid-phase polycondensation and thickening is as follows: terephthalic acid, ethylene glycol and heptane with t-butyl side groups are mixed uniformly, and then the esterification reaction and the polycondensation reaction are carried out successively;
  • R is -H (heptanediol with pendant tert-butyl group is 2,6,6-trimethyl-2,5heptanediol), -CH 2 CH 3 (with pendant tert-butyl group) Heptanediol is 2,6,6-trimethyl-5-ethyl-2,5-heptanediol), -CH(CH 3 ) 2 (heptanediol with tert-butyl pendant group is 2,6 ,6-trimethyl-5-isopropyl-2,5-heptanediol) or -C(CH 3 ) 3 (heptanediol with pendant tert-butyl group is 2,6,6-trimethyl -5-tert-butyl-2,5-heptanediol); the glycol with pendant tert-butyl groups of the present invention can increase the void free volume of the cationic modified polyester, and the pendant with pendant tert-butyl
  • the increase of the free volume of the cavity will help to diffuse some of the activator molecules into the fiber void during the activation process, improve the efficiency of the activator, reduce the activation temperature and shorten the activation time, reduce the mechanical properties of the polyester fiber due to activation Influence, improve the adhesion between products and rubber products.
  • the relaxation heat treatment refers to passing the modified polyester tow through a space of a certain temperature in an appropriate relaxation state
  • the appropriate relaxed state means that the overfeed rate of winding is 3.0 to 5.0%;
  • the certain temperature refers to 200-220°C.
  • the present invention reduces the shrinkage rate of polyester industrial yarn through the mutual coordination of heat treatment temperature and overfeed rate.
  • the macromolecular chains in the amorphous region of the fiber easily form folded chains, which is conducive to the further growth of crystal grains.
  • the crystallinity is increased, the fiber will shrink a certain amount along with the increase in the crystallinity.
  • the present invention eliminates the effect of high elastic deformation on winding, on the other hand, it eliminates the crystallinity. Improve the effect of fiber shrinkage during the process.
  • the high modulus low shrinkage activated polyester industrial yarn has a fineness of 930 to 1670 dtex, a breaking strength ⁇ 7.8 cN/dtex, and a linear density deviation rate of ⁇ 1.2%.
  • Breaking strength CV value ⁇ 2.5% breaking elongation rate is 11.0-13.5%, breaking elongation deviation rate is ⁇ 1.5%
  • breaking elongation CV value ⁇ 8.0% breaking 4.0cN/dtex load elongation rate is 6.0 ⁇ 7.0%
  • the deviation rate of elongation at 4.0 cN/dtex load is ⁇ 0.8%
  • the degree of network is 6 ⁇ 2 ⁇ 3 pieces/m.
  • the processing and mechanical properties of the high modulus low shrinkage activated polyester industrial yarn of the present invention are The performance of the existing low-shrink polyester industrial yarn is comparable;
  • the preparation method of high-modulus low-shrinkage activated polyester industrial yarn as described above has a dry heat shrinkage rate of 2.5 ⁇ 0.5% under the test conditions of 177°C ⁇ 10min ⁇ 0.05cN/dtex, and the vulcanized rubber and The static bonding strength of the fiber cord made from 1100dtex/192F high modulus low shrinkage activated polyester industrial yarn is 49 ⁇ 53N.
  • the vulcanized rubber and the fiber cord made from 1670dtex/192F high modulus low shrinkage activated polyester industrial yarn The static adhesive strength is 55 ⁇ 62N, the dry heat shrinkage rate of the prior art polyester industrial yarn under the same test conditions is 3.0 ⁇ 0.5%.
  • the space at a certain temperature refers to the space between a pair of parallel-arranged and non-coplanar hot plates, which are located in the last set of heat-setting rollers
  • the length of the two hot plates is 3.0 ⁇ 4.0m, the two ends of the two hot plates are flush;
  • the modified polyester tow passes through the middle of the two hot plates Outdated, the distance between it and the two hot plates is 5 ⁇ 10mm;
  • the distance between the last set of heat setting rollers and the winding roller is 300 ⁇ 400mm; the distance between the two hot plates and the last set of heat setting rollers is 200 ⁇ 300mm.
  • the present invention ensures that the rearrangement of large molecules can obtain energy by controlling the temperature of the hot plate (that is, the certain temperature), controlling the length of the hot plate to ensure sufficient crystallization time, and controlling the distance between the tow and the hot plate to ensure the efficiency of heat treatment. Cooperate with each other to improve the integrity of the fiber crystals and reduce the heat shrinkage during the fiber application process.
  • the hot plate temperature is too low, it is difficult to ensure that the large molecule rearrangement can obtain enough energy; too high hot plate temperature will destroy the original The structure formed; the length of the hot plate is too short, and the crystallization time is too short, which affects the integrity of the fiber crystallization and the thermal shrinkage of the fiber; the length of the hot plate is too long, the efficiency is reduced, and the equipment is wasted; Direct contact with the tow; the distance between the tow and the hot plate is too large and the thermal efficiency is reduced.
  • M respectively corresponds to 2,2 -Dimethylpropanal, 2,2-dimethyl-3-pentanone, 2,2,4-trimethyl-3-pentanone and 2,2,4,4-tetramethyl-3-pentan ketone.
  • the preparation steps of the modified polyester before solid-phase polycondensation and thickening are as follows:
  • the polycondensation reaction in the low-vacuum stage is started under negative pressure.
  • the pressure in this stage is steadily pumped from normal pressure to an absolute pressure of 500 Pa or less within 30 to 50 minutes.
  • the reaction temperature is 250 to 260°C and the reaction time is 30 ⁇ 50min, and then continue to evacuate to carry out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to below 100Pa absolute pressure, the reaction temperature is 270 ⁇ 282°C, and the reaction time is 50 ⁇ 90min.
  • the preparation method of the high-modulus low-shrinkage activated polyester industrial yarn as described above the molar ratio of the terephthalic acid, ethylene glycol and heptanediol with pendant t-butyl group is 1:1.2 ⁇ 2.0:0.03 ⁇ 0.05
  • the addition amounts of the catalyst, matting agent and stabilizer are 0.03-0.05wt%, 0.20-0.25wt% and 0.01-0.05wt% of the addition amount of terephthalic acid, respectively.
  • heptanediol with pendant tert-butyl groups can be adjusted within an appropriate range, but it should not be too high or too low, too high will have a certain effect on the mechanical properties of the fiber, too low will not affect the activation of polyester obvious.
  • the catalyst is antimony trioxide, ethylene glycol antimony or antimony acetate
  • the matting agent is titanium dioxide
  • the stabilizer is triphenyl phosphate , Trimethyl phosphate or trimethyl phosphite.
  • the number-average molecular weight of the modified polyester before solid-phase polycondensation and thickening is 30,000 to 35,000, and the molecular weight distribution index is 1.8 to 2.2; solid-phase polycondensation and thickening
  • the intrinsic viscosity of the modified polyester is 1.0 to 1.2 dL/g.
  • the preparation method of the high modulus low shrinkage activated polyester industrial yarn as described above, the spinning process parameters of the high modulus low shrinkage activated polyester industrial yarn are as follows:
  • the process parameters of stretching and heat setting are:
  • the macromolecular chains in the polymer are not completely tightly packed, there are always gaps between the macromolecular chains, and the volume of this part of the void is the free volume.
  • the permeability and diffusivity of the small molecule are related to the size of the void (ie, the size of the free volume) in the polymer structure.
  • the larger the size of the free volume the higher the permeability of small molecules and the better the diffusibility.
  • Free volume is divided into cavity free volume and slit free volume.
  • the cavity free body has a larger space size than the slit free volume.
  • the cavity free volume is more obvious than the slit free volume.
  • the size and type of free volume mainly depend on the structure of the polymer.
  • the main factors affecting the structure of the polymer are steric hindrance, side group size, side group structure, etc.
  • When a position on the polymer main chain is substituted with a pendant group it will inevitably cause changes in the main chain activity, thereby changing the interaction force between chains, and the distance between chains will also change accordingly. This leads to changes in cohesive energy and free volume.
  • the polarity, size, and length of the substituents on the side chain of the polymer have certain effects on the rigidity of the molecular chain, the interaction between molecules, and the free volume fraction of the polymer structure. Therefore, different substituents have different effects, which often lead to different permeation and separation properties of polymers.
  • the C atoms on the main chain are arranged in a zigzag pattern, when the H atom on a methylene group on the main chain is methyl (-CH 3 )
  • the C atom on the side group and the main chain C atom are not in the same plane, so the four sp3 hybrid orbitals on the center C overlap with the empty orbitals on the surrounding four C atoms, forming four identical
  • the ⁇ bond is arranged in a regular tetrahedron.
  • the four carbon atoms are located at the four vertices of the regular tetrahedron.
  • the molecular chains arranged in a regular tetrahedron shape have a much larger free volume of voids, which can significantly improve the permeability and diffusivity of small molecules.
  • the H atom on a methylene group is replaced by a long-branched substituent, the main increase is the free volume of the slit, the increase is small, and the effect of improving the permeability and diffusivity of small molecules is limited.
  • the rigidity of the long-chain branched substituent is small, and the molecular chains are prone to entanglement, which is not conducive to the increase of free volume.
  • the invention significantly improves the activation performance of high-modulus low-shrink activated polyester industrial yarn by introducing heptane with pendant tert-butyl group into the polyester molecular chain.
  • the structural formula of heptane with pendant tert-butyl group is as follows:
  • R is -H, -CH 2 CH 3 , -CH(CH 3 ) 2 or -C(CH 3 ) 3 ;
  • tert-butyl occupies a larger space position, and will obtain a larger free volume in the manner of molecular chain arrangement;
  • the increase in tertiary butyl is hollow, while the increase in long-chain branched substituents is the free volume of the slit, on the other hand, the rigidity of tertiary butyl is greater than that of long-chain branched substituents, reducing the molecular chain
  • the entanglement between the t-butyl longer-chain branched substituents has more free volume in the way the molecular chains are arranged.
  • this shrinkage recovery that is, the shrinkage rate of the fiber will greatly affect the performance of the fiber (such as safety performance, durability, etc.), assuming that the fiber is used as Tire cord, the cord is repeatedly stretched, compressed, and bent during use of the tire, causing the tire to heat, causing the cord to shrink and creep, but when the cord shrinks too much, the cord may be delaminated by the knife, which may cause the tire to disintegrate , Which brings great hidden danger to the safety of tires.
  • the activity of the molecular segment is improved under the condition of a certain temperature and a certain tension Ability to make the molecules more tightly bonded, improve the average size of the crystal grains and crystallinity of the fiber to reduce the shrinkage rate of the fiber, but because the fiber has a certain high elastic deformation during the drawing process, the tension is reduced Elastic recovery will occur, therefore, the speed of the winding head must be lower than the speed of the last set of heat setting rollers, that is, a certain overfeed rate is required to ensure that the stretched yarn is contracted to a certain degree of low tension and a satisfactory finished product is obtained. Quality and package to prevent the package from collapsing due to excessive tension.
  • the overfeed rate should be controlled within a certain range (1 to 2%).
  • the fiber heat setting method is not only tension heat setting, but also relaxation heat setting.
  • Relaxed heat setting is also called free shrink heat setting, that is, the fiber is heat-treated at a certain temperature under completely tension-free or low tension.
  • the fiber Under relaxed heat setting conditions, the fiber can shrink freely in the amorphous region
  • the macromolecular chain is easy to form a folded chain, which is conducive to the further growth of crystal grains, plus more abundant heat treatment time, so after relaxation and heat treatment, the crystallinity of the fiber increases more (compared to tension heat setting), so that the fiber
  • the internal high elasticity becomes restored and the internal stress is fully relaxed, which in turn reduces the shrinkage recovery of the fiber when subjected to heat treatment during application.
  • the current relaxation heat setting is mainly used for heat setting treatment of polyester staple fiber. Its heat treatment temperature is low (about 130 °C), the heat treatment time is long, and it is difficult to apply to filament production.
  • the invention increases the overfeed rate of polyester tow winding to 3 to 5% during the processing of polyester industrial yarn, and at the same time, a pair of up and down is set between the last heat setting roller and the winding roller in the FDY equipment
  • the hot plates arranged in parallel pass the polyester tow through the middle of the two hot plates, which improves the crystallinity of the polyester tow and restores the high elastic deformation inside the polyester tow, so that the internal stress of the polyester tow is certain
  • the amount of slack which in turn reduces the shrinkage recovery of polyester industrial yarns when subjected to heat treatment during application.
  • the present invention reduces the shrinkage of polyester industrial yarn through the combination of heat treatment temperature and higher overfeed rate.
  • the macromolecular chains in its amorphous region are easy to form folded chains, which is conducive to the further development of crystal grains During growth, the crystallinity will increase, and the fiber will shrink by a certain amount with the increase of the crystallinity.
  • the present invention eliminates the effect of high elastic deformation on winding, on the other hand The effect of fiber shrinkage during crystallinity improvement is discussed.
  • the present invention overcomes the defect that the prior art relaxation heat treatment is not suitable for filament production on the one hand through the coordination of the heat treatment temperature, the length of the hot plate and the distance between the tow and the hot plate, on the other hand, it improves the fiber crystallization
  • the integrity of the fiber improves the dimensional stability of the fiber and reduces the heat shrinkage during its application.
  • the preparation method of the high-modulus low-shrinkage activated polyester industrial yarn of the present invention improves the integrity of the fiber crystal and reduces the heat shrinkage during the application process through the cooperation of the heat treatment temperature and the higher overfeed rate ;
  • the preparation method of the high-modulus low-shrinkage activated polyester industrial yarn of the present invention modifies the polyester by heptane with tert-butyl pendant groups, improves the efficiency of the activator, reduces the activation temperature and shortens Activation time to reduce the effect of activation on the mechanical properties of polyester fibers;
  • the preparation method of the high-modulus low-shrinkage activated polyester industrial yarn of the present invention has a simple process, low cost, and great application prospects.
  • a preparation method of high modulus low shrinkage activated polyester industrial yarn the specific steps are as follows:
  • the esterification reaction is carried out under pressure in a nitrogen atmosphere.
  • the pressure is normal pressure
  • the temperature of the esterification reaction is 250°C
  • the addition amounts of antimony trioxide, titanium dioxide and triphenyl phosphate are 0.03wt%, 0.25wt% and 0.01wt% of the addition amount of terephthalic acid, respectively;
  • the polycondensation reaction in the low-vacuum stage is started under negative pressure.
  • the pressure in this stage is steadily pumped from normal pressure to an absolute pressure of 500 Pa within 30 minutes, the reaction temperature is 250° C., the reaction time is 30 minutes, and then the vacuum is continued Carry out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to 100Pa absolute pressure, the reaction temperature is 270°C, the reaction time is 50min, and a modified polyester with a number average molecular weight of 30,000 and a molecular weight distribution index of 1.8 is prepared;
  • the modified polyester is prepared by melting, metering, extruding, cooling, oiling, stretching, heat setting, relaxation heat treatment, oiling with activated oil agent, winding and pre-activation treatment to produce high-molecular low-shrinkage activated type Polyester industrial yarn;
  • Relaxation heat treatment refers to the winding of the polyester yarn bundle with an overfeed rate of 4.9% through a pair of parallel arranged and non-coplanar hot plates with a temperature of 200°C.
  • the hot plates are located in the last group of FDY equipment Between the heat setting roller and the winding roller, the length of the two hot plates is 3.0m along the running direction of the polyester tow. The two ends of the two hot plates are flush.
  • the distance between the two hot plates is 5mm
  • the distance between the last set of heat setting rollers and the winding roller is 300mm
  • the distance between the two hot plates and the last group of heat setting rollers is 200mm;
  • the spinning process parameters are shown in Table 1, and the drawing and heat setting process parameters are shown in Table 2.
  • the resulting high-modulus low-shrink activated polyester industrial yarn has a fineness of 930 dtex, a breaking strength of 7.8 cN/dtex, a linear density deviation of -1.2%, a breaking strength CV of 2.5%, and a breaking elongation of 11.0%
  • the deviation rate of elongation at break is ⁇ 1.5%
  • the CV value of elongation at break is 8.0%
  • the elongation at 4.0 cN/dtex load is 6.0%
  • the deviation at 4.0 cN/dtex load is -0.8%
  • the dry heat shrinkage rate is 2.0%
  • the network degree is 3 pieces/m
  • the vulcanized rubber and the 1100dtex/192F high modulus low shrinkage activated type are measured by the H extraction method
  • the static adhesion strength of the fiber cord made of polyester industrial yarn is 49N
  • a preparation method of polyester industrial yarn is basically the same as that in Example 1, except that the winding speed is 2680m/min without relaxing heat treatment process, the overfeed rate of winding is 1.47%, and the preparation of polyester does not Add 2,6,6-trimethyl-2,5 heptane.
  • the finished polyester industrial yarn has a fineness of 913 dtex, a breaking strength of 7.65 cN/dtex, a linear density deviation of -1.1%, a breaking strength CV of 2.5%, a breaking elongation of 12.7%, and a breaking elongation deviation Rate is ⁇ 1.5%, breaking elongation CV value is 8.0%, 4.0cN/dtex load elongation rate is 6.8%, 4.0cN/dtex load elongation rate deviation rate is -0.8%, at 177°C ⁇ 10min ⁇ 0.05cN/dtex under the test conditions, the dry heat shrinkage rate is 3.2%, the network degree is 3/m, the vulcanized rubber and the 1100dtex/192F high modulus low shrinkage activated polyester industrial yarn are measured by the H extraction method
  • the static bonding strength of the fiber cord is 46N, and the static bonding strength of the vulcanized rubber and the fiber cord made of 1670dtex/192F high modulus low shrinkage activated polyester industrial yarn is 52N
  • a preparation method of polyester industrial yarn is basically the same as that in Example 1, except that the winding speed is 2680 m/min without relaxing heat treatment, and the overfeed rate of winding is 1.47%.
  • the finished polyester industrial yarn has a fineness of 913 dtex, a breaking strength of 7.68 cN/dtex, a linear density deviation of -1.1%, a breaking strength CV of 2.5%, a breaking elongation of 12.5%, and a breaking elongation deviation Rate is ⁇ 1.5%, breaking elongation CV value is 8.0%, 4.0cN/dtex load elongation rate is 6.9%, 4.0cN/dtex load elongation rate deviation rate is -0.8%, at 177°C ⁇ 10min ⁇ 0.05cN/dtex under the test conditions, the dry heat shrinkage rate is 3.2%, the network degree is 3/m, the vulcanized rubber and the 1100dtex/192F high modulus low shrinkage activated polyester industrial yarn are measured by the H extraction method
  • the static bonding strength of the fiber cord is 49N, and the static bonding strength of the vulcanized rubber and the fiber cord made of 1670dtex/192F high-mode low-shrink activated polyester industrial yarn is
  • a method for preparing polyester industrial yarn is basically the same as that in Example 1, except that 2,6,6-trimethyl-2,5 heptane is not added when preparing polyester.
  • the finished polyester industrial yarn has a fineness of 930 dtex, a breaking strength of 7.78 cN/dtex, a linear density deviation of -1.1%, a breaking strength CV of 2.5%, a breaking elongation of 10.8%, and a breaking elongation deviation Rate is ⁇ 1.5%, breaking elongation CV value is 8.0%, 4.0cN/dtex load elongation rate is 6.1%, 4.0cN/dtex load elongation rate deviation rate is -0.8%, at 177°C ⁇ 10min ⁇ 0.05cN/dtex under the test conditions, the dry heat shrinkage rate is 2.1%, the network degree is 3/m, and the vulcanized rubber and the 1100dtex/192F high modulus low shrinkage activated polyester industrial yarn are measured by the H extraction method.
  • the static bonding strength of the fiber cord is 46N
  • the static bonding strength of the vulcanized rubber and the fiber cord made of 1670dtex/192F high modulus low shrinkage activated polyester industrial yarn is
  • Example 1 improves the use efficiency of the activator by adding 2,6,6-trimethyl-2,5 heptane, and significantly improves the activation of polyester industrial yarn Performance, relaxation heat treatment process can significantly reduce the dry heat shrinkage rate of polyester industrial yarn.
  • a method for preparing polyester industrial yarn is basically the same as in Example 1, except that 1,2-dodecyl diol is used instead of 2,6,6-trimethyl-2,5heptane when preparing polyester alcohol.
  • the finished polyester industrial yarn has a fineness of 930 dtex, a breaking strength of 7.77 cN/dtex, a linear density deviation of -1.1%, a breaking strength CV of 2.5%, a breaking elongation of 10.8%, and a breaking elongation deviation Rate is ⁇ 1.5%
  • breaking elongation CV value is 8.0%
  • 4.0cN/dtex load elongation rate is 6.0%
  • 4.0cN/dtex load elongation rate deviation rate is -0.8%
  • the dry heat shrinkage rate is 2.1%
  • the network degree is 3/m
  • the vulcanized rubber and the 1100dtex/192F high modulus low shrinkage activated polyester industrial yarn are measured by the H extraction method.
  • the static bonding strength of the fiber cord is 46N
  • the static bonding strength of the vulcanized rubber and the fiber cord made of 1670dtex/192F high modulus low shrinkage activated polyester industrial yarn is 52N.
  • Example 1 Compared with Example 1, it can be found that the glycol with pendant tert-butyl group is more beneficial to the activation performance of the fiber than the 1,2-dodecyl diol with long-chain branched substituents, mainly because In terms of tert-butyl pendant diols, the increased free volume of the tert-butyl group is more of the void free volume, and the increased free volume of the long-chain branched substituents is more of the slit free volume.
  • the rigidity of the tert-butyl group in the glycol with pendant tert-butyl groups is greater than that of long-chain branched substituents, which reduces the entanglement between the molecular chains, so the glycol with pendant tert-butyl groups contains longer
  • the 1,2-dodecyl diol with branched substituents has more free volume in the way the polyester molecular chains are arranged, which is conducive to the penetration of the activator, which is more conducive to improving the activation performance of the fiber.
  • a preparation method of high modulus low shrinkage activated polyester industrial yarn the specific steps are as follows:
  • the pressure is 0.15 MPa
  • the temperature of the esterification reaction is 252°C
  • the amount of water distilled in the esterification reaction reaches 91% of the theoretical value is
  • the addition amounts of antimony trioxide, titanium dioxide and triphenyl phosphate are 0.035wt%, 0.22wt% and 0.015wt% of the addition amount of terephthalic acid, respectively;
  • the polycondensation reaction in the low-vacuum stage starts under negative pressure.
  • the pressure in this stage is steadily pumped from normal pressure to absolute pressure within 498 Pa, the reaction temperature is 252 °C, the reaction time is 32 min, and then continue to evacuate Carry out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to 99Pa absolute pressure, the reaction temperature is 272°C, the reaction time is 55min, and a modified polyester with a number average molecular weight of 30500 and a molecular weight distribution index of 1.85 is prepared;
  • the modified polyester is prepared by melting, metering, extruding, cooling, oiling, stretching, heat setting, relaxation heat treatment, oiling with activated oil agent, winding and pre-activation treatment to produce high-molecular low-shrinkage activated type Polyester industrial yarn;
  • Relaxation heat treatment refers to the winding of the polyester yarn bundle with an overfeed rate of 4.2% through a pair of parallel arranged and non-coplanar hot plates with a temperature of 202°C.
  • the hot plates are located in the last group of FDY equipment Between the heat setting roller and the winding roller, along the running direction of the polyester tow, the length of the two hot plates is 3.2m, the two ends of the two hot plates are flush, when the polyester tow passes through the middle of the two hot plates, the The distance between the two hot plates is 6mm, the distance between the last set of heat setting rollers and the winding roller is 311mm, and the distance between the two hot plates and the last group of heat setting rollers is 220mm;
  • the spinning process parameters are shown in Table 1, and the drawing and heat setting process parameters are shown in Table 2.
  • the final high-density low-shrink activated polyester industrial yarn has a fineness of 1070 dtex, a breaking strength of 8.0 cN/dtex, a linear density deviation of -1.0%, a breaking strength CV of 2.1%, and a breaking elongation of 12.5%
  • the deviation rate of elongation at break is -1.2%
  • the CV value of elongation at break is 7.5%
  • the elongation at 4.0 cN/dtex load is 6.2%
  • the deviation at 4.0 cN/dtex load is -0.6%
  • the dry heat shrinkage rate is 2.2%
  • the network degree is 6/m
  • the vulcanized rubber and the high-mode low-shrinkage activated type measured by 1100dtex/192F are measured by the H extraction method.
  • the static adhesion strength of the fiber cord made of polyester industrial yarn is 50N, and the static adhesion strength of the vulcanized rubber and the fiber cord made of 1670dtex/192F high-mode low-shrink activated polyester industrial yarn is 57N.
  • a preparation method of high modulus low shrinkage activated polyester industrial yarn the specific steps are as follows:
  • the polycondensation reaction in the low-vacuum stage is started under negative pressure.
  • the pressure in this stage is steadily pumped from normal pressure to absolute pressure in 497 Pa, the reaction temperature is 253 °C, the reaction time is 35 min, and then continue to vacuum Carry out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to 98Pa absolute pressure, the reaction temperature is 274°C, the reaction time is 62min, and a modified polyester with a number average molecular weight of 32,000 and a molecular weight distribution index of 1.9 is prepared;
  • the modified polyester is prepared by melting, metering, extruding, cooling, oiling, stretching, heat setting, relaxation heat treatment, oiling with activated oil agent, winding and pre-activation treatment to produce high-molecular low-shrinkage activated type Polyester industrial yarn;
  • Relaxation heat treatment refers to the winding of the polyester yarn bundle with an overfeed rate of 3.3% through a pair of parallel arranged and non-coplanar hot plates with a temperature of 210°C.
  • the hot plates are located in the last group of FDY equipment Between the heat setting roller and the winding roller, along the running direction of the polyester tow, the length of the two hot plates is 3.3m, the two ends of the two hot plates are flush, when the polyester tow passes through the middle of the two hot plates, the The distance between the two hot plates is 7mm, the distance between the last set of heat setting rollers and the winding roller is 335mm, and the distance between the two hot plates and the last group of heat setting rollers is 235mm;
  • the spinning process parameters are shown in Table 1, and the drawing and heat setting process parameters are shown in Table 2.
  • the resulting high-modulus low-shrink activated polyester industrial yarn has a fineness of 1170 dtex, a breaking strength of 8.3 N/dtex, a linear density deviation of -0.2%, a breaking strength CV of 2.3%, and a breaking elongation of 12.5% ,
  • the elongation at break deviation rate is 1.0%
  • the elongation at break CV value is 7.0%
  • the elongation at 4.0 cN/dtex load is 6.6%
  • the elongation at 4.0 cN/dtex load is 0.3%.
  • the dry heat shrinkage rate is 2.6%
  • the network degree is 8 pieces/m.
  • the vulcanized rubber and the 1100dtex/192F high modulus low shrinkage activated polyester industry are measured by the H extraction method.
  • the static adhesion strength of the fiber cord made of silk is 52N
  • the static adhesion strength of the vulcanized rubber and the fiber cord made of 1670dtex/192F high modulus low shrinkage activated polyester industrial yarn is 58N.
  • a preparation method of high modulus low shrinkage activated polyester industrial yarn the specific steps are as follows:
  • the polycondensation reaction in the low-vacuum stage is started under negative pressure.
  • the pressure in this stage is steadily pumped from normal pressure to absolute pressure within 495 Pa, the reaction temperature is 255 °C, the reaction time is 38 minutes, and then continue to evacuate Carry out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to an absolute pressure of 97Pa, the reaction temperature is 276°C, the reaction time is 67min, and a modified polyester with a number average molecular weight of 32,000 and a molecular weight distribution index of 1.92 is prepared;
  • the modified polyester is prepared by melting, metering, extruding, cooling, oiling, stretching, heat setting, relaxation heat treatment, oiling with activated oil agent, winding and pre-activation treatment to produce high-molecular low-shrinkage activated type Polyester industrial yarn;
  • Relaxation heat treatment refers to the winding of the polyester yarn bundle with an overfeed rate of 4.8% through a pair of parallel arranged and non-coplanar hot plates with a temperature of 240°C.
  • the hot plates are located in the last group of FDY equipment Between the heat setting roller and the winding roller, along the running direction of the polyester tow, the length of the two hot plates is 3.4m, the two ends of the two hot plates are flush, when the polyester tow passes through the middle of the two hot plates, the The distance between the two hot plates is 8mm, the distance between the last set of heat setting rollers and the winding roller is 346mm, and the distance between the two hot plates and the last group of heat setting rollers is 250mm;
  • the spinning process parameters are shown in Table 1, and the drawing and heat setting process parameters are shown in Table 2.
  • the resulting high-modulus low-shrink activated polyester industrial yarn has a fineness of 1370 dtex, a breaking strength of 7.9 cN/dtex, a linear density deviation rate of 1.0%, a breaking strength CV value of 2.4%, and a breaking elongation rate of 12.0%.
  • the elongation at break deviation rate is 1.0%, the elongation at break CV value is 6.9%, the elongation at 4.0 cN/dtex load is 6.5%, and the elongation at 4.0 cN/dtex load is 0.3%, at 177
  • the dry heat shrinkage rate is 2.7%
  • the network degree is 7 pieces/m
  • the vulcanized rubber and the 1100dtex/192F high modulus low shrinkage activated polyester industrial yarn are measured by the H extraction method.
  • the static adhesion strength of the prepared fiber cord is 52N, and the static adhesion strength of the vulcanized rubber and the fiber cord made from 1670dtex/192F high-mode low-shrink activated polyester industrial yarn is 59N.
  • a preparation method of high modulus low shrinkage activated polyester industrial yarn the specific steps are as follows:
  • the polycondensation reaction in the low-vacuum stage starts under negative pressure.
  • the pressure in this stage is steadily pumped from normal pressure to absolute pressure within 492 Pa, the reaction temperature is 256 °C, the reaction time is 40 minutes, and then continue to vacuum Carry out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to 95Pa absolute pressure, the reaction temperature is 278°C, the reaction time is 72min, and a modified polyester with a number average molecular weight of 33030 and a molecular weight distribution index of 1.95 is prepared;
  • the modified polyester is prepared by melting, metering, extruding, cooling, oiling, stretching, heat setting, relaxation heat treatment, oiling with activated oil agent, winding and pre-activation treatment to produce high-molecular low-shrinkage activated type Polyester industrial yarn;
  • Relaxation heat treatment refers to passing the wound polyester tow with a 4.0% overfeed rate through a pair of parallel arranged and non-coplanar hot plates with a temperature of 220°C.
  • the hot plates are located in the last group of FDY equipment Between the heat setting roller and the winding roller, along the running direction of the polyester tow, the length of the two hot plates is 3.6m, the two ends of the two hot plates are flush, when the polyester tow passes through the middle of the two hot plates, the The distance between the two hot plates is 8.5mm, the distance between the last set of heat setting rollers and the winding roller is 368mm, and the distance between the two hot plates and the last group of heat setting rollers is 260mm;
  • the spinning process parameters are shown in Table 1, and the drawing and heat setting process parameters are shown in Table 2.
  • the final high-density low-shrink activated polyester industrial yarn has a fineness of 1290 dtex, a breaking strength of 8.3 cN/dtex, a linear density deviation rate of 1.0%, a breaking strength CV value of 2.3%, and a breaking elongation of 12.9%.
  • the deviation rate of elongation at break is 1.0%, the CV value of elongation at break is 6.6%, the elongation at 4.0 cN/dtex load is 6.2%, and the deviation at 4.0 cN/dtex load is 0.1%, at 177
  • the dry heat shrinkage rate is 2.6%
  • the network degree is 8 pieces/m
  • the vulcanized rubber and the 1100dtex/192F high-mode low-shrink activated polyester industrial yarn are measured by the H extraction method.
  • the static bonding strength of the prepared fiber cord is 42N, and the static bonding strength of the vulcanized rubber and the fiber cord made from 1670dtex/192F high-mode low-shrink activated polyester industrial yarn is 60N.
  • a preparation method of high modulus low shrinkage activated polyester industrial yarn the specific steps are as follows:
  • the addition amounts of antimony acetate, titanium dioxide and trimethyl phosphite are 0.05wt%, 0.20wt% and 0.04wt% of the addition amount of terephthalic acid, respectively;
  • the polycondensation reaction in the low-vacuum stage is started under negative pressure.
  • the pressure in this stage is steadily pumped from atmospheric pressure to absolute pressure within 490 Pa, the reaction temperature is 258 °C, the reaction time is 42 minutes, and then continue to vacuum Carry out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to an absolute pressure of 94Pa, the reaction temperature is 280°C, the reaction time is 82min, and a modified polyester with a number average molecular weight of 34400 and a molecular weight distribution index of 1.96 is prepared;
  • the modified polyester is prepared by melting, metering, extruding, cooling, oiling, stretching, heat setting, relaxation heat treatment, oiling with activated oil agent, winding and pre-activation treatment to produce high-molecular low-shrinkage activated type Polyester industrial yarn;
  • Relaxation heat treatment refers to passing the wound polyester tow with a 3.0% overfeed rate through a pair of parallel arranged and non-coplanar hot plates with a temperature of 215°C.
  • the hot plates are located in the last group of FDY equipment Between the heat setting roller and the winding roller, along the running direction of the polyester tow, the length of the two hot plates is 3.8m, the two ends of the two hot plates are flush, when the polyester tow passes through the middle of the two hot plates, the The distance between the two hot plates is 9mm, the distance between the last set of heat setting rollers and the winding roller is 384mm, and the distance between the two hot plates and the last group of heat setting rollers is 280mm;
  • the resulting high-modulus low-shrink activated polyester industrial yarn has a fineness of 1570 dtex, a breaking strength of 7.9 cN/dtex, a linear density deviation rate of 1.0%, a breaking strength CV value of 2.4%, and a breaking elongation of 13.0%.
  • the elongation at break deviation rate is 1.2%
  • the elongation at break CV value is 6.6%
  • the elongation at 4.0 cN/dtex load is 7.0%
  • the elongation at 4.0 cN/dtex load is 0.8%, at 177
  • the dry heat shrinkage rate is 2.7%
  • the network degree is 6 pieces/m
  • the vulcanized rubber and the 1100dtex/192F high-mode low-shrink activated polyester industrial yarn are measured by the H extraction method.
  • the static bonding strength of the prepared fiber cord is 51N
  • the static bonding strength of the vulcanized rubber and the fiber cord made from 1670dtex/192F high-mode low-shrink activated polyester industrial yarn is 61N.
  • a preparation method of high modulus low shrinkage activated polyester industrial yarn the specific steps are as follows:
  • Potassium isobutoxide is prepared by mixing potassium hydroxide aqueous solution and isobutanol at a molar ratio of 5.5:1 of isobutanol to potassium hydroxide, and reacting at a temperature of 100°C for 4 hours. With stirring, the mass concentration of the potassium hydroxide aqueous solution is 46%;
  • the polycondensation reaction in the low-vacuum stage is started under negative pressure.
  • the pressure in this stage is steadily pumped from normal pressure to absolute pressure 490 Pa within 50 minutes, the reaction temperature is 260 °C, the reaction time is 50 minutes, and then continue to vacuum Carry out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to an absolute pressure of 92Pa, the reaction temperature is 282°C, the reaction time is 90min, and a modified polyester with a number average molecular weight of 35,000 and a molecular weight distribution index of 2.2 is prepared;
  • the modified polyester is prepared by melting, metering, extruding, cooling, oiling, stretching, heat setting, relaxation heat treatment, oiling with activated oil agent, winding and pre-activation treatment to produce high-molecular low-shrinkage activated type Polyester industrial yarn;
  • Relaxation heat treatment refers to passing the wound polyester tow with a super-feed rate of 5.0% through a pair of parallel arranged and non-coplanar hot plates with a temperature of 220°C.
  • the hot plates are located in the last group of FDY equipment Between the heat setting roller and the winding roller, the length of the two hot plates is 4.0m along the running direction of the polyester tow. The two ends of the two hot plates are flush.
  • the distance between the two hot plates is 10mm
  • the distance between the last set of heat setting rollers and the winding roller is 400mm
  • the distance between the two hot plates and the last group of heat setting rollers is 300mm;
  • the spinning process parameters are shown in Table 1, and the drawing and heat setting process parameters are shown in Table 2.
  • the resulting high-modulus low-shrink activated polyester industrial yarn has a fineness of 1670 dtex, a breaking strength of 8.5 cN/dtex, a linear density deviation rate of 1.2%, a breaking strength CV value of 2.0%, and a breaking elongation rate of 13.5%.
  • the elongation at break deviation rate is 1.5%
  • the elongation at break CV value is 6.4%
  • the elongation at 4.0 cN/dtex load is 7.0%
  • the elongation at 4.0 cN/dtex load is 0.8%, at 177
  • the dry heat shrinkage rate is 3.0%
  • the network degree is 9 pieces/m.
  • the vulcanized rubber and the 1100dtex/192F high modulus low shrinkage activated polyester industrial yarn are measured by the H extraction method.
  • the static adhesion strength of the prepared fiber cord is 53N
  • the static adhesion strength of the vulcanized rubber and the fiber cord made from 1670dtex/192F high-mode low-shrink activated polyester industrial yarn is 62N.

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Abstract

本发明涉及一种高模低缩活化型涤纶工业丝及其制备方法，制备方法为：先将对苯二甲酸、乙二醇和带叔丁基侧基的庚二醇混合均匀后先后进行酯化反应和缩聚反应制得改性聚酯，然后将改性聚酯经固相缩聚增粘、熔融、计量、挤出、冷却、上油、拉伸、热定型、松弛热处理、活化油剂上油、卷绕和预活化处理制得高模低缩活化型涤纶工业丝，松弛热处理是指将聚酯丝束在适当的松弛状态经过一定温度的空间，适当的松弛状态是指卷绕的超喂率为3.0～5.0％，一定温度是指200～220℃。本发明通过带叔丁基侧基的庚二醇对聚酯进行改性，提高了活化剂的使用效率，又通过热处理温度与较高的超喂率的相互配合，减少了其应用过程中的热收缩，工艺简单。

Description

高模低缩活化型涤纶工业丝及其制备方法 技术领域
本发明属于聚酯纤维技术领域，涉及一种高模低缩活化型涤纶工业丝及其制备方法。
背景技术
涤纶是我国聚酯纤维的商品名称，是合成纤维中的一个重要品种，是以对苯二甲酸(PAT)或对苯二甲酸二甲酯(DMT)和乙二醇(EG)为原料经酯化或酯交换和缩聚反应而制得的成纤高聚物—聚对苯二甲酸乙二醇酯(PET)，经纺丝和后处理制成的纤维。PET纤维自问世以来，具有断裂强度和弹性模量高、回弹性适中、热定型优异、耐热耐光性好以及耐酸耐碱耐腐蚀性等一系列优良性能，广泛地应用于工业和汽车等领域。
活化型涤纶工业长丝具有断裂强度高、断裂伸长率小、干热收缩率稳定的优点；然而与粘胶和尼龙相比，它的粘合性能比较差。因此，在生产过程中，一般要先进行预处理使涤纶工业丝活化。活化、熟成工序可提高其与橡胶制品间的粘合力。
但由于PET属于对称性的直链大分子，其结晶部分分子链相互平行，且分子链不含有侧链基团，规整性非常好，它的主链含有刚性的苯环和柔性的烃基，而直接与苯环相连接的酯基与苯环又构成了刚性的共轭体系，所有的芳环几乎都在同一平面上，因此大分子结构致密，易于结晶且结晶度较大，导致纤维取向度较高，活化剂分子不易进入纤维内部，在工业丝活化的过程中需在较高温度、较长时间条件下进行处理，在过程中造成应力松驰，影响到活化涤纶纤维力学性能。
另外，随着基础工业发展、高新技术应用和消费水平的提高，行业对涤纶工业丝的质量和性能提出了更高的要求。此外，随着市场的逐渐饱和，开发性能更为优异的产品也是发展的必然要求。收缩率是工业丝的一项重要性能指标，与一般固体物质可逆的热胀冷缩现象不同，化学纤维受热后，往往发生不可逆热收缩，在热水洗涤和熨烫时，收缩表现得更为明显。工业丝(如帘子线、运输带和传送带等)更在长时间的高温下进行使用，其收缩率的表现就更加成为一项重要的评价指标。低收缩型涤纶工业丝具有受热后收缩小的特点，其织物或由其制成的橡胶制品具有良好的尺寸稳定性和耐热稳定性，能吸收冲击负荷。主要用于制备涂层织物、输送带纬线等。虽然现有技术通过控制超喂率并进行紧张热定型也能制得低收缩型涤纶工业丝，但由于紧张热定型过程中纤维的长度被固定不可改变，会抑制大分子链的折叠，限制晶粒的生长，导致结晶存在缺陷，这会影响工业丝的热收缩率的进一步减小。
因此，研究一种活化效果好以及热收缩率小的高模低缩活化型涤纶工业丝的制备方法极具现实意义。
发明内容
本发明的目的是针对现有技术的不足，提供一种活化效果好以及热收缩小的高模低缩活化型涤纶工业丝的制备方法。
为实现上述目的，本发明采用如下技术方案：
高模低缩活化型涤纶工业丝的制备方法，将改性聚酯经固相缩聚增粘、熔融、计量、挤出、冷却、上油、拉伸、热定型、松弛热处理、活化油剂上油、卷绕和预活化处理制得高模低缩活化型涤纶工业丝；
固相缩聚增粘前的改性聚酯的制备方法为：将对苯二甲酸、乙二醇和带叔丁基侧基的庚二醇混合均匀后先后进行酯化反应和缩聚反应；
带叔丁基侧基的庚二醇的结构式如下：
Figure PCTCN2019113658-appb-000001
式中，R为-H(带叔丁基侧基的庚二醇为2,6,6-三甲基-2,5庚二醇)、-CH 2CH 3(带叔丁基侧基的庚二醇为2,6,6-三甲基-5-乙基-2,5-庚二醇)、-CH(CH 3) 2(带叔丁基侧基的庚二醇为2,6,6-三甲基-5-异丙基-2,5-庚二醇)或-C(CH 3) 3(带叔丁基侧基的庚二醇为2,6,6-三甲基-5-叔丁基-2,5-庚二醇)；本发明的带叔丁基侧基的二元醇能够增大阳离子改性聚酯的空洞自由体积，带叔丁基侧基的二元醇中的叔丁基的存在会引起主链活动性的变化，从而改变了链单元间 的相互作用力，分子链单元间的距离亦会发生相应的改变，导致改性聚酯的空洞自由体积增大。空洞自由体积的增大将有助于在活化过程中使部分活化剂分子扩散进入到纤维空隙中，提高了活化剂的效率，降低活化温度和缩短活化时间，降低因活化对聚酯纤维力学性能的影响，提高产品与橡胶制品间的粘合作用。
所述松弛热处理是指将改性聚酯丝束在适当的松弛状态经过一定温度的空间；
所述适当的松弛状态是指卷绕的超喂率为3.0～5.0％；
所述一定温度是指200～220℃。
本发明通过热处理温度与超喂率的相互配合以降低聚酯工业丝的收缩率，纤维在热处理时，其非晶区内的大分子链容易形成折叠链，有利于晶粒的进一步生长，此时结晶度升高，伴随着结晶度的升高，纤维会产生一定量的收缩，本发明通过提高超喂率，一方面消除了高弹形变对卷绕的影响，另一方面消除了结晶度提高过程中纤维的收缩的影响。
作为优选的技术方案：
如上所述的高模低缩活化型涤纶工业丝的制备方法，高模低缩活化型涤纶工业丝的纤度为930～1670dtex，断裂强度≥7.8cN/dtex，线密度偏差率为±1.2％，断裂强度CV值≤2.5％，断裂伸长率为11.0～13.5％，断裂伸长率偏差率为±1.5％，断裂伸长CV值≤8.0％，4.0cN/dtex负荷的伸长率为6.0～7.0％，4.0cN/dtex负荷的伸长率的偏差率为±0.8％，网络度为6±2～3个/m，本发明的高模低缩活化型涤纶工业丝的加工及机械性能与现有技术的低收缩聚酯工业丝性能相当；
如上所述的高模低缩活化型涤纶工业丝的制备方法，在177℃×10min×0.05cN/dtex的测试条件下的干热收缩率为2.5±0.5％，采用H抽出法测得硫化橡胶与由1100dtex/192F高模低缩活化型涤纶工业丝制得的纤维帘线的静态粘合强度为49～53N，硫化橡胶与由1670dtex/192F高模低缩活化型涤纶工业丝制得的纤维帘线的静态粘合强度55～62N，现有技术的聚酯工业丝在相同测试条件下的干热收缩率3.0±0.5％。
如上所述的高模低缩活化型涤纶工业丝的制备方法，所述一定温度的空间是指一对平行排列且非共面的热板之间的空间，热板位于最后一组热定型辊与卷绕辊之间；沿改性聚酯丝束的运行方向，两热板的长度为3.0～4.0m，两热板的两端齐平；改性聚酯丝束从两热板中间穿过时，其与两热板之间的距离为5～10mm；最后一组热定型辊与卷绕辊之间的间距为300～400mm；两热板与最后一组热定型辊之间的间距为200～300mm。本发明通过控制热板温度(即所述一定温度)保证大分子重排能够获得能量，控制热板的长度以保证足够结晶时间，控制丝束与热板的距离以保证热处理的效率，三者相互协同配合，提高纤维结晶的完整性，进而减少纤维应用过程中的热收缩，其中，热板温度过低，难以保证大分子重排能够获得足够的能量；热板温度过高会破坏原已形成的结构；热板长度过短，结晶时间过短，影响纤维结晶的完整性，影响纤维热收缩率；热板长度过长效率下降造设备浪费；丝束与热板的距离过小容易造成与丝束的直接接触；丝束与热板的距离过大热效率降低。
如上所述的高模低缩活化型涤纶工业丝的制备方法，所述带叔丁基侧基的庚二醇的合成步骤如下：
(1)按异丁醇与氢氧化钾的摩尔比为5～6:1的比例将氢氧化钾水溶液和异丁醇混合，在100～110℃的温度条件下反应4～5h制得异丁醇钾，反应时伴以搅拌，氢氧化钾水溶液的质量浓度为40～50％；
(2)去除(1)的体系内的杂质并降至常温后，按异丁醇钾与二甲苯的摩尔比为1.3～1.5:2.0～3.0的比例向(1)的体系内加入二甲苯，冷却至0～5℃；
(3)向(2)的体系内加入3-甲基-3-羟基丁炔和M后，在25～35℃的温度条件下反应3h，再进行冷却结晶、离心分离和干燥得到辛炔二醇，反应开始时，3-甲基-3-羟基丁炔、M与二甲苯的摩尔比为1:1.2～1.3:2.0～3.0；
(4)按2～3:10:0.01～0.03的重量比将辛炔二醇、乙醇和钯催化剂混合，在40～50℃的温度条件下反应50～60min，反应过程中持续通入氢气，反应结束后进行分离和提纯得到带叔丁基侧基的庚二醇；
所述带叔丁基侧基的庚二醇的结构式中R为-H、-CH 2CH 3、-CH(CH 3) 2和-C(CH 3) 3时，M分别对应为2,2-二甲基丙醛、2,2-二甲基-3-戊酮、2,2,4-三甲基-3-戊酮和2,2,4,4-四甲基-3-戊酮。
如上所述的高模低缩活化型涤纶工业丝的制备方法，固相缩聚增粘前的改性聚酯的制备步骤如下：
(1)酯化反应；
将对苯二甲酸、乙二醇和带叔丁基侧基的庚二醇配成浆料，加入催化剂、消光剂和稳定剂混合均匀后，在氮气氛围中加压进行酯化反应，加压压力为常压～0.3MPa，酯化反应的温度为250～260℃，当酯化反应中的水馏出量达到理论值的90％以上时为酯化反应终点；
(2)缩聚反应；
酯化反应结束后，在负压条件下开始低真空阶段的缩聚反应，该阶段压力在30～50min内由常压平稳抽至绝对压力500Pa以下，反应温度为250～260℃，反应时间为30～50min，然后继续抽真空，进行高真空阶段的缩聚反应，使反应压力进一步降至绝对压力100Pa以下，反应温度为270～282℃，反应时间为50～90min。
如上所述的高模低缩活化型涤纶工业丝的制备方法，所述对苯二甲酸、乙二醇和带叔丁基侧基的庚二醇的摩尔比为1:1.2～2.0:0.03～0.05，所述催化剂、消光剂和稳定剂的加入量分别为对苯二甲酸加入量的0.03～0.05wt％、0.20～0.25wt％和0.01～0.05wt％。带叔丁基侧基的庚二醇的含量可在适当范围内进行调整，但是不宜过高或过低，过高会对纤维的力学性能产生一定的影响，过低对聚酯的活化作用不明显。
如上所述的高模低缩活化型涤纶工业丝的制备方法，所述催化剂为三氧化二锑、乙二醇锑或醋酸锑，所述消光剂为二氧化钛，所述稳定剂为磷酸三苯酯、磷酸三甲酯或亚磷酸三甲酯。
如上所述的高模低缩活化型涤纶工业丝的制备方法，固相缩聚增粘前的改性聚酯的数均分子量为30000～35000，分子量分布指数为1.8～2.2；固相缩聚增粘后的改性聚酯的特性粘度为1.0～1.2dL/g。
如上所述的高模低缩活化型涤纶工业丝的制备方法，所述高模低缩活化型涤纶工业丝的纺丝工艺参数如下：
Figure PCTCN2019113658-appb-000002
拉伸、热定型的工艺参数为：
Figure PCTCN2019113658-appb-000003
发明机理：
聚合物中的大分子链不是完全紧密的堆砌，在大分子链之间总是有空隙存在，这部分空隙体积即为自由体积。要使小分子渗透到高分子内部，高分子内或高分子间要有足够大的空隙，所以小分子的渗透率和扩散性与高分子结构中的空隙大小(即自由体积的尺寸)有关，在一定范围内，自由体积的尺寸越大，小分子的渗透率越高，扩散性越好。自由体积又分为空洞自由体积和狭缝自由体积，空洞自由体较狭缝自由体积具更大的空间尺寸，对于小分子的渗透率的提升，空洞自由体积较狭缝自由体积效果更加明显。
自由体积的尺寸和类型主要取决于聚合物的结构，影响聚合物结构的主要因素为立体阻碍、侧基大小、侧基结构等。当聚合物主链上某一位置被侧基取代时，必然引起主链活动性的变化，从而改变了链与链间的相互作用力，链与链间的距离亦会发生相应的改变，结果导致内聚能和自由体积的变化，高分子侧链上的取代基的极性、大小、长短等对分子链的刚性、分子间的相互作用乃至聚合物结构的自由体积分数都有一定的影响，因此，取代基不同产生的效应不同，往往导致聚合物的渗透分离性能也各不相同。
对于乙二醇、丁二醇等二元醇直链分子，主链上的C原子处于一上一下呈锯齿形排列，当主链上某个亚甲基上 的H原子被甲基(-CH 3)取代时，侧基上的C原子与主链C原子不在同一平面内，于是，中心C上的四个sp3杂化轨道分别与周围四个C原子上的空轨道重叠，形成四个完全相同的σ键，呈正四面体排列，四个碳原子分别位于正四面体的四个顶点，当甲基的三个氢进一步被甲基取代时，这时就相当于叔丁基取代，形成一个更大的四面体结构，这种呈正四面体形排列的分子链相对于呈锯齿形排列的分子链，空洞自由体积明显增大了很多，能够显著提高小分子的渗透率和扩散性；而当主链上某个亚甲基上的H原子被长支链取代基取代时，主要增大的是狭缝自由体积，增大幅度较小，对小分子的渗透率和扩散性的提升效果有限，同时由于长支链取代基的刚性较小，分子链之间容易发生缠结，不利于自由体积的增大。
本发明通过在聚酯分子链中引入带叔丁基侧基的庚二醇显著提升了高模低缩活化型涤纶工业丝的活化性能，带叔丁基侧基的庚二醇的结构式如下：
Figure PCTCN2019113658-appb-000004
式中，R为-H、-CH 2CH 3、-CH(CH 3) 2或-C(CH 3) 3；
带叔丁基侧基的庚二醇中叔丁基的存在会引起主链活动性的变化，从而改变了链单元间的相互作用力，分子链单元间的距离亦会发生相应的改变，导致改性聚酯的空洞自由体积增大。与短支链取代基(如甲基、乙基等基团)相比，叔丁基占据了较大的空间位置，在分子链排列的方式上将获得更大的自由体积；与长支链取代基相比，一方面叔丁基增大的是空洞，而长支链取代基增大的是狭缝自由体积，另一方面叔丁基的刚性大于长支链取代基，减少了分子链之间的缠结，因而叔丁基较长支链取代基在分子链排列的方式上具有更多的自由体积。由于聚酯结晶度高且表面光滑，表面活性基团很少，活化效果不够理想，带叔丁基侧基的庚二醇的引入使得改性聚酯的空洞自由体积增大，空洞自由体积的增大将有助于在活化过程中使部分活化剂分子扩散进入到纤维空隙中，提高了活化剂的效率，降低活化温度和缩短活化时间，降低因活化对聚酯纤维力学性能的影响，从而显著提高产品与橡胶材料间的粘合作用。
另外，在聚酯纤维的制备过程中，尤其是纤维在后加工拉伸工序中，由于机械应力的作用，纤维取向度大幅增加并且具有一定结晶度，从而使纤维伸长和总形变功减小，但在拉伸过程中，虽然纤维发生的形变大部分是常温下不可恢复的塑性形变，往往已因结晶作用得到固定，然而还有一部分会在室温下因拉伸应力的松弛而恢复，或会在随后的受热处理中发生收缩回复，在纤维的应用过程中这种收缩回复即纤维的收缩率将很大程度地影响纤维的性能(如安全性能、耐久性能等)，假设该纤维用作轮胎帘子线，轮胎在使用过程中，帘子线被反复拉伸、压缩、弯曲，致使轮胎受热，导致帘子线收缩蠕变，但帘子线收缩过大时可能刀子帘子布脱层，进而导致轮胎解体，这给轮胎的使用安全带来极大地隐患。目前在聚酯工业丝的纺丝拉伸过程中，为尽可能地降低聚酯工业丝的收缩率，在进行多道拉伸后往往需要进行紧张热定型(采用热定型辊在一定张力下对纤维进行定型)，在紧张热定型后到卷绕有超喂率为1～2％的超喂，通过对纤维进行紧张热定型，在一定温度和一定张力的条件下，提高分子链段的活动能力，使得分子间结合得更加紧密，提高纤维的晶粒平均尺寸和结晶度，以降低纤维的收缩率，但由于纤维在拉伸过程中存在一定的高弹形变，在张力减小的情况下会产生弹性回复，因此，卷绕头的速度必须低于最后一组热定型辊的速度即需要一定的超喂率，以保证拉伸后的丝得到一定程度的低张力收缩，得到满意的成品质量和卷装，防止卷装因张力过大而造成塌边，超喂率需控制在一定范围内(1～2％)，过大会对成品质量和卷装产生不良影响。虽然通过紧张热定型+超喂能够一定程度上降低收缩率，但是在紧张热定型过程中，由于纤维的长度被固定不可改变，抑制了大分子链的折叠，因而晶粒生长的速率受到限制，导致结晶存在缺陷(结晶度增加较少)，而单单通过控制超喂无法减少结晶缺陷，这会导致制得的纤维在应用过程中受到热处理时，纤维的大分子链及链段具备较高的活动性，容易产生解取向作用，导致纤维发生一定量的收缩(收缩率较大)。
其实，纤维的热定型方式并不仅为紧张热定型，还包括松弛热定型。松弛热定型又称为自由收缩热定型，即是纤维在完全无张力或张力较小的情况下，通过一定温度对纤维进行热处理，在松弛热定型条件下，纤维可自由收缩，非晶区内的大分子链容易形成折叠链，有利于晶粒的进一步生长，加上较充裕的热处理时间，故经过松弛热处理后，纤维的结晶度增加较多(相比于紧张热定型)，从而使纤维内部高弹形变得到恢复同时内应力得到充分松弛，进而 使得在应用过程中受到热处理时纤维发生的收缩回复较小。目前的松弛热定型主要用于对聚酯短纤维进行热定型处理，其热处理温度较低(130℃左右)，热处理时间较长，难以适用于长丝生产。
本发明通过在聚酯工业丝的加工过程中将聚酯丝束卷绕的超喂率提升至3～5％，同时在FDY设备中最后一道热定型辊与卷绕辊之间设置一对上下平行排列的热板，将聚酯丝束从两热板中间穿过，提高了聚酯丝束的结晶度，恢复了聚酯丝束内部的高弹形变，使得聚酯丝束内应力得到一定量的松弛，进而减少了在应用过程中受到热处理时聚酯工业丝发生的收缩回复。本发明通过热处理温度与较高的超喂率的相互配合以降低聚酯工业丝的收缩率，纤维在热处理时，其非晶区内的大分子链容易形成折叠链，有利于晶粒的进一步生长，此时结晶度升高，伴随着结晶度的升高，纤维会产生一定量的收缩，本发明通过提高超喂率，一方面消除了高弹形变对卷绕的影响，另一方面消除了结晶度提高过程中纤维的收缩的影响。此外，本发明通过热处理温度、热板长度及丝束与热板距离三者的相互配合，一方面克服了现有技术松弛热处理不适用于长丝生产的缺陷，另一方面，提高了纤维结晶的完整性，提高了纤维尺寸的稳定性，减少了其应用过程中的热收缩。
有益效果：
(1)本发明的高模低缩活化型涤纶工业丝的制备方法，通过热处理温度与较高的超喂率的相互配合，提高了纤维结晶的完整性，减少了其应用过程中的热收缩；
(2)本发明的高模低缩活化型涤纶工业丝的制备方法，通过带叔丁基侧基的庚二醇对聚酯进行改性，提高了活化剂的使用效率，降低活化温度和缩短活化时间，降低因活化对聚酯纤维力学性能的影响；
(3)本发明的高模低缩活化型涤纶工业丝的制备方法，工艺简单，成本低廉，极具应用前景。
具体实施方式
下面结合具体实施方式，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
Figure PCTCN2019113658-appb-000005
实施例1
一种高模低缩活化型涤纶工业丝的制备方法，具体步骤如下：
(1)制备改性聚酯；
(1.1)制备2,6,6-三甲基-2,5庚二醇；
(a)按异丁醇与氢氧化钾的摩尔比为5:1的比例将氢氧化钾水溶液和异丁醇混合，在100℃的温度条件下反应4h制得异丁醇钾，反应时伴以搅拌，氢氧化钾水溶液的质量浓度为43％；
(b)去除(a)的体系内的杂质并降至常温后，按异丁醇钾与二甲苯的摩尔比为1.3:2.2的比例向(a)的体系内加入二甲苯，冷却至1℃；
(c)向(b)的体系内加入3-甲基-3-羟基丁炔和2,2-二甲基丙醛后，在25℃的温度条件下反应3h，再进行冷却结晶、离心分离和干燥得到辛炔二醇，反应开始时，3-甲基-3-羟基丁炔、2,2-二甲基丙醛与二甲苯的摩尔比为1:1.2:2.2；
(d)按2.2:10:0.01的重量比将辛炔二醇、乙醇和钯催化剂混合，在50℃的温度条件下反应50min，反应过程中持续通入氢气，反应结束后进行分离和提纯得到2,6,6-三甲基-2,5庚二醇，2,6,6-三甲基-2,5庚二醇的结构式如式(Ⅰ)所示，式中，R为-H；
(1.2)酯化反应；
将摩尔比为1:1.2:0.05的对苯二甲酸、乙二醇和2,6,6-三甲基-2,5庚二醇配成浆料，加入三氧化二锑、二氧化钛和磷酸三苯酯混合均匀后，在氮气氛围中加压进行酯化反应，加压压力为常压，酯化反应的温度为250℃，当酯 化反应中的水馏出量达到理论值的90％时为酯化反应终点，三氧化二锑、二氧化钛和磷酸三苯酯的加入量分别为对苯二甲酸加入量的0.03wt％、0.25wt％和0.01wt％；
(1.3)缩聚反应；
酯化反应结束后，在负压条件下开始低真空阶段的缩聚反应，该阶段压力在30min内由常压平稳抽至绝对压力500Pa，反应温度为250℃，反应时间为30min，然后继续抽真空，进行高真空阶段的缩聚反应，使反应压力进一步降至绝对压力100Pa，反应温度为270℃，反应时间为50min，制得数均分子量为30000，分子量分布指数为1.8的改性聚酯；
(1.4)固相缩聚增粘至特性粘度为1.0dL/g；
(2)将改性聚酯经熔融、计量、挤出、冷却、上油、拉伸、热定型、松弛热处理、活化油剂上油、卷绕和预活化处理制得高模低缩活化型涤纶工业丝；
松弛热处理是指将卷绕的超喂率为4.9％的聚酯丝束经过一对平行排列且非共面同时温度为200℃的热板之间的空间，热板位于FDY设备中最后一组热定型辊与卷绕辊之间，沿聚酯丝束的运行方向，两热板的长度为3.0m，两热板的两端齐平，聚酯丝束从两热板中间穿过时，其与两热板之间的距离为5mm，最后一组热定型辊与卷绕辊之间的间距为300mm，两热板与最后一组热定型辊之间的间距为200mm；
纺丝工艺参数如表1所示，拉伸、热定型的工艺参数如表2所示。
最终制得的高模低缩活化型涤纶工业丝的纤度为930dtex，断裂强度为7.8cN/dtex，线密度偏差率为-1.2％，断裂强度CV值为2.5％，断裂伸长率为11.0％，断裂伸长率偏差率为±1.5％，断裂伸长CV值为8.0％，4.0cN/dtex负荷的伸长率为6.0％，4.0cN/dtex负荷的伸长率的偏差率为-0.8％，在177℃×10min×0.05cN/dtex的测试条件下的干热收缩率为2.0％，网络度为3个/m，采用H抽出法测得硫化橡胶与由1100dtex/192F高模低缩活化型涤纶工业丝制得的纤维帘线的静态粘合强度为49N，硫化橡胶与由1670dtex/192F高模低缩活化型涤纶工业丝制得的纤维帘线的静态粘合强度55N。
对比例1
一种涤纶工业丝的制备方法，基本与实施例1相同，不同之处在于不经过松弛热处理工序，卷绕速度为2680m/min，卷绕的超喂率为1.47％，并制备聚酯时不添加2,6,6-三甲基-2,5庚二醇。
最终制得的涤纶工业丝的纤度为913dtex，断裂强度为7.65cN/dtex，线密度偏差率为-1.1％，断裂强度CV值为2.5％，断裂伸长率为12.7％，断裂伸长率偏差率为±1.5％，断裂伸长CV值为8.0％，4.0cN/dtex负荷的伸长率为6.8％，4.0cN/dtex负荷的伸长率的偏差率为-0.8％，在177℃×10min×0.05cN/dtex的测试条件下的干热收缩率为3.2％，网络度为3个/m，采用H抽出法测得硫化橡胶与由1100dtex/192F高模低缩活化型涤纶工业丝制得的纤维帘线的静态粘合强度为46N，硫化橡胶与由1670dtex/192F高模低缩活化型涤纶工业丝制得的纤维帘线的静态粘合强度52N。
对比例2
一种涤纶工业丝的制备方法，基本与实施例1相同，不同之处在于不经过松弛热处理工序，卷绕速度为2680m/min，卷绕的超喂率为1.47％。
最终制得的涤纶工业丝的纤度为913dtex，断裂强度为7.68cN/dtex，线密度偏差率为-1.1％，断裂强度CV值为2.5％，断裂伸长率为12.5％，断裂伸长率偏差率为±1.5％，断裂伸长CV值为8.0％，4.0cN/dtex负荷的伸长率为6.9％，4.0cN/dtex负荷的伸长率的偏差率为-0.8％，在177℃×10min×0.05cN/dtex的测试条件下的干热收缩率为3.2％，网络度为3个/m，采用H抽出法测得硫化橡胶与由1100dtex/192F高模低缩活化型涤纶工业丝制得的纤维帘线的静态粘合强度为49N，硫化橡胶与由1670dtex/192F高模低缩活化型涤纶工业丝制得的纤维帘线的静态粘合强度55N。
对比例3
一种涤纶工业丝的制备方法，基本与实施例1相同，不同之处在于制备聚酯时不添加2,6,6-三甲基-2,5庚二醇。
最终制得的涤纶工业丝的纤度为930dtex，断裂强度为7.78cN/dtex，线密度偏差率为-1.1％，断裂强度CV值为2.5％，断裂伸长率为10.8％，断裂伸长率偏差率为±1.5％，断裂伸长CV值为8.0％，4.0cN/dtex负荷的伸长率为6.1％，4.0cN/dtex负荷的伸长率的偏差率为-0.8％，在177℃×10min×0.05cN/dtex的测试条件下的干热收缩率为2.1％，网络度为3个/m，采用H抽出法测得硫化橡胶与由1100dtex/192F高模低缩活化型涤纶工业丝制得的纤维帘线的静态粘合强度为46N，硫化橡胶与由1670dtex/192F高模低缩活化型涤纶工业丝制得的纤维帘线的静态粘合强度52N。
综合分析实施例1及对比例1～3可以发现，本发明通过添加2,6,6-三甲基-2,5庚二醇提高了活化剂的使用效率， 显著提升了涤纶工业丝的活化性能，松弛热处理工序能够显著降低了涤纶工业丝的干热收缩率。
对比例4
一种涤纶工业丝的制备方法，基本与实施例1相同，不同之处在于制备聚酯时采用1,2十二烷基二醇替代2,6,6-三甲基-2,5庚二醇。
最终制得的涤纶工业丝的纤度为930dtex，断裂强度为7.77cN/dtex，线密度偏差率为-1.1％，断裂强度CV值为2.5％，断裂伸长率为10.8％，断裂伸长率偏差率为±1.5％，断裂伸长CV值为8.0％，4.0cN/dtex负荷的伸长率为6.0％，4.0cN/dtex负荷的伸长率的偏差率为-0.8％，在177℃×10min×0.05cN/dtex的测试条件下的干热收缩率为2.1％，网络度为3个/m，采用H抽出法测得硫化橡胶与由1100dtex/192F高模低缩活化型涤纶工业丝制得的纤维帘线的静态粘合强度为46N，硫化橡胶与由1670dtex/192F高模低缩活化型涤纶工业丝制得的纤维帘线的静态粘合强度52N。
与实施例1对比可以发现，带叔丁基侧基的二元醇相对于含长支链取代基的1,2十二烷基二醇更有利于提升纤维的活化性能，这主要是因为一方面带叔丁基侧基的二元醇中的叔丁基增大的自由体积更多的是空洞自由体积，而长支链取代基增大的自由体积更多的是狭缝自由体积，另一方面带叔丁基侧基的二元醇中的叔丁基的刚性大于长支链取代基，减少了分子链之间的缠结，因而带叔丁基侧基的二元醇较含长支链取代基的1,2十二烷基二醇在聚酯分子链排列的方式上具有更多的自由体积，利于活化剂的渗入，进而更有利于提升纤维的活化性能。
实施例2
一种高模低缩活化型涤纶工业丝的制备方法，具体步骤如下：
(1)制备改性聚酯；
(1.1)制备2,6,6-三甲基-2,5庚二醇；
(a)按异丁醇与氢氧化钾的摩尔比为5.5:1的比例将氢氧化钾水溶液和异丁醇混合，在100℃的温度条件下反应5h制得异丁醇钾，反应时伴以搅拌，氢氧化钾水溶液的质量浓度为40％；
(b)去除(a)的体系内的杂质并降至常温后，按异丁醇钾与二甲苯的摩尔比为1.3:2.0的比例向(a)的体系内加入二甲苯，冷却至3℃；
(c)向(b)的体系内加入3-甲基-3-羟基丁炔和2,2-二甲基丙醛后，在30℃的温度条件下反应3h，再进行冷却结晶、离心分离和干燥得到辛炔二醇，反应开始时，3-甲基-3-羟基丁炔、2,2-二甲基丙醛与二甲苯的摩尔比为1:1.3:2.5；
(d)按2.5:10:0.01的重量比将辛炔二醇、乙醇和钯催化剂混合，在50℃的温度条件下反应55min，反应过程中持续通入氢气，反应结束后进行分离和提纯得到2,6,6-三甲基-2,5庚二醇，2,6,6-三甲基-2,5庚二醇的结构式如式(Ⅰ)所示，式中，R为-H；
(1.2)酯化反应；
将摩尔比为1:1.3:0.04的对苯二甲酸、乙二醇和2,6,6-三甲基-2,5庚二醇配成浆料，加入三氧化二锑、二氧化钛和磷酸三苯酯混合均匀后，在氮气氛围中加压进行酯化反应，加压压力为0.15MPa，酯化反应的温度为252℃，当酯化反应中的水馏出量达到理论值的91％时为酯化反应终点，三氧化二锑、二氧化钛和磷酸三苯酯的加入量分别为对苯二甲酸加入量的0.035wt％、0.22wt％和0.015wt％；
(1.3)缩聚反应；
酯化反应结束后，在负压条件下开始低真空阶段的缩聚反应，该阶段压力在32min内由常压平稳抽至绝对压力498Pa，反应温度为252℃，反应时间为32min，然后继续抽真空，进行高真空阶段的缩聚反应，使反应压力进一步降至绝对压力99Pa，反应温度为272℃，反应时间为55min，制得数均分子量为30500，分子量分布指数为1.85的改性聚酯；
(1.4)固相缩聚增粘至特性粘度为1.05dL/g；
(2)将改性聚酯经熔融、计量、挤出、冷却、上油、拉伸、热定型、松弛热处理、活化油剂上油、卷绕和预活化处理制得高模低缩活化型涤纶工业丝；
松弛热处理是指将卷绕的超喂率为4.2％的聚酯丝束经过一对平行排列且非共面同时温度为202℃的热板之间的空间，热板位于FDY设备中最后一组热定型辊与卷绕辊之间，沿聚酯丝束的运行方向，两热板的长度为3.2m，两热板的两端齐平，聚酯丝束从两热板中间穿过时，其与两热板之间的距离为6mm，最后一组热定型辊与卷绕辊之间的间距为311mm，两热板与最后一组热定型辊之间的间距为220mm；
纺丝工艺参数如表1所示，拉伸、热定型的工艺参数如表2所示。
最终制得的高模低缩活化型涤纶工业丝的纤度为1070dtex，断裂强度为8.0cN/dtex，线密度偏差率为-1.0％，断裂强度CV值为2.1％，断裂伸长率为12.5％，断裂伸长率偏差率为-1.2％，断裂伸长CV值为7.5％，4.0cN/dtex负荷的伸长率为6.2％，4.0cN/dtex负荷的伸长率的偏差率为-0.6％，在177℃×10min×0.05cN/dtex的测试条件下的干热收缩率为2.2％，网络度为6个/m，采用H抽出法测得硫化橡胶与由1100dtex/192F高模低缩活化型涤纶工业丝制得的纤维帘线的静态粘合强度为50N，硫化橡胶与由1670dtex/192F高模低缩活化型涤纶工业丝制得的纤维帘线的静态粘合强度57N。
实施例3
一种高模低缩活化型涤纶工业丝的制备方法，具体步骤如下：
(1)制备改性聚酯；
(1.1)制备2,6,6-三甲基-5-乙基-2,5-庚二醇；
(a)按异丁醇与氢氧化钾的摩尔比为5:1的比例将氢氧化钾水溶液和异丁醇混合，在105℃的温度条件下反应4.5h制得异丁醇钾，反应时伴以搅拌，氢氧化钾水溶液的质量浓度为48％；
(b)去除(a)的体系内的杂质并降至常温后，按异丁醇钾与二甲苯的摩尔比为1.5:2.5的比例向(a)的体系内加入二甲苯，冷却至0℃；
(c)向(b)的体系内加入3-甲基-3-羟基丁炔和2,2-二甲基-3-戊酮后，在30℃的温度条件下反应3h，再进行冷却结晶、离心分离和干燥得到辛炔二醇，反应开始时，3-甲基-3-羟基丁炔、2,2-二甲基-3-戊酮与二甲苯的摩尔比为1:1.25:2.0；
(d)按2:10:0.02的重量比将辛炔二醇、乙醇和钯催化剂混合，在42℃的温度条件下反应60min，反应过程中持续通入氢气，反应结束后进行分离和提纯得到2,6,6-三甲基-5-乙基-2,5-庚二醇，2,6,6-三甲基-5-乙基-2,5-庚二醇的结构式如式(Ⅰ)所示，式中，R为-CH 2CH 3；
(1.2)酯化反应；
将摩尔比为1:1.4:0.035的对苯二甲酸、乙二醇和2,6,6-三甲基-5-乙基-2,5-庚二醇配成浆料，加入乙二醇锑、二氧化钛和磷酸三苯酯混合均匀后，在氮气氛围中加压进行酯化反应，加压压力为0.18MPa，酯化反应的温度为253℃，当酯化反应中的水馏出量达到理论值的92％时为酯化反应终点，乙二醇锑、二氧化钛和磷酸三苯酯的加入量分别为对苯二甲酸加入量的0.04wt％、0.23wt％和0.02wt％；
(1.3)缩聚反应；
酯化反应结束后，在负压条件下开始低真空阶段的缩聚反应，该阶段压力在35min内由常压平稳抽至绝对压力497Pa，反应温度为253℃，反应时间为35min，然后继续抽真空，进行高真空阶段的缩聚反应，使反应压力进一步降至绝对压力98Pa，反应温度为274℃，反应时间为62min，制得数均分子量为32000，分子量分布指数为1.9的改性聚酯；
(1.4)固相缩聚增粘至特性粘度为1.08dL/g；
(2)将改性聚酯经熔融、计量、挤出、冷却、上油、拉伸、热定型、松弛热处理、活化油剂上油、卷绕和预活化处理制得高模低缩活化型涤纶工业丝；
松弛热处理是指将卷绕的超喂率为3.3％的聚酯丝束经过一对平行排列且非共面同时温度为210℃的热板之间的空间，热板位于FDY设备中最后一组热定型辊与卷绕辊之间，沿聚酯丝束的运行方向，两热板的长度为3.3m，两热板的两端齐平，聚酯丝束从两热板中间穿过时，其与两热板之间的距离为7mm，最后一组热定型辊与卷绕辊之间的间距为335mm，两热板与最后一组热定型辊之间的间距为235mm；
纺丝工艺参数如表1所示，拉伸、热定型的工艺参数如表2所示。
最终制得的高模低缩活化型涤纶工业丝的纤度为1170dtex，断裂强度为8.3N/dtex，线密度偏差率为-0.2％，断裂强度CV值为2.3％，断裂伸长率为12.5％，断裂伸长率偏差率为1.0％，断裂伸长CV值为7.0％，4.0cN/dtex负荷的伸长率为6.6％，4.0cN/dtex负荷的伸长率的偏差率为0.3％，在177℃×10min×0.05cN/dtex的测试条件下的干热收缩率为2.6％，网络度为8个/m，采用H抽出法测得硫化橡胶与由1100dtex/192F高模低缩活化型涤纶工业丝制得的纤维帘线的静态粘合强度为52N，硫化橡胶与由1670dtex/192F高模低缩活化型涤纶工业丝制得的纤维帘线的静态粘合强度58N。
实施例4
一种高模低缩活化型涤纶工业丝的制备方法，具体步骤如下：
(1)制备改性聚酯；
(1.1)制备2,6,6-三甲基-5-乙基-2,5-庚二醇；
(a)按异丁醇与氢氧化钾的摩尔比为6:1的比例将氢氧化钾水溶液和异丁醇混合，在110℃的温度条件下反应4.8h制得异丁醇钾，反应时伴以搅拌，氢氧化钾水溶液的质量浓度为41％；
(b)去除(a)的体系内的杂质并降至常温后，按异丁醇钾与二甲苯的摩尔比为1.4:3.0的比例向(a)的体系内加入二甲苯，冷却至0℃；
(c)向(b)的体系内加入3-甲基-3-羟基丁炔和2,2-二甲基-3-戊酮后，在35℃的温度条件下反应3h，再进行冷却结晶、离心分离和干燥得到辛炔二醇，反应开始时，3-甲基-3-羟基丁炔、2,2-二甲基-3-戊酮与二甲苯的摩尔比为1:1.3:2.6；
(d)按3:10:0.01的重量比将辛炔二醇、乙醇和钯催化剂混合，在40℃的温度条件下反应60min，反应过程中持续通入氢气，反应结束后进行分离和提纯得到2,6,6-三甲基-5-乙基-2,5-庚二醇，2,6,6-三甲基-5-乙基-2,5-庚二醇的结构式如式(Ⅰ)所示，式中，R为-CH 2CH 3；
(1.2)酯化反应；
将摩尔比为1:1.5:0.03的对苯二甲酸、乙二醇和2,6,6-三甲基-5-乙基-2,5-庚二醇配成浆料，加入乙二醇锑、二氧化钛和磷酸三甲酯混合均匀后，在氮气氛围中加压进行酯化反应，加压压力为0.2MPa，酯化反应的温度为255℃，当酯化反应中的水馏出量达到理论值的93％时为酯化反应终点，乙二醇锑、二氧化钛和磷酸三甲酯的加入量分别为对苯二甲酸加入量的0.045wt％、0.24wt％和0.025wt％；
(1.3)缩聚反应；
酯化反应结束后，在负压条件下开始低真空阶段的缩聚反应，该阶段压力在38min内由常压平稳抽至绝对压力495Pa，反应温度为255℃，反应时间为38min，然后继续抽真空，进行高真空阶段的缩聚反应，使反应压力进一步降至绝对压力97Pa，反应温度为276℃，反应时间为67min，制得数均分子量为32000，分子量分布指数为1.92的改性聚酯；
(1.4)固相缩聚增粘至特性粘度为1.1dL/g；
(2)将改性聚酯经熔融、计量、挤出、冷却、上油、拉伸、热定型、松弛热处理、活化油剂上油、卷绕和预活化处理制得高模低缩活化型涤纶工业丝；
松弛热处理是指将卷绕的超喂率为4.8％的聚酯丝束经过一对平行排列且非共面同时温度为240℃的热板之间的空间，热板位于FDY设备中最后一组热定型辊与卷绕辊之间，沿聚酯丝束的运行方向，两热板的长度为3.4m，两热板的两端齐平，聚酯丝束从两热板中间穿过时，其与两热板之间的距离为8mm，最后一组热定型辊与卷绕辊之间的间距为346mm，两热板与最后一组热定型辊之间的间距为250mm；
纺丝工艺参数如表1所示，拉伸、热定型的工艺参数如表2所示。
最终制得的高模低缩活化型涤纶工业丝的纤度为1370dtex，断裂强度为7.9cN/dtex，线密度偏差率为1.0％，断裂强度CV值为2.4％，断裂伸长率为12.0％，断裂伸长率偏差率为1.0％，断裂伸长CV值为6.9％，4.0cN/dtex负荷的伸长率为6.5％，4.0cN/dtex负荷的伸长率的偏差率为0.3％，在177℃×10min×0.05cN/dtex的测试条件下的干热收缩率为2.7％，网络度为7个/m，采用H抽出法测得硫化橡胶与由1100dtex/192F高模低缩活化型涤纶工业丝制得的纤维帘线的静态粘合强度为52N，硫化橡胶与由1670dtex/192F高模低缩活化型涤纶工业丝制得的纤维帘线的静态粘合强度59N。
实施例5
一种高模低缩活化型涤纶工业丝的制备方法，具体步骤如下：
(1)制备改性聚酯；
(1.1)制备2,6,6-三甲基-5-异丙基-2,5-庚二醇；
(a)按异丁醇与氢氧化钾的摩尔比为5.4:1的比例将氢氧化钾水溶液和异丁醇混合，在110℃的温度条件下反应5h制得异丁醇钾，反应时伴以搅拌，氢氧化钾水溶液的质量浓度为50％；
(b)去除(a)的体系内的杂质并降至常温后，按异丁醇钾与二甲苯的摩尔比为1.4:2.6的比例向(a)的 体系内加入二甲苯，冷却至4℃；
(c)向(b)的体系内加入3-甲基-3-羟基丁炔和2,2,4-三甲基-3-戊酮后，在28℃的温度条件下反应3h，再进行冷却结晶、离心分离和干燥得到辛炔二醇，反应开始时，3-甲基-3-羟基丁炔、2,2,4-三甲基-3-戊酮与二甲苯的摩尔比为1:1.2:3.0；
(d)按2.5:10:0.03的重量比将辛炔二醇、乙醇和钯催化剂混合，在44℃的温度条件下反应53min，反应过程中持续通入氢气，反应结束后进行分离和提纯得到2,6,6-三甲基-5-异丙基-2,5-庚二醇，2,6,6-三甲基-5-异丙基-2,5-庚二醇的结构式如式(Ⅰ)所示，式中，R为-CH(CH 3) 2；
(1.2)酯化反应；
将摩尔比为1:1.6:0.04的对苯二甲酸、乙二醇和2,6,6-三甲基-5-异丙基-2,5-庚二醇配配成浆料，加入醋酸锑、二氧化钛和磷酸三甲酯混合均匀后，在氮气氛围中加压进行酯化反应，加压压力为0.25MPa，酯化反应的温度为256℃，当酯化反应中的水馏出量达到理论值的94％时为酯化反应终点，醋酸锑、二氧化钛和磷酸三甲酯的加入量分别为对苯二甲酸加入量的0.05wt％、0.20wt％和0.03wt％；
(1.3)缩聚反应；
酯化反应结束后，在负压条件下开始低真空阶段的缩聚反应，该阶段压力在40min内由常压平稳抽至绝对压力492Pa，反应温度为256℃，反应时间为40min，然后继续抽真空，进行高真空阶段的缩聚反应，使反应压力进一步降至绝对压力95Pa，反应温度为278℃，反应时间为72min，制得数均分子量为33030，分子量分布指数为1.95的改性聚酯；
(1.4)固相缩聚增粘至特性粘度为1.15dL/g；
(2)将改性聚酯经熔融、计量、挤出、冷却、上油、拉伸、热定型、松弛热处理、活化油剂上油、卷绕和预活化处理制得高模低缩活化型涤纶工业丝；
松弛热处理是指将卷绕的超喂率为4.0％的聚酯丝束经过一对平行排列且非共面同时温度为220℃的热板之间的空间，热板位于FDY设备中最后一组热定型辊与卷绕辊之间，沿聚酯丝束的运行方向，两热板的长度为3.6m，两热板的两端齐平，聚酯丝束从两热板中间穿过时，其与两热板之间的距离为8.5mm，最后一组热定型辊与卷绕辊之间的间距为368mm，两热板与最后一组热定型辊之间的间距为260mm；
纺丝工艺参数如表1所示，拉伸、热定型的工艺参数如表2所示。
最终制得的高模低缩活化型涤纶工业丝的纤度为1290dtex，断裂强度为8.3cN/dtex，线密度偏差率为1.0％，断裂强度CV值为2.3％，断裂伸长率为12.9％，断裂伸长率偏差率为1.0％，断裂伸长CV值为6.6％，4.0cN/dtex负荷的伸长率为6.2％，4.0cN/dtex负荷的伸长率的偏差率为0.1％，在177℃×10min×0.05cN/dtex的测试条件下的干热收缩率为2.6％，网络度为8个/m，采用H抽出法测得硫化橡胶与由1100dtex/192F高模低缩活化型涤纶工业丝制得的纤维帘线的静态粘合强度为42N，硫化橡胶与由1670dtex/192F高模低缩活化型涤纶工业丝制得的纤维帘线的静态粘合强度60N。
实施例6
一种高模低缩活化型涤纶工业丝的制备方法，具体步骤如下：
(1)制备改性聚酯；
(1.1)制备2,6,6-三甲基-5-异丙基-2,5-庚二醇；
(a)按异丁醇与氢氧化钾的摩尔比为5:1的比例将氢氧化钾水溶液和异丁醇混合，在106℃的温度条件下反应4.5h制得异丁醇钾，反应时伴以搅拌，氢氧化钾水溶液的质量浓度为40％；
(b)去除(a)的体系内的杂质并降至常温后，按异丁醇钾与二甲苯的摩尔比为1.3:2.0的比例向(a)的体系内加入二甲苯，冷却至2℃；
(c)向(b)的体系内加入3-甲基-3-羟基丁炔和2,2,4-三甲基-3-戊酮后，在32℃的温度条件下反应3h，再进行冷却结晶、离心分离和干燥得到辛炔二醇，反应开始时，3-甲基-3-羟基丁炔、2,2,4-三甲基-3-戊酮与二甲苯的摩尔比为1:1.3:2.5；
(d)按2:10:0.01的重量比将辛炔二醇、乙醇和钯催化剂混合，在48℃的温度条件下反应50min，反应过程中持续通入氢气，反应结束后进行分离和提纯得到2,6,6-三甲基-5-异丙基-2,5-庚二醇，2,6,6-三甲基-5-异丙基-2,5-庚二醇的结构式如式(Ⅰ)所示，式中，R为-CH(CH 3) 2；
(1.2)酯化反应；
将摩尔比为1:1.8:0.05的对苯二甲酸、乙二醇和2,6,6-三甲基-5-异丙基-2,5-庚二醇配成浆料，加入醋酸锑、二氧化钛和亚磷酸三甲酯混合均匀后，在氮气氛围中加压进行酯化反应，加压压力为0.28MPa，酯化反应的温度为258℃，当酯化反应中的水馏出量达到理论值的95％时为酯化反应终点，醋酸锑、二氧化钛和亚磷酸三甲酯的加入量分别为对苯二甲酸加入量的0.05wt％、0.20wt％和0.04wt％；
(1.3)缩聚反应；
酯化反应结束后，在负压条件下开始低真空阶段的缩聚反应，该阶段压力在42min内由常压平稳抽至绝对压力490Pa，反应温度为258℃，反应时间为42min，然后继续抽真空，进行高真空阶段的缩聚反应，使反应压力进一步降至绝对压力94Pa，反应温度为280℃，反应时间为82min，制得数均分子量为34400，分子量分布指数为1.96的改性聚酯；
(1.4)固相缩聚增粘至特性粘度为1.18dL/g；
(2)将改性聚酯经熔融、计量、挤出、冷却、上油、拉伸、热定型、松弛热处理、活化油剂上油、卷绕和预活化处理制得高模低缩活化型涤纶工业丝；
松弛热处理是指将卷绕的超喂率为3.0％的聚酯丝束经过一对平行排列且非共面同时温度为215℃的热板之间的空间，热板位于FDY设备中最后一组热定型辊与卷绕辊之间，沿聚酯丝束的运行方向，两热板的长度为3.8m，两热板的两端齐平，聚酯丝束从两热板中间穿过时，其与两热板之间的距离为9mm，最后一组热定型辊与卷绕辊之间的间距为384mm，两热板与最后一组热定型辊之间的间距为280mm；
纺丝工艺参数如表1所示，
拉伸、热定型的工艺参数如表2所示。
最终制得的高模低缩活化型涤纶工业丝的纤度为1570dtex，断裂强度为7.9cN/dtex，线密度偏差率为1.0％，断裂强度CV值为2.4％，断裂伸长率为13.0％，断裂伸长率偏差率为1.2％，断裂伸长CV值为6.6％，4.0cN/dtex负荷的伸长率为7.0％，4.0cN/dtex负荷的伸长率的偏差率为0.8％，在177℃×10min×0.05cN/dtex的测试条件下的干热收缩率为2.7％，网络度为6个/m，采用H抽出法测得硫化橡胶与由1100dtex/192F高模低缩活化型涤纶工业丝制得的纤维帘线的静态粘合强度为51N，硫化橡胶与由1670dtex/192F高模低缩活化型涤纶工业丝制得的纤维帘线的静态粘合强度61N。
实施例7
一种高模低缩活化型涤纶工业丝的制备方法，具体步骤如下：
(1)制备改性聚酯；
(1.1)制备2,6,6-三甲基-5-叔丁基-2,5-庚二醇；
(a)按异丁醇与氢氧化钾的摩尔比为5.5:1的比例将氢氧化钾水溶液和异丁醇混合，在100℃的温度条件下反应4h制得异丁醇钾，反应时伴以搅拌，氢氧化钾水溶液的质量浓度为46％；
(b)去除(a)的体系内的杂质并降至常温后，按异丁醇钾与二甲苯的摩尔比为1.3:2.6的比例向(a)的体系内加入二甲苯，冷却至5℃；
(c)向(b)的体系内加入3-甲基-3-羟基丁炔和2,2,4,4-四甲基-3-戊酮后，在25℃的温度条件下反应3h，再进行冷却结晶、离心分离和干燥得到辛炔二醇，反应开始时，3-甲基-3-羟基丁炔、2,2,4,4-四甲基-3-戊酮与二甲苯的摩尔比为1:1.24:3.0；
(d)按3:10:0.03的重量比将辛炔二醇、乙醇和钯催化剂混合，在40℃的温度条件下反应56min，反应过程中持续通入氢气，反应结束后进行分离和提纯得到2,6,6-三甲基-5-叔丁基-2,5-庚二醇，2,6,6-三甲基-5-叔丁基-2,5-庚二醇的结构式如式(Ⅰ)所示，式中，R为-C(CH 3) 3；
(1.2)酯化反应；
将摩尔比为1:2.0:0.03的对苯二甲酸、乙二醇和2,6,6-三甲基-5-叔丁基-2,5-庚二醇配成浆料，加入醋酸锑、二氧化钛和亚磷酸三甲酯混合均匀后，在氮气氛围中加压进行酯化反应，加压压力为0.3MPa，酯化反应的温度为260℃，当酯化反应中的水馏出量达到理论值的96％时为酯化反应终点，醋酸锑、二氧化钛和亚磷酸三甲酯的加入量分别为对苯二甲酸加入量的0.05wt％、0.20wt％和0.05wt％；
(1.3)缩聚反应；
酯化反应结束后，在负压条件下开始低真空阶段的缩聚反应，该阶段压力在50min内由常压平稳抽至绝对压力490Pa，反应温度为260℃，反应时间为50min，然后继续抽真空，进行高真空阶段的缩聚反应，使反应压力进一步降至绝对压力92Pa，反应温度为282℃，反应时间为90min，制得数均分子量为35000，分子量分布指数为2.2的改性聚酯；
(1.4)固相缩聚增粘至特性粘度为1.2dL/g；
(2)将改性聚酯经熔融、计量、挤出、冷却、上油、拉伸、热定型、松弛热处理、活化油剂上油、卷绕和预活化处理制得高模低缩活化型涤纶工业丝；
松弛热处理是指将卷绕的超喂率为5.0％的聚酯丝束经过一对平行排列且非共面同时温度为220℃的热板之间的空间，热板位于FDY设备中最后一组热定型辊与卷绕辊之间，沿聚酯丝束的运行方向，两热板的长度为4.0m，两热板的两端齐平，聚酯丝束从两热板中间穿过时，其与两热板之间的距离为10mm，最后一组热定型辊与卷绕辊之间的间距为400mm，两热板与最后一组热定型辊之间的间距为300mm；
纺丝工艺参数如表1所示，拉伸、热定型的工艺参数如表2所示。
最终制得的高模低缩活化型涤纶工业丝的纤度为1670dtex，断裂强度为8.5cN/dtex，线密度偏差率为1.2％，断裂强度CV值为2.0％，断裂伸长率为13.5％，断裂伸长率偏差率为1.5％，断裂伸长CV值为6.4％，4.0cN/dtex负荷的伸长率为7.0％，4.0cN/dtex负荷的伸长率的偏差率为0.8％，在177℃×10min×0.05cN/dtex的测试条件下的干热收缩率为3.0％，网络度为9个/m，采用H抽出法测得硫化橡胶与由1100dtex/192F高模低缩活化型涤纶工业丝制得的纤维帘线的静态粘合强度为53N，硫化橡胶与由1670dtex/192F高模低缩活化型涤纶工业丝制得的纤维帘线的静态粘合强度62N。
表1
Figure PCTCN2019113658-appb-000006
表2
Figure PCTCN2019113658-appb-000007
Figure PCTCN2019113658-appb-000008

Claims (10)

  1. 高模低缩活化型涤纶工业丝的制备方法，其特征是：将改性聚酯经固相缩聚增粘、熔融、计量、挤出、冷却、上油、拉伸、热定型、松弛热处理、活化油剂上油、卷绕和预活化处理制得高模低缩活化型涤纶工业丝；
    固相缩聚增粘前的改性聚酯的制备方法为：将对苯二甲酸、乙二醇和带叔丁基侧基的庚二醇混合均匀后先后进行酯化反应和缩聚反应；
    带叔丁基侧基的庚二醇的结构式如下：
    Figure PCTCN2019113658-appb-100001
    式中，R为-H、-CH 2CH 3、-CH(CH 3) 2或-C(CH 3) 3；
    所述松弛热处理是指将改性聚酯丝束在适当的松弛状态经过一定温度的空间；
    所述适当的松弛状态是指卷绕的超喂率为3.0～5.0％；
    所述一定温度是指200～220℃。
  2. 根据权利要求1所述的高模低缩活化型涤纶工业丝的制备方法，其特征在于，高模低缩活化型涤纶工业丝的纤度为930～1670dtex，断裂强度≥7.8cN/dtex，线密度偏差率为±1.2％，断裂强度CV值≤2.5％，断裂伸长率为11.0～13.5％，断裂伸长率偏差率为±1.5％，断裂伸长CV值≤8.0％，4.0cN/dtex负荷的伸长率为6.0～7.0％，4.0cN/dtex负荷的伸长率的偏差率为±0.8％，网络度为6±2～3个/m。
  3. 根据权利要求2所述的高模低缩活化型涤纶工业丝的制备方法，其特征在于，高模低缩活化型涤纶工业丝在177℃×10min×0.05cN/dtex的测试条件下的干热收缩率为2.5±0.5％，采用H抽出法测得硫化橡胶与由1100dtex/192F高模低缩活化型涤纶工业丝制得的纤维帘线的静态粘合强度为49～53N，硫化橡胶与由1670dtex/192F高模低缩活化型涤纶工业丝制得的纤维帘线的静态粘合强度55～62N。
  4. 根据权利要求1所述的高模低缩活化型涤纶工业丝的制备方法，其特征在于，所述一定温度的空间是指一对平行排列且非共面的热板之间的空间，热板位于最后一组热定型辊与卷绕辊之间；沿改性聚酯丝束的运行方向，两热板的 长度为3.0～4.0m，两热板的两端齐平；改性聚酯丝束从两热板中间穿过时，其与两热板之间的距离为5～10mm；最后一组热定型辊与卷绕辊之间的间距为300～400mm；两热板与最后一组热定型辊之间的间距为200～300mm。
  5. 根据权利要求1所述的高模低缩活化型涤纶工业丝的制备方法，其特征在于，所述带叔丁基侧基的庚二醇的合成步骤如下：
    (1)按异丁醇与氢氧化钾的摩尔比为5～6:1的比例将氢氧化钾水溶液和异丁醇混合，在100～110℃的温度条件下反应4～5h制得异丁醇钾，反应时伴以搅拌，氢氧化钾水溶液的质量浓度为40～50％；
    (2)去除(1)的体系内的杂质并降至常温后，按异丁醇钾与二甲苯的摩尔比为1.3～1.5:2.0～3.0的比例向(1)的体系内加入二甲苯，冷却至0～5℃；
    (3)向(2)的体系内加入3-甲基-3-羟基丁炔和M后，在25～35℃的温度条件下反应3h，再进行冷却结晶、离心分离和干燥得到辛炔二醇，反应开始时，3-甲基-3-羟基丁炔、M与二甲苯的摩尔比为1:1.2～1.3:2.0～3.0；
    (4)按2～3:10:0.01～0.03的重量比将辛炔二醇、乙醇和钯催化剂混合，在40～50℃的温度条件下反应50～60min，反应过程中持续通入氢气，反应结束后进行分离和提纯得到带叔丁基侧基的庚二醇；
    所述带叔丁基侧基的庚二醇的结构式中R为-H、-CH 2CH 3、-CH(CH 3) 2和-C(CH 3) 3时，M分别对应为2,2-二甲基丙醛、2,2-二甲基-3-戊酮、2,2,4-三甲基-3-戊酮和2,2,4,4-四甲基-3-戊酮。
  6. 根据权利要求5所述的高模低缩活化型涤纶工业丝的制备方法，其特征在于，固相缩聚增粘前的改性聚酯的制备步骤如下：
    (1)酯化反应；
    将对苯二甲酸、乙二醇和带叔丁基侧基的庚二醇配成浆料，加入催化剂、消光剂和稳定剂混合均匀后，在氮气氛围中加压进行酯化反应，加压压力为常压～0.3MPa，酯化反应的温度为250～260℃，当酯化反应中的水馏出量达到理论值的90％以上时为酯化反应终点；
    (2)缩聚反应；
    酯化反应结束后，在负压条件下开始低真空阶段的缩聚反应，该阶段压力在30～50min内由常压平稳抽至绝对压力500Pa以下，反应温度为 250～260℃，反应时间为30～50min，然后继续抽真空，进行高真空阶段的缩聚反应，使反应压力进一步降至绝对压力100Pa以下，反应温度为270～282℃，反应时间为50～90min。
  7. 根据权利要求6所述的高模低缩活化型涤纶工业丝的制备方法，其特征在于，所述对苯二甲酸、乙二醇和带叔丁基侧基的庚二醇的摩尔比为1:1.2～2.0:0.03～0.05，所述催化剂、消光剂和稳定剂的加入量分别为对苯二甲酸加入量的0.03～0.05wt％、0.20～0.25wt％和0.01～0.05wt％。
  8. 根据权利要求7所述的高模低缩活化型涤纶工业丝的制备方法，其特征在于，所述催化剂为三氧化二锑、乙二醇锑或醋酸锑，所述消光剂为二氧化钛，所述稳定剂为磷酸三苯酯、磷酸三甲酯或亚磷酸三甲酯。
  9. 根据权利要求8所述的高模低缩活化型涤纶工业丝的制备方法，其特征在于，固相缩聚增粘前的改性聚酯的数均分子量为30000～35000，分子量分布指数为1.8～2.2；固相缩聚增粘后的改性聚酯的特性粘度为1.0～1.2dL/g。
  10. 根据权利要求1所述的高模低缩活化型涤纶工业丝的制备方法，其特征在于，所述高模低缩活化型涤纶工业丝的纺丝工艺参数如下：
    Figure PCTCN2019113658-appb-100002
    拉伸、热定型的工艺参数为：
    Figure PCTCN2019113658-appb-100003
    Figure PCTCN2019113658-appb-100004
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