WO2018040689A1 - 一种高均匀性有色聚酯工业丝及其制备方法 - Google Patents

一种高均匀性有色聚酯工业丝及其制备方法 Download PDF

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WO2018040689A1
WO2018040689A1 PCT/CN2017/089944 CN2017089944W WO2018040689A1 WO 2018040689 A1 WO2018040689 A1 WO 2018040689A1 CN 2017089944 W CN2017089944 W CN 2017089944W WO 2018040689 A1 WO2018040689 A1 WO 2018040689A1
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segment
industrial yarn
spinneret
terephthalic acid
polyester industrial
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PCT/CN2017/089944
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English (en)
French (fr)
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范红卫
王丽丽
范晓兵
杨大矛
宋光坤
赵慧荣
王山水
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江苏恒力化纤股份有限公司
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Priority to ES17844995T priority Critical patent/ES2854075T3/es
Priority to JP2018557072A priority patent/JP6605756B2/ja
Priority to EP17844995.5A priority patent/EP3508624B1/en
Priority to US16/322,949 priority patent/US10801132B2/en
Publication of WO2018040689A1 publication Critical patent/WO2018040689A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • D01D4/00—Spinnerette packs; Cleaning thereof
    • D01D4/02—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
    • 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
    • D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
    • 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
    • D01F1/04—Pigments
    • 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
    • D01F1/06—Dyes
    • 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
    • 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
    • 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
    • D01F6/86—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from polyetheresters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/12—Applications used for fibers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2310/00—Masterbatches

Definitions

  • the invention belongs to the technical field of polyester fibers, and relates to a high uniformity colored polyester industrial yarn and a preparation method thereof.
  • PET fiber or polyester fiber Since the advent of polyethylene terephthalate (PET fiber or polyester fiber) fiber, it has high breaking strength and elastic modulus, moderate resilience, excellent heat setting, good heat and light resistance, and acid and alkali resistance. A series of excellent properties such as sex, and the fabric has the advantages of anti-wrinkle and capital-free, good rigidity, and is widely used in clothing, home textile and other fields.
  • PET is a symmetrical linear macromolecule.
  • the molecular chain does not contain a side chain group. The regularity is very good. Its main chain contains a rigid benzene ring and a flexible hydrocarbon group, and the ester group and benzene directly connected to the benzene ring.
  • the ring constitutes a rigid conjugate system which gives the polyester a higher melting point. Generally, the melting point of the polyester is around 260 °C. With the further expansion of production applications, higher requirements are placed on the heat resistance of polyester.
  • the introduction of unsaturated double bonds in the polyester and the completion of the crosslinking reaction in the fiber spinning process greatly increase the heat resistance of the fibers. The introduction of unsaturated double bonds in polyester fibers and effective and safe control of cross-linking will improve the mechanical properties, heat resistance, chemical resistance and flame retardancy of polyester fibers. How to use unsaturated Double bonds are an important issue in the production process of polyester fibers.
  • the influence of the polyester structure on the glass transition temperature is obvious, and the wall ridge of the molecular segment movement is increased.
  • the glass transition temperature of PET is high, and it is required to dye at a very high temperature to promote the diffusion of dye molecules into the fiber interior.
  • the molecular chain of PET is regular, the crystallinity is good, the molecular chains are closely arranged, and there are no polar groups on the molecular chain that interact with the dye molecules, making the coloring of the polyester fibers more difficult.
  • polyester industrial yarn is dyed by dyeing, on the one hand, it needs to be dyed under high temperature and high pressure, and the fiber has a certain amount of boiling water shrinkage, which causes the fiber quality to decrease; on the other hand, dyeing black mostly makes the dye, and the dye has weather resistance. Poor, will affect the life cycle of the fiber.
  • the ring blowing has obvious advantages, it still cannot solve the problem of uneven cooling of the porous wire: since the spun yarn is extruded from the circular spinneret, it is cooled by the ring blower. Due to the large number of round spinneret rings, it is difficult for the ring blowing to enter the innermost layer, so that the innermost layer of wire may not be cooled after the outermost wire has been cooled, so that the resulting wire has unevenness. Problems such as uneven strength make it difficult to further process the yarn.
  • the technical problem to be solved by the present invention is to provide a high uniformity colored polyester industrial yarn and a preparation method thereof according to the deficiencies of the prior art, and the raw material of the high uniformity colored polyester industrial yarn of the invention is modified polyester.
  • the polyester chain of branched polyester is introduced into the molecular chain of the polyester, and the modified high-uniformity colored polyester industrial yarn prepared by the modified polyester, under certain temperature conditions, the high uniformity of the colored polyester industrial yarn interior
  • the increase of the spatial gap between the molecular chains is far greater than that of the non-branched colored polyester industrial yarn at the same temperature.
  • the melt viscosity of the high-uniformity colored polyester industrial yarn is reduced, the processing temperature is lowered, the degradation rate is reduced, and the processing is facilitated. .
  • the arrangement of the spinning holes on the porous spinneret of the high uniformity colored polyester industrial yarn of the present invention is an elliptical arrangement, and the elliptical arrangement means that the center of the hole of the spinning hole is located on a concentric ellipse, and the concentric ellipse is a series of ellipse.
  • the long axis of all ellipse is collinear, and the short axis is collinear; it can achieve higher cooling efficiency and better cooling effect.
  • a high uniformity colored polyester industrial yarn refers to a polyester industrial yarn to which a black masterbatch is added, and the high uniformity colored polyester industrial yarn is solidified by a modified polyester. Spinning after phase-gluing; the material of the high-uniformity colored polyester industrial yarn is a modified polyester composed of a terephthalic acid segment, an ethylene glycol segment, and a branched chain.
  • a diol segment comprising a branched chain on a non-terminal carbon in the diol segment and a branched chain having 5-10 carbon atoms a carbon chain diol segment
  • the high uniformity colored polyester industrial yarn breaking strength ⁇ 7.0 cN/dtex, linear density deviation rate ⁇ 1.0%, breaking strength CV value ⁇ 2.0%, elongation at break CV value ⁇ 5.5%
  • the high uniformity colored polyester industrial yarn at 260-290 ° C, the melt viscosity decreased by 10-20%, under the test conditions of temperature 177 ° C ⁇ 10 min ⁇ 0.05 cN / dtex, dry heat shrinkage The rate is 2.5 ⁇ 0.5%.
  • a high-uniformity colored polyester industrial yarn is a modified polyester, and a branched-chain diol segment is introduced on a long chain of a modified polyester macromolecule, and the length and the amount of the branch are modified to the polyester.
  • the crystallization property and flow behavior have great influences.
  • the length of the branch chain is too short to achieve the purpose of polyester modification. If the length is too long, it will cause new entanglement and affect its flow behavior.
  • the increase in the spatial gap between the molecular chains inside the filament is much greater than that of unbranched industrial filaments at the same temperature. It is beneficial to reduce the viscosity of industrial silk melt and facilitate further processing.
  • the invention relates to a method for preparing a high uniformity colored polyester industrial yarn, which comprises solid phase polycondensation, viscosity measurement, metering, black masterbatch addition, porous spinneret extrusion, cooling, oiling, stretching , heat setting and winding to produce high uniformity colored polyester industrial yarn;
  • the arrangement of the orifices on the porous spinneret is elliptical.
  • the elliptical arrangement means that the center of the orifice of the orifice is located on a concentric ellipse, and the concentric ellipse is a series of ellipse, and the long axes of all the ellipse are Line, and the short axis is collinear;
  • the preparation process of the modified polyester includes the following steps:
  • the esterification reaction is carried out under the catalytic action of concentrated sulfuric acid to obtain a terephthalic acid glycol ester;
  • the branched binary An alcohol is a diol which is branched and located on a non-terminal carbon in the diol segment and branched as a linear carbon chain having 5 to 10 carbon atoms;
  • the branch is an alkyl group, which is an electron withdrawing group.
  • the space volume of the molecular chain is increased, the solvation is reduced, and the protons in the diol are not easily dissociated.
  • the reaction of the branched diol with terephthalic acid is less than that of ethylene glycol. If the reaction with ethylene glycol is mixed with terephthalic acid, the reaction of the branched diol is incomplete, thereby affecting The proportion of branched diols in the polyester macromolecules, which in turn affects the properties of the polyester.
  • the invention adopts the esterification reaction of the branched diol with terephthalic acid under the catalysis of sulfuric acid, and the product is added after the esterification of ethylene glycol and terephthalic acid, thereby ensuring the inclusion.
  • the stability of the chain's glycol ratio is a critical parameter for the esterification reaction of the branched diol with terephthalic acid under the catalysis of sulfuric acid, and the product is added after the esterification of ethylene glycol and terephthalic acid, thereby ensuring the inclusion.
  • the terephthalic acid glycol ester prepared in the step (1) is added, stirred and mixed, under the action of the catalyst and the stabilizer, under the condition of the negative pressure, The polycondensation reaction in a low vacuum stage and the polycondensation reaction in a high vacuum stage are carried out to obtain a modified polyester.
  • the terephthalic acid and the branched diol are slurried into a reactor, and the esterification reaction is carried out under the catalysis of concentrated sulfuric acid.
  • the esterification reaction is pressurized under a nitrogen atmosphere, and the pressure is At normal pressure ⁇ 0.3MPa, the temperature is 180-240 ° C, when the water distillation amount in the esterification reaction reaches 90% of the theoretical value is the end of the esterification reaction; obtaining terephthalic acid glycol ester;
  • the terephthalic acid and ethylene glycol are slurried and added to the reactor to carry out an esterification reaction.
  • the esterification reaction is carried out under a nitrogen atmosphere, and the pressure is from normal pressure to 0.3 MPa, and the temperature is from 250 to 260. °C, when the water distillation amount in the esterification reaction reaches 90% or more of the theoretical value, it is the end point of the esterification reaction, and ethylene terephthalate is obtained;
  • the terephthalic acid glycol ester prepared in the step (1) is added, stirred and mixed for 15-20 minutes, under the action of the catalyst and the stabilizer, under a negative pressure.
  • the polycondensation reaction starts in the low vacuum stage.
  • the pressure is smoothly pumped from normal pressure to below 500Pa, the temperature is controlled at 260 ⁇ 270°C, and the reaction time is 30 ⁇ 50 minutes.
  • vacuum is continued to carry out the high vacuum stage.
  • the polycondensation reaction is carried out to reduce the reaction pressure to an absolute pressure of less than 100 Pa, the reaction temperature is controlled at 275 to 280 ° C, and the reaction time is 50 to 90 minutes to obtain a modified polyester;
  • the modified polyester is then pelletized to obtain a modified polyester chip, and the obtained polyester chip is thickened by solid phase polycondensation, so that the intrinsic viscosity of the polyester chip is increased to 1.0-1.2 dL/g, which is a high-viscosity slice;
  • the high uniformity colored polyester industrial yarn is obtained by metering, black masterbatch addition, porous spinneret extrusion, cooling, oiling, drawing, heat setting and winding;
  • the black masterbatch is added in an amount of 0.01% to 0.03% of the mass of the modified polyester chip;
  • the main process parameters of spinning are:
  • the extrusion temperature is 290-320 ° C;
  • the cooled air temperature is 20 to 30 ° C;
  • the winding speed is 2600 to 3200 m/min.
  • the method for preparing a high-uniformity colored polyester industrial yarn as described above, wherein in the step (1), the molar ratio of terephthalic acid to the branched-chain diol is 1:1.3-1.5; concentrated sulfuric acid The amount of addition is 0.3-0.5% by weight of terephthalic acid; the concentration of concentrated sulfuric acid is 50-60% by weight; in the step (2), the molar ratio of terephthalic acid to ethylene glycol is 1:1.2 ⁇ 2.0; in the step (3), the molar percentage of the terephthalic acid glycol ester to ethylene terephthalate is 2 to 5%; the catalyst is antimony trioxide, ethylene Alcohol or barium acetate, the catalyst is added in an amount of 0.01% to 0.05% by weight of the total terephthalic acid; the stabilizer is triphenyl phosphate, trimethyl phosphate or trimethyl phosphite, and the amount of stabilizer added is The total weight of terephthalic acid is 0.01%
  • the porous spinneret is a circular spinneret or an elliptical spinneret; the diameter of the circular spinneret is the largest with a series of ovals
  • the difference in the length of the major axis is greater than 10 mm, and the difference between the elliptical spinneret and the largest major axis length of the series of ellipse is greater than 10 mm.
  • the diameter of the guide hole of the wire hole is increased by 1.5 mm; the ratio of the length of the major axis to the minor axis of the ellipse is 1.3 to 1.8.
  • the number of layers of the elliptical array of the spinneret holes is smaller than the number of layers of the circular array, and the number of holes of the spinneret oval is larger than
  • the number of holes arranged in a circular shape therefore, the elliptical arrangement of the spinning holes facilitates the cooling of the ring blowing, improves the cooling efficiency of the ring blowing, and the fiber properties are also more excellent.
  • the ratio of the length of the major axis to the minor axis is closer to 1, and the ellipse is closer to a circle. The difference between the cooling efficiency and the cooling effect is not large.
  • the cooling effect is significantly improved.
  • the ratio of the major axis to the minor axis length of the series ellipse is 1.3 to 1.8, which can achieve higher cooling efficiency and better cooling effect.
  • the cross-sectional shape of the spinning micropores of the wire plate is circular, square, diamond, inline, triangular, trilobal, hollow or flat.
  • the raw material of the high uniformity colored polyester industrial yarn of the invention is a modified polyester, and the branched polyester diol segment contained in the modified polyester macromolecule, when the temperature is higher than the glass transition temperature, the branch first In the main chain movement, the increase of the free volume is much larger than that of the unbranched polyester macromolecular chain.
  • the free volume of the industrial yarn prepared by the modified polyester is much larger than that of the unconstrained industrial yarn at the same temperature. It is beneficial to reduce its melt viscosity.
  • the arrangement of the orifices on the spinneret of the present invention is elliptical.
  • the effective area of the spinneret is the same, the number of layers of the orifices in the elliptical arrangement is smaller than the number of layers arranged in the circle, and the ring blower is more easily blown through.
  • the spinning fine flow the spinning fine flow has a better cooling effect, and the prepared industrial yarn is also more excellent.
  • the effective area of the spinneret is the same, the number of holes in the elliptical shape of the spinneret hole is larger than the number of holes arranged in the circle, and the elliptical arrangement can achieve a greater degree of cooling, and the cooling efficiency is remarkably improved.
  • the raw material of the high uniformity colored polyester industrial yarn obtained by the invention is a modified polyester, and the branched polyester diol segment contained in the modified polyester macromolecule is branched when the temperature is higher than the glass transition temperature. Before the main chain moves, the increase of the free volume is much larger than that of the unbranched polyester macromolecular chain. The increase of the free volume is beneficial to reduce the melt viscosity and improve the processing performance.
  • the raw material of the high uniformity colored polyester industrial yarn obtained by the invention is a modified polyester, and the structural modification of the modified polyester containing the branched diol segment is not greatly damaged, and the polyester is maintained. Excellent performance of fiber.
  • the arrangement of the spinnerets on the high uniformity colored polyester industrial silk spinneret of the present invention is elliptical.
  • the effective area of the spinneret is the same, the number of layers of the spinneret elliptical is smaller than that of the circular array.
  • the number of rings is easier to blow through the spinning stream, the cooling effect of the spinning stream is better, and the prepared fiber performance is also better.
  • the arrangement of the spinning holes of the high uniformity colored polyester industrial silk spinneret of the invention is elliptical.
  • the effective area of the spinneret is the same, the number of holes of the spinneret elliptical is larger than that of the circular array.
  • the number, elliptical arrangement enables a greater degree of cooling and significantly increases cooling efficiency.
  • Figure 1 is an elliptical arrangement diagram of 374 spinnerets, the orifice diameter of the orifice is 2.0 mm, and the length ratio of the major axis of the ellipse to the minor axis is 1.3;
  • Figure 2 is a circular arrangement diagram of 370 orifices, the orifice of the orifice is 2.0 mm;
  • Fig. 3 is an elliptical arrangement diagram of 382 spinnerets having a hole diameter of 2.0 mm and a length ratio of the major axis to the minor axis of 1.6.
  • a preparation method of a modified polyester comprising the following steps:
  • the terephthalic acid with a molar ratio of A and B is slurried into the reactor, and the esterification reaction is carried out under the catalysis of a concentration of Cwt% and a concentration of D% concentrated sulfuric acid of the weight of terephthalic acid.
  • the esterification reaction is pressurized under a nitrogen atmosphere at a pressure of E MPa and a temperature of F ° C. When the water distillation amount in the esterification reaction reaches G% of the theoretical value, it is the end point of the esterification reaction, and the benzene is obtained.
  • the molar ratio of H terephthalic acid and ethylene glycol is slurried and added to the reactor for esterification reaction.
  • the esterification reaction is pressurized under a nitrogen atmosphere at a pressure of I MPa and a temperature of J ° C.
  • the amount of water distilled in the esterification reaction reaches K% of the theoretical value, the end point of the esterification reaction is obtained, and ethylene terephthalate is obtained;
  • the terephthalic acid glycol ester prepared in the step (1) After the end of the esterification reaction in the step (2), the terephthalic acid glycol ester prepared in the step (1), the molar percentage of the terephthalic acid glycol ester and the ethylene terephthalate are added.
  • the value is L%, stirred and mixed for M minutes, under the action of the catalyst O added in an amount of N% by weight of terephthalic acid and the stabilizer Q added in an amount of P% by weight of the terephthalic acid, under the condition of negative pressure
  • the pressure is smoothly pumped from normal pressure to absolute pressure R Pa, the temperature is controlled at S ° C, and the reaction time is T minutes.
  • vacuum is continued to carry out the polycondensation reaction in the high vacuum stage.
  • the reaction pressure was reduced to an absolute pressure of U Pa , the reaction temperature was controlled at V ° C, and the reaction time was W minutes to obtain a modified
  • the modified polyester obtained has a number average molecular weight of X and consists of a terephthalic acid segment, an ethylene glycol segment and a B segment, and the molar percentage of the B segment to the ethylene glycol segment is Y%.
  • the parameters of the variation in the different examples are shown in the following table.
  • the invention discloses a preparation method of high uniformity colored polyester industrial yarn, wherein the high uniformity colored polyester industrial yarn is obtained by using a porous spinneret, and the arrangement of the orifices on the spinneret is elliptical, and the elliptical arrangement means The center of the hole of the orifice is located on a concentric ellipse, the concentric ellipse is a series of ellipse, the long axes of all the ellipse are collinear, and the short axis is collinear.
  • the ratio of the major axis to the minor axis length of the ellipse is 1.3
  • the spacing of the adjacent orifices is equal to the diameter of the pilot hole of the orifice and 1.5 mm
  • the spinneret is a circular spinneret.
  • the diameter of the spinneret is 11mm from the largest long axis length of the series ellipse
  • the diameter of the pilot hole of the spinneret is 2.0mm
  • the number of spinnerets of the spinneret is 374
  • the spinneret of the spinneret The cross-sectional shape is circular.
  • the modified polyester obtained in Example 1 was subjected to solid phase polycondensation and viscosity-increasing, metering, black masterbatch addition, porous spinneret extrusion, cooling, oiling, drawing, heat setting and winding to obtain high uniformity.
  • a colored polyester industrial yarn in which the extrusion temperature is 290 ° C; the cooled air temperature is 20 ° C; the winding speed is 2600 m / min, and the black masterbatch is added in an amount of 0.01% by mass of the modified polyester chip.
  • the obtained high uniformity colored polyester industrial yarn has a breaking strength of 7.3 cN/dtex; a linear density deviation rate of 0.6%, a breaking strength CV value of 1.8%, a breaking elongation CV value of 4.5%, and an elongation at break of 11.0.
  • the melt viscosity decreased by 11%, and under the test conditions of a temperature of 177 ° C ⁇ 10 min ⁇ 0.05 cN / dtex, the dry heat shrinkage rate was 2.5%.
  • the invention discloses a preparation method of high uniformity colored polyester industrial yarn, wherein the high uniformity colored polyester industrial yarn is obtained by using a porous spinneret, and the arrangement of the orifices on the spinneret is elliptical, and the elliptical arrangement means The center of the hole of the orifice is located on a concentric ellipse, the concentric ellipse is a series of ellipse, the long axes of all the ellipse are collinear, and the short axis is collinear.
  • the ratio of the major axis to the minor axis length of the ellipse is 1.6
  • the spacing of adjacent orifices is equal to the diameter of the pilot hole of the orifice and 1.5 mm
  • the spinneret is a circular spinneret.
  • the diameter of the spinneret is 11 mm from the largest long axis length of the series ellipse
  • the diameter of the pilot hole of the spinneret is 2.0 mm
  • the number of spinnerets of the spinneret is 382
  • the spinneret of the spinneret The cross-sectional shape is circular.
  • the modified polyester obtained in Example 1 was subjected to solid phase polycondensation and viscosity-increasing, metering, black masterbatch addition, porous spinneret extrusion, cooling, oiling, drawing, heat setting and winding to obtain high uniformity.
  • a colored polyester industrial yarn in which the extrusion temperature is 290 ° C; the cooled air temperature is 20 ° C; the winding speed is 2600 m / min, and the black masterbatch is added in an amount of 0.01% by mass of the modified polyester chip.
  • the high uniformity colored polyester industrial yarn obtained has a breaking strength of 7.2 cN/dtex; a linear density deviation rate of 0.7%, a breaking strength CV value of 1.7%, a breaking elongation CV value of 4.8%, and an elongation at break of 11.0.
  • the melt viscosity decreased by 11%, and under the test conditions of a temperature of 177 ° C ⁇ 10 min ⁇ 0.05 cN / dtex, the dry heat shrinkage rate was 2.5%.
  • the invention discloses a preparation method of high uniformity colored polyester industrial yarn, wherein the high uniformity colored polyester industrial yarn is obtained by using a porous spinneret, and the arrangement of the spinning holes on the spinneret is circularly arranged, and the circular arrangement means The center of the hole of the spinneret is located on a concentric circle, and the concentric circles are a series of circles.
  • the spacing between adjacent orifices is equal to the diameter of the orifice of the orifice plus 1.5mm
  • the spinneret is a circular spinneret
  • the diameter of the circular spinneret and the largest diameter of the series circle The difference is 11 mm
  • the diameter of the orifice of the orifice is 2.0 mm
  • the number of orifices of the spinneret is 370
  • the cross-sectional shape of the orifice of the spinneret is circular.
  • the modified polyester obtained in Example 1 was subjected to solid phase polycondensation and viscosity-increasing, metering, black masterbatch addition, porous spinneret extrusion, cooling, oiling, drawing, heat setting and winding to obtain high uniformity.
  • a colored polyester industrial yarn in which the extrusion temperature is 290 ° C; the cooled air temperature is 20 ° C; the winding speed is 2600 m / min, and the black masterbatch is added in an amount of 0.01% by mass of the modified polyester chip.
  • the obtained high uniformity colored polyester industrial yarn has a breaking strength of 7.6 cN/dtex; a linear density deviation rate of 1%, a breaking strength CV value of 1.9%, a breaking elongation CV value of 5.3%, and an elongation at break of 12.1.
  • the melt viscosity decreased by 11%, and under the test conditions of a temperature of 177 ° C ⁇ 10 min ⁇ 0.05 cN / dtex, the dry heat shrinkage rate was 2.75%.
  • Example 29 Comparing with Example 29, it can be seen that when the effective area of the spinneret is the same, when the number of orifices is similar (the number of orifices arranged in a circular array is 370, the number of orifices in an elliptical arrangement is 374), elliptical arrangement The number of layers of the orifice is 6, which is smaller than the number 8 of the orifice arrays arranged in a circular arrangement, and the cooling effect is better; compared with the embodiment 30, it can be seen that when the effective area of the spinneret is the same, the orifices are arranged in an elliptical shape.
  • the number of layers is 5, which is smaller than the number 8 of the number of the orifice holes arranged in a circular arrangement, and the cooling effect is better.
  • the number of holes 382 of the oval-shaped orifices is larger than the number of holes 341 of the circularly arranged orifices, and the cooling efficiency is higher. .
  • the comparison of the fiber properties showed that the fiber linear density deviation rate, the breaking strength CV value, and the elongation at break CV value obtained in Example 29 and Example 30 were smaller than that in Comparative Example 1, indicating that the same process conditions were used, and the spinneret oval was used. Arranged spinneret The resulting fiber performance is superior to that of a spinneret having a circular arrangement of spinnerets.
  • the invention discloses a preparation method of a high uniformity colored polyester industrial yarn, which is obtained by using a porous spinneret.
  • the arrangement of the orifices on the spinneret is elliptical, and the elliptical arrangement means that the center of the orifice of the spinneret is concentric.
  • the concentric ellipse is a series of ellipse, the long axes of all ellipse are collinear, and the short axes are collinear.
  • the arrangement of the orifices is long axis symmetry, the ratio of the length of the major axis of the ellipse to the length of the minor axis is 1.4, the spacing of the adjacent orifices is equal to the diameter of the orifice of the orifice and 1.6 mm, and the spinneret is a circular spray.
  • the difference between the diameter of the wire plate and the circular spinneret and the length of the long axis of the series ellipse is 12mm, the diameter of the guide hole of the spinning hole is 1.5mm, and the number of the spinning holes of the spinneret is 384.
  • the cross-sectional shape of the spinneret is square.
  • the invention discloses a preparation method of a high uniformity colored polyester industrial yarn, which is obtained by using a porous spinneret.
  • the arrangement of the orifices on the spinneret is elliptical, and the elliptical arrangement means that the center of the orifice of the spinneret is concentric.
  • the concentric ellipse is a series of ellipse, the long axes of all ellipse are collinear, and the short axes are collinear.
  • the arrangement of the orifices is long axis symmetry, the ratio of the length of the major axis of the ellipse to the length of the minor axis is 1.4, the spacing of the adjacent orifices is equal to the diameter of the orifice of the orifice and 1.6 mm, and the spinneret is a circular spray.
  • the difference between the diameter of the wire plate and the circular spinneret and the length of the long axis of the series ellipse is 12mm, the diameter of the guide hole of the spinning hole is 1.5mm, and the number of the spinning holes of the spinneret is 192.
  • the cross-sectional shape of the spinneret is square.
  • the obtained high homogeneity colored polyester industrial yarn has a percent melt viscosity decrease at 290 ° C, the mechanical properties of the industrial yarn at normal temperature, and the industrial yarn under the test conditions of a temperature of 177 ° C ⁇ 10 min ⁇ 0.05 cN / dtex
  • the dry heat shrinkage rate is shown in the table below.
  • the invention discloses a preparation method of a high uniformity colored polyester industrial yarn, which is obtained by using a porous spinneret.
  • the arrangement of the orifices on the spinneret is elliptical, and the elliptical arrangement means that the center of the orifice of the spinneret is concentric.
  • the concentric ellipse is a series of ellipse, the long axes of all ellipse are collinear, and the short axes are collinear.
  • the arrangement of the orifices is long axis symmetry, the ratio of the length of the major axis of the ellipse to the length of the minor axis is 1.4, the spacing of the adjacent orifices is equal to the diameter of the orifice of the orifice and 1.6 mm, and the spinneret is a circular spray.
  • the difference between the diameter of the wire plate and the circular spinneret and the length of the long axis of the series ellipse is 12mm, the diameter of the guide hole of the spinning hole is 1.5mm, and the number of the orifice of the spinneret is 288.
  • the cross-sectional shape of the spinneret is square.
  • the obtained high homogeneity colored polyester industrial yarn has a percent melt viscosity decrease at 270 ° C, the mechanical properties of the industrial yarn at normal temperature, and the industrial yarn under the test conditions of a temperature of 177 ° C ⁇ 10 min ⁇ 0.05 cN / dtex
  • the dry heat shrinkage rate is shown in the table below.
  • the invention discloses a preparation method of a high uniformity colored polyester industrial yarn, which is obtained by using a porous spinneret.
  • the arrangement of the orifices on the spinneret is elliptical, and the elliptical arrangement means that the center of the orifice of the spinneret is concentric.
  • the concentric ellipse is a series of ellipse, the long axes of all ellipse are collinear, and the short axes are collinear.
  • the arrangement of the orifices is long axis symmetry, the ratio of the length of the major axis of the ellipse to the length of the minor axis is 1.4, the spacing of the adjacent orifices is equal to the diameter of the orifice of the orifice and 1.6 mm, and the spinneret is a circular spray.
  • the difference between the diameter of the wire plate and the circular spinneret and the length of the long axis of the series ellipse is 12mm, the diameter of the guide hole of the spinning hole is 1.5mm, and the number of the spinning holes of the spinneret is 192.
  • the cross-sectional shape of the spinneret is square.
  • Highly uniform colored polyester industrial yarn by metering, black masterbatch addition, porous spinneret extrusion, cooling, oiling, drawing, heat setting and winding, to produce high uniformity colored polyester industrial yarn, which squeezes
  • the temperature was 300 ° C; the cooled air temperature was 28 ° C; the winding speed was 3000 m / min, and the black masterbatch addition amount was 0.02% of the mass of the modified polyester chip.
  • the obtained high homogeneity colored polyester industrial yarn has a percent decrease in melt viscosity at 260 ° C, mechanical properties of industrial yarn at normal temperature, and industrial yarn under the test conditions of temperature of 177 ° C ⁇ 10 min ⁇ 0.05 cN / dtex
  • the dry heat shrinkage rate is shown in the table below.
  • the invention discloses a preparation method of a high uniformity colored polyester industrial yarn, which is obtained by using a porous spinneret.
  • the arrangement of the orifices on the spinneret is elliptical, and the elliptical arrangement means that the center of the orifice of the spinneret is concentric.
  • the concentric ellipse is a series of ellipse, the long axes of all ellipse are collinear, and the short axes are collinear.
  • the arrangement of the orifices is long axis symmetry, the ratio of the length of the major axis of the ellipse to the length of the minor axis is 1.4, the spacing of the adjacent orifices is equal to the diameter of the orifice of the orifice and 1.6 mm, and the spinneret is a circular spray.
  • the difference between the diameter of the wire plate and the circular spinneret and the length of the long axis of the series ellipse is 12mm, the diameter of the guide hole of the spinning hole is 1.5mm, and the number of the spinning holes of the spinneret is 244.
  • the cross-sectional shape of the spinneret is square.
  • the invention discloses a preparation method of a high uniformity colored polyester industrial yarn, which is obtained by using a porous spinneret.
  • the arrangement of the orifices on the spinneret is elliptical, and the elliptical arrangement means that the center of the orifice of the spinneret is concentric.
  • the concentric ellipse is a series of ellipse, the long axes of all ellipse are collinear, and the short axes are collinear.
  • the arrangement of the orifices is long axis symmetry, the ratio of the length of the major axis of the ellipse to the length of the minor axis is 1.4, the spacing of the adjacent orifices is equal to the diameter of the orifice of the orifice and 1.6 mm, and the spinneret is a circular spray.
  • the difference between the diameter of the wire plate and the circular spinneret and the length of the long axis of the series ellipse is 12mm, the diameter of the guide hole of the spinning hole is 1.5mm, and the number of the spinning holes of the spinneret is 192.
  • the cross-sectional shape of the spinneret is square.
  • the obtained high homogeneity colored polyester industrial yarn has a percent melt viscosity decrease at 280 ° C, the mechanical properties of the industrial yarn at normal temperature, and the industrial yarn under the test conditions of a temperature of 177 ° C ⁇ 10 min ⁇ 0.05 cN / dtex
  • the dry heat shrinkage rate is shown in the table below.
  • the invention discloses a preparation method of a high uniformity colored polyester industrial yarn, which is obtained by using a porous spinneret.
  • the arrangement of the orifices on the spinneret is elliptical, and the elliptical arrangement means that the center of the orifice of the spinneret is concentric.
  • the concentric ellipse is a series of ellipse, the long axes of all ellipse are collinear, and the short axes are collinear.
  • the arrangement of the orifices is long axis symmetry, the ratio of the length of the major axis of the ellipse to the length of the minor axis is 1.4, the spacing of the adjacent orifices is equal to the diameter of the orifice of the orifice and 1.6 mm, and the spinneret is a circular spray.
  • the difference between the diameter of the wire plate and the circular spinneret and the length of the long axis of the series ellipse is 12mm, the diameter of the guide hole of the spinning hole is 1.5mm, and the number of the spinning holes of the spinneret is 192.
  • the cross-sectional shape of the spinneret is square.
  • the invention discloses a preparation method of a high uniformity colored polyester industrial yarn, which is obtained by using a porous spinneret.
  • the arrangement of the orifices on the spinneret is elliptical, and the elliptical arrangement means that the center of the orifice of the spinneret is concentric.
  • the concentric ellipse is a series of ellipse, the long axes of all ellipse are collinear, and the short axes are collinear.
  • the arrangement of the orifices is long axis symmetry, the ratio of the length of the major axis of the ellipse to the length of the minor axis is 1.4, the spacing of the adjacent orifices is equal to the diameter of the orifice of the orifice and 1.6 mm, and the spinneret is a circular spray.
  • the difference between the diameter of the wire plate and the circular spinneret and the length of the long axis of the series ellipse is 12mm, the diameter of the guide hole of the spinning hole is 1.5mm, and the number of the spinning holes of the spinneret is 192.
  • the cross-sectional shape of the spinneret is square.
  • Highly uniform colored polyester industrial yarn by metering, black masterbatch addition, porous spinneret extrusion, cooling, oiling, drawing, heat setting and winding, to produce high uniformity colored polyester industrial yarn, which squeezes
  • the temperature was 320 ° C; the cooled air temperature was 30 ° C, the winding speed was 3000 m / min, and the black masterbatch addition amount was 0.03% of the mass of the modified polyester chip.
  • the obtained high homogeneity colored polyester industrial yarn has a percent decrease in melt viscosity at 280 ° C, mechanical properties of industrial yarn at normal temperature, and industrial yarn under the test conditions of temperature of 177 ° C ⁇ 10 min ⁇ 0.05 cN / dtex
  • the dry heat shrinkage rate is shown in the table below.

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Abstract

一种高均匀性有色聚酯工业丝及其制备方法，高均匀性有色聚酯工业丝的原料为由对苯二甲酸链段、乙二醇链段和含支链的二元醇链段组成的改性聚酯。高均匀性有色聚酯工业丝的制备方法为将对苯二甲酸与含支链的二元醇，在浓硫酸的催化，进行酯化反应得到对苯二甲酸二元醇酯；然后将对苯二甲酸和乙二醇配成进行酯化反应，得到对苯二甲酸乙二醇酯；最后将两者搅拌混合，在催化剂和稳定剂的作用下，进行低真空阶段和高真空阶段的缩聚反应，制得改性聚酯，改性聚酯经计量、黑色母粒添加、多孔喷丝板挤出、冷却、上油、拉伸、热定型和卷绕，制得高均匀性有色聚酯工业丝。

Description

一种高均匀性有色聚酯工业丝及其制备方法 技术领域
本发明属聚酯纤维技术领域，涉及一种高均匀性有色聚酯工业丝及其制备方法。
背景技术
聚对苯二甲酸乙二醇酯(PET纤维或聚酯纤维)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，且织物具有抗皱免资，挺括性好等优点，广泛应用于服装、家纺等领域。
PET属于对称性的直链大分子，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，使聚酯具有较高的熔点，一般聚酯的熔点在260℃左右。随着生产应用的进行一步拓展，对聚酯的耐热性提出了更高的要求。在聚酯中引入不饱和双键，并在纤维纺制过程中完成交联反应，使纤维在耐热性方面有了较大幅度的提高。在聚酯纤维引入不饱和双键，并有效、安全地控制其交联，将对聚酯纤维的力学性能、耐热性能、耐化学性能、阻燃性能有较幅度的提高，如何运用好不饱和双键是聚酯纤维生产工艺中十分重要的课题。
聚酯结构对玻璃化转变温度的影响是明显的，增加了分子链段运动的壁垄，PET的玻璃化转变温度较高，需要在很高的温度下染色，促进染料分子向纤维内部的扩散。另外，PET的分子链规整，结晶性好，分子链排列紧密，并且分子链上没有与染料分子发生作用的极性基团，使聚酯纤维的上色更加困难。
聚酯工业丝若采用染色方法进行上色，一方面需在高温高压下进行染色，纤维存在一定量的沸水收缩，造成纤维的品质下降；另一方面染黑色大都使染料，而染料的耐候性较差，将影响纤维的使用周期。
熔融纺丝过程中有许多参数，这些参数决定纤维成型的历程和纺出纤维的结构和性能，生产上就是通过控制这些参数来制得所需性能的纤维。长期以来化纤生产都采用侧吹风作为冷却方式，能源消耗占到长丝生产成本的很大部分，随着人们对化纤性能和品质要求日益提高，化纤长丝新产品的开发向高附加值的差别化纤维方向发展，要求更高的冷却吹风条件，于是提出了环吹风装置。环吹风装置不仅具备每束丝受风均匀的优势，而且能耗相比较低，有效的解决了侧吹风由于吹风面积大而造成的风能损失问题。
在纺丝过程中，尽管环吹风有着明显的优势，但仍无法很好地解决多孔丝的冷却不均的问题：由于纺出的丝从圆形喷丝板挤出后，通过环吹风冷却，由于圆形喷丝板圈数较多，使得环吹风很难进入最内层，导致在最外层的丝已经冷却后最内层的丝可能还未冷却，从而所得的丝出现纤度不匀，强度不匀等问题，致使后续对丝的进一步加工出现难度。
发明内容
本发明要解决的技术问题是针对现有技术的不足，提供一种高均匀性有色聚酯工业丝及其制备方法，本发明高均匀性有色聚酯工业丝的原料为改性聚酯，改性聚酯的分子链中引入含支链的二元醇链段，经改性聚酯制备的改性高均匀性有色聚酯工业丝，一定温度条件下，高均匀性有色聚酯工业丝内部分子链间的空间间隙的增加幅度远远大于同等温度下无支链的有色聚酯工业丝，高均匀性有色聚酯工业丝的熔体粘度降低，降低加工温度，减少降解速率，有利于加工。另外本发明的高均匀性有色聚酯工业丝的多孔喷丝板上喷丝孔的排列方式为椭圆形排列，椭圆形排列是指喷丝孔的孔中心位于同心椭圆上，同心椭圆为系列椭圆，所有椭圆的长轴共线，且短轴共线；能够达到较高的冷却效率和较好的冷却效果。
一种高均匀性有色聚酯工业丝，所述高均匀性有色聚酯工业丝是指添加黑色母粒的聚酯工业丝，所述高均匀性有色聚酯工业丝由改性聚酯经固相增粘后纺丝得；所述高均匀性有色聚酯工业丝的材质为改性聚酯，所述改性聚酯由对苯二甲酸链段、乙二醇链段和含支链的二元醇链段组成，所述含支链的二元醇链段是指支链位于二元醇链段中的一个非端基碳上且支链为含有5-10个碳原子的直链碳链的二元醇链段，所述高均匀性有色聚酯工业丝的，断裂强度≥7.0cN/dtex，线密度偏差率≤1.0％，断裂强度CV值≤2.0％，断裂伸长CV值≤5.5％；所述高均匀性有色聚酯工业丝线在260～290℃下，熔体粘度下降10-20％，在温度为177℃×10min×0.05cN/dtex的测试条件下，干热收缩率为2.5±0.5％。
一种高均匀性有色聚酯工业丝为改性聚酯，在改性聚酯大分子长链上引入含支链的二元醇链段，而支链的长短和数量对改性聚酯的结晶性能和流动行为的影响较大，支链长度太短达不到聚酯改性的目的，长度太长会引起新的缠结，影响其流动行为，当支链位于二元醇链段中的一个非端基碳上且支链为含有5-10个碳原子的直链碳链时，经改性聚酯制备的一种高均匀性有色聚酯工业丝，在一定温度条件下，工业丝内部分子链间的空间间隙的增加幅度远远大于同等温度下无支链的工业丝， 有利于工业丝熔体粘度降低，便于进一步的加工。
作为优选的技术方案：
如上所述的一种高均匀性有色聚酯工业丝，所述高均匀性有色聚酯工业丝的断裂伸长为12.0±1.5％；所述改性聚酯的数均分子量为15000-30000。
如上所述的一种高均匀性有色聚酯工业丝，所述含支链的二元醇链段为2-戊基-1,3丙二醇链段、2-己基-1,3丙二醇链段、2-庚基-1,3丙二醇链段、2-辛基-1,3丙二醇链段、2-壬基-1,3丙二醇链段、2-癸基-1,3丙二醇链段、2-戊基-1,4丁二醇链段、2-己基-1,4丁二醇链段、2-庚基-1,4丁二醇链段、2-辛基-1,4丁二醇链段、2-壬基-1,4丁二醇链段、2-癸基-1,4丁二醇链段、2-戊基-1,5戊二醇链段、2-己基-1,5戊二醇链段、2-庚基-1,5戊二醇链段、2-辛基-1,5戊二醇链段、2-壬基-1,5戊二醇链段、2-癸基-1,5戊二醇链段、2-戊基-1,6己二醇链段、2-己基-1,6己二醇链段、2-庚基-1,6己二醇链段、2-辛基-1,6己二醇链段、2-壬基-1,6己二醇链段或2-癸基-1,6己二醇链段中的一种以上；所述含支链的二元醇链段与乙二醇链段的摩尔百分比值为2～5％。
本发明的一种高均匀性有色聚酯工业丝的制备方法，将改性聚酯经固相缩聚增粘、计量、黑色母粒添加、多孔喷丝板挤出、冷却、上油、拉伸、热定型和卷绕，制得高均匀性有色聚酯工业丝；
所述多孔喷丝板上喷丝孔的排列方式为椭圆形排列，所述椭圆形排列是指喷丝孔的孔中心位于同心椭圆上，所述同心椭圆为系列椭圆，所有椭圆的长轴共线，且短轴共线；
改性聚酯的制备过程包括以下步骤：
(1)对苯二甲酸二元醇酯的制备：
将对苯二甲酸与含支链的二元醇配成浆料后，在浓硫酸的催化作用下，进行酯化反应，得到对苯二甲酸二元醇酯；所述含支链的二元醇是支链位于二元醇链段中的一个非端基碳上且支链为含有5-10个碳原子的直链碳链的二元醇；
对于含支链的二元醇，其支链为烷基，是吸电子基团，在支链的存在，使分子链的空间体积增加，溶剂化作用变小，二元醇中质子不易离解，使得含支链的二元醇与对苯二甲酸的反应活性小于乙二醇，若采用同乙二醇混合与对苯二甲酸反应，会造成含支链的二元醇反应不完整，从而影响含支链的二元醇在聚酯大分子中的比例，进而影响聚酯的性能。本发明采用先将含支链的二元醇在硫酸的催化作用下与对苯二甲酸进行酯化反应，其产物在乙二醇与对苯二甲酸酯化结束后加入，保证了含支链的二元醇配比的稳定性。
(2)对苯二甲酸乙二醇酯的制备：
将对苯二甲酸和乙二醇配成浆料后，进行酯化反应，得到对苯二甲酸乙二醇酯；
(3)改性聚酯的制备：
在步骤(2)中的酯化反应结束后，加入步骤(1)中制备的对苯二甲酸二元醇酯，搅拌混合，在催化剂和稳定剂的作用下，在负压的条件下，依次进行低真空阶段的缩聚反应和高真空阶段的缩聚反应，制得改性聚酯。
如上所述的一种高均匀性有色聚酯工业丝的制备方法，所述改性聚酯制备的具体步骤为：
(1)对苯二甲酸二元醇酯的制备：
将对苯二甲酸与含支链的二元醇配成浆料加入反应器中，在浓硫酸的催化作用下，进行酯化反应，酯化反应在氮气氛围中加压反应，加压压力为常压～0.3MPa，温度为180～240℃，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；得到对苯二甲酸二元醇酯；
(2)对苯二甲酸乙二醇酯的制备：
将对苯二甲酸和乙二醇配成浆料后加入反应器中，进行酯化反应，酯化反应在氮气氛围中加压反应，加压压力为常压～0.3MPa，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，得到对苯二甲酸乙二醇酯；
(3)改性聚酯的制备：
在步骤(2)中的酯化反应结束后，加入步骤(1)中制备的对苯二甲酸二元醇酯，搅拌混合15-20分钟，在催化剂和稳定剂的作用下，在负压的条件下开始低真空阶段的缩聚反应，该阶段压力由常压平稳抽至绝对压力500Pa以下，温度控制在260～270℃，反应时间为30～50分钟；然后继续抽真空，进行高真空阶段的缩聚反应，使反应压力降至绝对压力小于100Pa，反应温度控制在275～280℃，反应时间50～90分钟，制得改性聚酯；
再将改性聚酯经切粒得到改性聚酯切片，所得到聚酯切片通过固相缩聚增粘，使聚酯切片的特性粘度提高到1.0～1.2dL/g，即为高粘切片；再经计量、黑色母粒添加、多孔喷丝板挤出、冷却、上油、拉伸、热定型和卷绕，制得高均匀性有色聚酯工业丝；
所述黑色母粒添加量为所述改性聚酯切片质量的0.01％～0.03％；
纺丝主要工艺参数为：
所述挤出的温度为290～320℃；
所述冷却的风温为20～30℃；
所述卷绕的速度为2600～3200m/min。
如上所述的一种高均匀性有色聚酯工业丝的制备方法，所述步骤(1)中，对苯二甲酸与含支链的二元醇的摩尔比为1:1.3-1.5；浓硫酸加入量为对苯二甲酸重量的0.3-0.5％；所述浓硫酸的浓度为50-60wt％；所述步骤(2)中，对苯二甲酸与乙二醇的摩尔比为1:1.2～2.0；所述步骤(3)中，所述对苯二甲酸二元醇酯与对苯二甲酸乙二醇酯的摩尔百分比值为2～5％；所述催化剂为三氧化二锑、乙二醇锑或醋酸锑，催化剂加入量为对苯二甲酸总重量的0.01％～0.05％；所述稳定剂为磷酸三苯酯、磷酸三甲酯或亚磷酸三甲酯，稳定剂加入量为所述对苯二甲酸总重量的0.01％～0.05％。
如上所述的一种高均匀性有色聚酯工业丝的制备方法，所述含支链的二元醇为2-戊基-1,3丙二醇、2-己基-1,3丙二醇、2-庚基-1,3丙二醇、2-辛基-1,3丙二醇、2-壬基-1,3丙二醇、2-癸基-1,3丙二醇、2-戊基-1,4丁二醇、2-己基-1,4丁二醇、2-庚基-1,4丁二醇、2-辛基-1,4丁二醇、2-壬基-1,4丁二醇、2-癸基-1,4丁二醇、2-戊基-1,5戊二醇、2-己基-1,5戊二醇、2-庚基-1,5戊二醇、2-辛基-1,5戊二醇、2-壬基-1,5戊二醇、2-癸基-1,5戊二醇、2-戊基-1,6己二醇、2-己基-1,6己二醇，2-庚基-1,6己二醇、2-辛基-1,6己二醇、2-壬基-1,6己二醇或2-癸基-1,6己二醇中的一种以上。
如上所述的一种高均匀性有色聚酯工业丝的制备方法，所述多孔喷丝板为圆形喷丝板或椭圆形喷丝板；所述圆形喷丝板的直径与系列椭圆最大的长轴长度的差值大于10mm，所述椭圆形喷丝板与系列椭圆最大的长轴长度的差值大于10mm。
如上所述的一种高均匀性有色聚酯工业丝的制备方法，所述多孔喷丝板上喷丝孔的排列为长轴和/或短轴对称，相邻喷丝孔的间距大于等于喷丝孔的导孔直径加上1.5mm；椭圆的长轴与短轴长度的比值为1.3～1.8。
当喷丝板的有效面积相同时，由于椭圆形的周长大于圆形的周长，喷丝孔椭圆形排列的层数小于圆形排列的层数，喷丝孔椭圆形排列的孔数大于圆形排列的孔数，因此，喷丝孔椭圆形排列有利于环吹风的冷却，提高环吹风的冷却效率，制备的纤维性能也更加优良。长轴与短轴长度的比值越接近于1，椭圆越近似于圆，冷却效率和冷却效果的差别不大；长轴与短轴长度的比值为1.3时，冷却效果显著提高，单圈孔数相应增加16％；长轴与短轴长度的比值为1.8时，冷却效果提高较大，单圈孔数相应增加33％，相同孔数情况下，本发明的椭圆形排列比常规同心圆排列的圈数减少，易于冷却风吹透，使内外圈的纤维冷却条件更均匀；长轴与短轴长度的比值大于1.8时，椭圆偏向于形成扁平的形状，不易打孔，同时冷却效果不再升高。因此，系列椭圆的长轴与短轴长度的比值为1.3～1.8，能够达到较高的冷却效率和较好的冷却效果。
如上所述的一种高均匀性有色聚酯工业丝的制备方法，所述喷丝孔的导孔直径为1.5～2.5mm；所述喷丝板的喷丝孔数大于等于192，所述喷丝板的喷丝微孔的横截面形状为圆形、正方形、菱形、一字型、三角型、三叶型、中空型或扁平型
本发明的原理为：
本发明的高均匀性有色聚酯工业丝的原料为改性聚酯，改性聚酯大分子中含有的含支链的二元醇链段，当温度高于玻璃化温度时，支链先于主链运动，使自由体积的增加幅度远远大于无支链的聚酯大分子链的特性,经改性聚酯制备的工业丝的自由体积远远大于同等温度下无支链的工业丝，有利于降低其熔体粘度。
本发明的喷丝板上喷丝孔的排列方式为椭圆形排列，喷丝板的有效面积相同时，喷丝孔椭圆形排列的层数小于圆形排列的层数，环吹风更容易吹透纺丝细流，纺丝细流的冷却效果更好，制备的工业丝也更加优良。喷丝板的有效面积相同时，喷丝孔椭圆形排列的孔数大于圆形排列的孔数，椭圆形排列能够实现更大程度的冷却，显著提高冷却效率。
有益效果：
本发明所得的高均匀性有色聚酯工业丝的原料为改性聚酯，改性聚酯大分子中含有的含支链的二元醇链段，当温度高于玻璃化温度时，支链先于主链运动，使自由体积的增加幅度远远大于无支链的聚酯大分子链的特性，自由体积的增加有利于降低熔体粘度，改善其加工性能。
本发明所得的高均匀性有色聚酯工业丝的原料为改性聚酯，含支链的二元醇链段的引入对的改性聚酯的结构规整性没有大的破坏，保持了聚酯纤维的优良性能。
本发明的高均匀性有色聚酯工业丝喷丝板上喷丝孔的排列方式为椭圆形排列，喷丝板的有效面积相同时，喷丝孔椭圆形排列的层数小于圆形排列的层数，环吹风更容易吹透纺丝细流，纺丝细流的冷却效果更好，制备的纤维性能也更加优良。
本发明的高均匀性有色聚酯工业丝喷丝板上喷丝孔的排列方式为椭圆形排列，喷丝板的有效面积相同时，喷丝孔椭圆形排列的孔数大于圆形排列的孔数，椭圆形排列能够实现更大程度的冷却，显著提高冷却效率。
附图说明
图1为374个喷丝孔的椭圆形排列图，喷丝孔的孔径为2.0mm，椭圆长轴与短轴的长度比值为1.3；
图2为370个喷丝孔的圆形排列图，喷丝孔的孔径为2.0mm；
图3为382个喷丝孔的椭圆形排列图，喷丝孔的孔径为2.0mm，椭圆长轴与短轴的长度比值为1.6。
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。
实施例1～28
一种改性聚酯的制备方法，具体包括以下步骤：
(1)对苯二甲酸二元醇酯的制备：
将摩尔比为A的对苯二甲酸与B配成浆料加入反应器中，在浓度为Cwt％，加入量为对苯二甲酸重量的D％的浓硫酸的催化作用下，进行酯化反应，酯化反应在氮气氛围中加压反应，加压压力为E MPa，温度为F℃，当酯化反应中的水馏出量达到理论值的G％时为酯化反应终点，得到对苯二甲酸二元醇酯；
(2)对苯二甲酸乙二醇酯的制备：
将摩尔比为H对苯二甲酸和乙二醇配成浆料后加入反应器中，进行酯化反应，酯化反应在氮气氛围中加压反应，加压压力为I MPa，温度为J℃，当酯化反应中的水馏出量达到理论值的K％时为酯化反应终点，得到对苯二甲酸乙二醇酯；
(3)改性聚酯的制备：
在步骤(2)中的酯化反应结束后，加入步骤(1)中制备的对苯二甲酸二元醇酯，对苯二甲酸二元醇酯与对苯二甲酸乙二醇酯的摩尔百分比值为L％，搅拌混合M分钟，在加入量为对苯二甲酸重量的N％的催化剂O和加入量为对苯二甲酸重量的P％的稳定剂Q的作用下，在负压的条件下开始低真空阶段的缩聚反应，该阶段压力由常压平稳抽至绝对压力为R Pa，温度控制在S℃，反应时间为T分钟；然后继续抽真空，进行高真空阶段的缩聚反应，使反应压力降至绝对压力为U Pa，反应温度控制在V℃，反应时间W分钟，制得改性聚酯。
制得的改性聚酯的数均分子量为X，由对苯二甲酸链段、乙二醇链段和B链段组成，B链段与乙二醇链段的摩尔百分比值为Y％。不同实施例中变化的参数如下表所示，表中“戊丙”代表2-戊基-1,3丙二醇，“己丙”代表2-己基-1,3丙二醇，“庚丙”代表2-庚基-1,3丙二醇，“辛丙”代表2-辛基-1,3丙二醇，“壬丙”代表2-壬基-1,3丙二醇，“癸丙”代表2-癸基-1,3丙二醇，“戊丁”代表2-戊基-1,4丁二醇，“己丁”代表2-己基-1,4丁二醇，“庚丁”代表2-庚基-1,4丁二醇，“辛丁”代表2-辛基-1,4丁二醇，“壬丁”代表2-壬基-1,4丁二醇，“癸丁”代表2-癸基-1,4丁二醇，“戊戊”代表2-戊基-1,5戊二醇，“己戊”代表2-己基-1,5戊二醇，“庚戊”代表2-庚基-1,5戊二醇，“辛戊”代表2-辛基-1,5戊二醇，“壬戊”代表2-壬基-1,5戊二醇，“癸戊”代表2-癸基-1,5戊二醇，“戊己”代表2-戊基-1,6己二醇，“己己”代表2-己基-1,6己二醇，“庚己”代表2-庚基-1,6己二醇，“辛己”代表2-辛基-1,6己二醇，“壬己”代表2-壬基-1,6己二醇，“癸己”代表2-癸基-1,6己二醇，“三”代表三氧化二锑，“乙”代表乙二醇锑，“醋”代表醋酸锑，“苯”代表磷酸三苯酯，“甲”代表磷酸三甲酯，“亚”代表亚磷酸三甲酯，比例关系为摩尔比。
Figure PCTCN2017089944-appb-000001
Figure PCTCN2017089944-appb-000002
Figure PCTCN2017089944-appb-000003
Figure PCTCN2017089944-appb-000004
实施例29
一种高均匀性有色聚酯工业丝的制备方法，高均匀性有色聚酯工业丝采用多孔喷丝板制得，喷丝板上喷丝孔的排列方式为椭圆形排列，椭圆形排列是指喷丝孔的孔中心位于同心椭圆上，同心椭圆为系列椭圆，所有椭圆的长轴共线，且短轴共线。
如图1所示，椭圆的长轴与短轴长度的比值为1.3，相邻喷丝孔的间距等于喷丝孔的导孔直径加上1.5mm，喷丝板为圆形喷丝板，圆形喷丝板的直径与系列椭圆最大的长轴长度的差值为11mm，喷丝孔的导孔直径为2.0mm，喷丝板的喷丝孔数为374，喷丝板的喷丝微孔的横截面形状为圆形。
实施例1制得的改性聚酯经固相缩聚增粘、计量、黑色母粒添加、多孔喷丝板挤出、冷却、上油、拉伸、热定型和卷绕，制得高均匀性有色聚酯工业丝，其中挤出的温度为290℃；冷却的风温为20℃；卷绕的速度为2600m/min，黑色母粒添加量为改性聚酯切片质量的0.01％。制得的高均匀性有色聚酯工业丝的断裂强度为7.3cN/dtex；线密度偏差率为0.6％，断裂强度CV值为1.8％，断裂伸长CV值为4.5％，断裂伸长为11.0，在260℃下，熔体粘度下降11％，在温度为177℃×10min×0.05cN/dtex的测试条件下，干热收缩率为2.5％。
实施例30
一种高均匀性有色聚酯工业丝的制备方法，高均匀性有色聚酯工业丝采用多孔喷丝板制得，喷丝板上喷丝孔的排列方式为椭圆形排列，椭圆形排列是指喷丝孔的孔中心位于同心椭圆上，同心椭圆为系列椭圆，所有椭圆的长轴共线，且短轴共线。
如图3所示，椭圆的长轴与短轴长度的比值为1.6，相邻喷丝孔的间距等于喷丝孔的导孔直径加上1.5mm，喷丝板为圆形喷丝板，圆形喷丝板的直径与系列椭圆最大的长轴长度的差值为11mm，喷丝孔的导孔直径为2.0mm，喷丝板的喷丝孔数为382，喷丝板的喷丝微孔的横截面形状为圆形。
实施例1制得的改性聚酯经固相缩聚增粘、计量、黑色母粒添加、多孔喷丝板挤出、冷却、上油、拉伸、热定型和卷绕，制得高均匀性有色聚酯工业丝，其中挤出的温度为290℃；冷却的风温为20℃；卷绕的速度为2600m/min，黑色母粒添加量为改性聚酯切片质量的0.01％。制得的高均匀性有色聚酯工业丝的断裂强度为7.2cN/dtex；线密度偏差率为0.7％，断裂强度CV值为1.7％，断裂伸长CV值为4.8％，断裂伸长为11.0，在260℃下，熔体粘度下降11％，在温度为177℃×10min×0.05cN/dtex的测试条件下，干热收缩率为2.5％。
对比例1
一种高均匀性有色聚酯工业丝的制备方法，高均匀性有色聚酯工业丝采用多孔喷丝板制得，喷丝板上喷丝孔的排列方式为圆形排列，圆形排列是指喷丝孔的孔中心位于同心圆上，同心圆为系列圆形。如图2所示，相邻喷丝孔的间距等于喷丝孔的导孔直径加上1.5mm，喷丝板为圆形喷丝板，圆形喷丝板的直径与系列圆形最大的直径的差值为11mm，喷丝孔的导孔直径为2.0mm，喷丝板的喷丝孔数为370，喷丝板的喷丝微孔的横截面形状为圆形。
实施例1制得的改性聚酯经固相缩聚增粘、计量、黑色母粒添加、多孔喷丝板挤出、冷却、上油、拉伸、热定型和卷绕，制得高均匀性有色聚酯工业丝，其中挤出的温度为290℃；冷却的风温为20℃；卷绕的速度为2600m/min，黑色母粒添加量为改性聚酯切片质量的0.01％。制得的高均匀性有色聚酯工业丝的断裂强度为7.6cN/dtex；线密度偏差率为1％，断裂强度CV值为1.9％，断裂伸长CV值为5.3％，断裂伸长为12.1，在260℃下，熔体粘度下降11％，在温度为177℃×10min×0.05cN/dtex的测试条件下，干热收缩率为2.75％。
与实施例29对比可以看出，喷丝板的有效面积相同时，喷丝孔数相近时(圆形排列喷丝孔数为370，椭圆形排列喷丝孔数为374)，椭圆形排列的喷丝孔层数为6，小于圆形排列的喷丝孔层数8，冷却效果更好；与实施例30对比可以看出，喷丝板的有效面积相同时，椭圆形排列的喷丝孔层数为5，小于圆形排列的喷丝孔层数8，冷却效果更好，椭圆形排列的喷丝孔的孔数382大于圆形排列的喷丝孔的孔数370，冷却效率更高。纤维性能的对比结果表明，实施例29和实施例30制得的纤维线密度偏差率、断裂强度CV值、断裂伸长CV值小于对比例1，说明相同工艺条件下，采用喷丝孔椭圆形排列的喷丝板制 得的纤维性能优于采用喷丝板圆形排列的喷丝板。
实施例31～33
一种高均匀性有色聚酯工业丝的制备方法，采用多孔喷丝板制得，喷丝板上喷丝孔的排列方式为椭圆形排列，椭圆形排列是指喷丝孔的孔中心位于同心椭圆上，同心椭圆为系列椭圆，所有椭圆的长轴共线，且短轴共线。
喷丝孔的排列为长轴对称，椭圆的长轴与短轴长度的比值为1.4，相邻喷丝孔的间距等于喷丝孔的导孔直径加上1.6mm，喷丝板为圆形喷丝板，圆形喷丝板的直径与系列椭圆最大的长轴长度的差值为12mm，喷丝孔的导孔直径为1.5mm，喷丝板的喷丝孔数为384，喷丝板的喷丝微孔的横截面形状为正方形。
高均匀性有色聚酯工业丝经计量、黑色母粒添加、多孔喷丝板挤出、冷却、上油、拉伸、热定型和卷绕，制得高均匀性有色聚酯工业丝，其中挤出的温度为290℃；冷却的风温为30℃；卷绕的速度为3100m/min，黑色母粒添加量为改性聚酯切片质量的0.03％。制得的高均匀性有色聚酯工业丝在280℃下，熔体粘度下降百分数，常温下工业丝的力学性能数据，以及在温度为177℃×10min×0.05cN/dtex的测试条件下，工业丝的干热收缩率如下表。
Figure PCTCN2017089944-appb-000005
实施例34～36
一种高均匀性有色聚酯工业丝的制备方法，采用多孔喷丝板制得，喷丝板上喷丝孔的排列方式为椭圆形排列，椭圆形排列是指喷丝孔的孔中心位于同心椭圆上，同心椭圆为系列椭圆，所有椭圆的长轴共线，且短轴共线。
喷丝孔的排列为长轴对称，椭圆的长轴与短轴长度的比值为1.4，相邻喷丝孔的间距等于喷丝孔的导孔直径加上1.6mm，喷丝板为圆形喷丝板，圆形喷丝板的直径与系列椭圆最大的长轴长度的差值为12mm，喷丝孔的导孔直径为1.5mm，喷丝板的喷丝孔数为192，喷丝板的喷丝微孔的横截面形状为正方形。
高均匀性有色聚酯工业丝经计量、黑色母粒添加、多孔喷丝板挤出、冷却、上油、拉伸、热定型和卷绕，制得高均匀性有色聚酯工业丝，挤出的温度为290℃；冷却的风温为22℃；卷绕的速度为3200m/min，黑色母粒添加量为改性聚酯切片质量的0.02％。制得的高均匀性有色聚酯工业丝在290℃下熔体粘度下降百分比，常温下工业丝的力学性能数据，以及在温度为177℃×10min×0.05cN/dtex的测试条件下，工业丝的干热收缩率如下表。
Figure PCTCN2017089944-appb-000006
实施例37～39
一种高均匀性有色聚酯工业丝的制备方法，采用多孔喷丝板制得，喷丝板上喷丝孔的排列方式为椭圆形排列，椭圆形排列是指喷丝孔的孔中心位于同心椭圆上，同心椭圆为系列椭圆，所有椭圆的长轴共线，且短轴共线。
喷丝孔的排列为长轴对称，椭圆的长轴与短轴长度的比值为1.4，相邻喷丝孔的间距等于喷丝孔的导孔直径加上1.6mm，喷丝板为圆形喷丝板，圆形喷丝板的直径与系列椭圆最大的长轴长度的差值为12mm，喷丝孔的导孔直径为1.5mm，喷丝板的喷丝孔数为288，喷丝板的喷丝微孔的横截面形状为正方形。
高均匀性有色聚酯工业丝经计量、黑色母粒添加、多孔喷丝板挤出、冷却、上油、拉伸、热定型和卷绕，制得高均匀性有色聚酯工业丝，其中挤出的温度为310℃；冷却的风温为28℃；卷绕的速度为3000m/min，黑色母粒添加量为改性聚酯切片质量的0.025％。制得的高均匀性有色聚酯工业丝在270℃下熔体粘度下降百分数，常温下工业丝的力学性能数据，以及在温度为177℃×10min×0.05cN/dtex的测试条件下，工业丝的干热收缩率如下表。
Figure PCTCN2017089944-appb-000007
Figure PCTCN2017089944-appb-000008
实施例40～42
一种高均匀性有色聚酯工业丝的制备方法，采用多孔喷丝板制得，喷丝板上喷丝孔的排列方式为椭圆形排列，椭圆形排列是指喷丝孔的孔中心位于同心椭圆上，同心椭圆为系列椭圆，所有椭圆的长轴共线，且短轴共线。
喷丝孔的排列为长轴对称，椭圆的长轴与短轴长度的比值为1.4，相邻喷丝孔的间距等于喷丝孔的导孔直径加上1.6mm，喷丝板为圆形喷丝板，圆形喷丝板的直径与系列椭圆最大的长轴长度的差值为12mm，喷丝孔的导孔直径为1.5mm，喷丝板的喷丝孔数为192，喷丝板的喷丝微孔的横截面形状为正方形。
高均匀性有色聚酯工业丝经计量、黑色母粒添加、多孔喷丝板挤出、冷却、上油、拉伸、热定型和卷绕，制得高均匀性有色聚酯工业丝，其中挤出的温度为300℃；冷却的风温为28℃；卷绕的速度为3000m/min，黑色母粒添加量为改性聚酯切片质量的0.02％。制得的高均匀性有色聚酯工业丝在260℃下熔体粘度下降百分比，常温下工业丝的力学性能数据，以及在温度为177℃×10min×0.05cN/dtex的测试条件下，工业丝的干热收缩率如下表。
Figure PCTCN2017089944-appb-000009
实施例43～45
一种高均匀性有色聚酯工业丝的制备方法，采用多孔喷丝板制得，喷丝板上喷丝孔的排列方式为椭圆形排列，椭圆形排列是指喷丝孔的孔中心位于同心椭圆上，同心椭圆为系列椭圆，所有椭圆的长轴共线，且短轴共线。
喷丝孔的排列为长轴对称，椭圆的长轴与短轴长度的比值为1.4，相邻喷丝孔的间距等于喷丝孔的导孔直径加上1.6mm，喷丝板为圆形喷丝板，圆形喷丝板的直径与系列椭圆最大的长轴长度的差值为12mm，喷丝孔的导孔直径为1.5mm，喷丝板的喷丝孔数为244，喷丝板的喷丝微孔的横截面形状为正方形。
高均匀性有色聚酯工业丝经计量、黑色母粒添加、多孔喷丝板挤出、冷却、上油、拉伸、热定型和卷绕，制得高均匀性有色聚酯工业丝，其中挤出的温度为290℃；冷却的风温为30℃；卷绕的速度为3100m/min，黑色母粒添加量为改性聚酯切片质量的0.018％。制得的高均匀性有色聚酯工业丝在280℃下，熔体粘度，常温下工业丝的力学性能数据，以及在温度为177℃×10min×0.05cN/dtex的测试条件下，工业丝的干热收缩率如下表。
Figure PCTCN2017089944-appb-000010
实施例46～48
一种高均匀性有色聚酯工业丝的制备方法，采用多孔喷丝板制得，喷丝板上喷丝孔的排列方式为椭圆形排列，椭圆形排列是指喷丝孔的孔中心位于同心椭圆上，同心椭圆为系列椭圆，所有椭圆的长轴共线，且短轴共线。
喷丝孔的排列为长轴对称，椭圆的长轴与短轴长度的比值为1.4，相邻喷丝孔的间距等于喷丝孔的导孔直径加上1.6mm，喷丝板为圆形喷丝板，圆形喷丝板的直径与系列椭圆最大的长轴长度的差值为12mm，喷丝孔的导孔直径为1.5mm，喷丝板的喷丝孔数为192，喷丝板的喷丝微孔的横截面形状为正方形。
高均匀性有色聚酯工业丝经计量、黑色母粒添加、多孔喷丝板挤出、冷却、上油、拉伸、热定型和卷绕，制得高均匀性有色聚酯工业丝，其中挤出的温度为310℃；冷却的风温为30℃；卷绕的速度为3200m/min，黑色母粒添加量为改性聚酯切片质量的0.018％。制得的高均匀性有色聚酯工业丝在280℃下熔体粘度下降百分数，常温下工业丝的力学性能数据，以及在温度为177℃×10min×0.05cN/dtex的测试条件下，工业丝的干热收缩率如下表。
Figure PCTCN2017089944-appb-000011
Figure PCTCN2017089944-appb-000012
实施例49～51
一种高均匀性有色聚酯工业丝的制备方法，采用多孔喷丝板制得，喷丝板上喷丝孔的排列方式为椭圆形排列，椭圆形排列是指喷丝孔的孔中心位于同心椭圆上，同心椭圆为系列椭圆，所有椭圆的长轴共线，且短轴共线。
喷丝孔的排列为长轴对称，椭圆的长轴与短轴长度的比值为1.4，相邻喷丝孔的间距等于喷丝孔的导孔直径加上1.6mm，喷丝板为圆形喷丝板，圆形喷丝板的直径与系列椭圆最大的长轴长度的差值为12mm，喷丝孔的导孔直径为1.5mm，喷丝板的喷丝孔数为192，喷丝板的喷丝微孔的横截面形状为正方形。
高均匀性有色聚酯工业丝经计量、黑色母粒添加、多孔喷丝板挤出、冷却、上油、拉伸、热定型和卷绕，制得高均匀性有色聚酯工业丝，其中挤出的温度为300℃；冷却的风温为25℃；卷绕的速度为2800m/min，黑色母粒添加量为改性聚酯切片质量的0.01％。制得的高均匀性有色聚酯工业丝在280℃下熔体粘度，常温下工业丝的力学性能数据，以及在温度为177℃×10min×0.05cN/dtex的测试条件下，工业丝的干热收缩率如下表。
Figure PCTCN2017089944-appb-000013
实施例52～57
一种高均匀性有色聚酯工业丝的制备方法，采用多孔喷丝板制得，喷丝板上喷丝孔的排列方式为椭圆形排列，椭圆形排列是指喷丝孔的孔中心位于同心椭圆上，同心椭圆为系列椭圆，所有椭圆的长轴共线，且短轴共线。
喷丝孔的排列为长轴对称，椭圆的长轴与短轴长度的比值为1.4，相邻喷丝孔的间距等于喷丝孔的导孔直径加上1.6mm，喷丝板为圆形喷丝板，圆形喷丝板的直径与系列椭圆最大的长轴长度的差值为12mm，喷丝孔的导孔直径为1.5mm，喷丝板的喷丝孔数为192，喷丝板的喷丝微孔的横截面形状为正方形。
高均匀性有色聚酯工业丝经计量、黑色母粒添加、多孔喷丝板挤出、冷却、上油、拉伸、热定型和卷绕，制得高均匀性有色聚酯工业丝，其中挤出的温度为320℃；冷却的风温为30℃，卷绕的速度为3000m/min，黑色母粒添加量为改性聚酯切片质量的0.03％。制得的高均匀性有色聚酯工业丝在280℃下熔体粘度下降百分比，常温下工业丝的力学性能数据，以及在温度为177℃×10min×0.05cN/dtex的测试条件下，工业丝的干热收缩率如下表。
Figure PCTCN2017089944-appb-000014

Claims (10)

  1. 一种高均匀性有色聚酯工业丝，其特征是：所述高均匀性有色聚酯工业丝是指添加黑色母粒的聚酯工业丝，所述高均匀性有色聚酯工业丝由改性聚酯经固相增粘后纺丝得；所述高均匀性有色聚酯工业丝的材质为改性聚酯，所述改性聚酯由对苯二甲酸链段、乙二醇链段和含支链的二元醇链段组成，所述含支链的二元醇链段是指支链位于二元醇链段中的一个非端基碳上且支链为含有5-10个碳原子的直链碳链的二元醇链段；所述高均匀性有色聚酯工业丝的断裂强度≥7.0cN/dtex，线密度偏差率≤1.0％，断裂强度CV值≤2.0％，断裂伸长CV值≤5.5％；所述高均匀性有色聚酯工业丝在260～290℃下，熔体粘度下降10-20％，在温度为177℃×10min×0.05cN/dtex的测试条件下，干热收缩率为2.5±0.5％，所述熔体粘度下降是指改性聚酯与常规聚酯在相同温度的熔体粘度的对比。
  2. 根据权利要求1所述的一种高均匀性有色聚酯工业丝，其特征在于，所述高均匀性有色聚酯工业丝的断裂伸长为12.0±1.5％；所述改性聚酯的数均分子量为15000-30000。
  3. 根据权利要求1所述的一种高均匀性有色聚酯工业丝，其特征在于，所述含支链的二元醇链段为2-戊基-1,3丙二醇链段、2-己基-1,3丙二醇链段、2-庚基-1,3丙二醇链段、2-辛基-1,3丙二醇链段、2-壬基-1,3丙二醇链段、2-癸基-1,3丙二醇链段、2-戊基-1,4丁二醇链段、2-己基-1,4丁二醇链段、2-庚基-1,4丁二醇链段、2-辛基-1,4丁二醇链段、2-壬基-1,4丁二醇链段、2-癸基-1,4丁二醇链段、2-戊基-1,5戊二醇链段、2-己基-1,5戊二醇链段、2-庚基-1,5戊二醇链段、2-辛基-1,5戊二醇链段、2-壬基-1,5戊二醇链段、2-癸基-1,5戊二醇链段、2-戊基-1,6己二醇链段、2-己基-1,6己二醇链段、2-庚基-1,6己二醇链段、2-辛基-1,6己二醇链段、2-壬基-1,6己二醇链段或2-癸基-1,6己二醇链段中的一种以上；所述含支链的二元醇链段与乙二醇链段的摩尔百分比值为2～5％。
  4. 如权利要求1-3中任一项所述的一种高均匀性有色聚酯工业丝的制备方法，其特征是：将改性聚酯经固相缩聚增粘、计量、黑色母粒添加、多孔喷丝板挤出、冷却、上油、拉伸、热定型和卷绕，制得高均匀性有色聚酯工业丝；
    所述多孔喷丝板上喷丝孔的排列方式为椭圆形排列，所述椭圆形排列是指喷丝孔的孔中心位于同心椭圆上，所述同心椭圆为系列椭圆，所有椭圆的长轴共线，且短轴共线；
    改性聚酯的制备过程包括以下步骤：
    (1)对苯二甲酸二元醇酯的制备：
    将对苯二甲酸与含支链的二元醇配成浆料后，在浓硫酸的催化作用下，进行酯化反应，得到对苯二甲酸二元醇酯；所述含支链的二元醇是支链位于二元醇链段中的一个非端基碳上且支链为含有5-10个碳原子的直链碳链的二元醇；
    (2)对苯二甲酸乙二醇酯的制备：
    将对苯二甲酸和乙二醇配成浆料后，进行酯化反应，得到对苯二甲酸乙二醇酯；
    (3)改性聚酯的制备：
    在步骤(2)中的酯化反应结束后，加入步骤(1)中制备的对苯二甲酸二元醇酯，搅拌混合，在催化剂和稳定剂的作用下，在负压的条件下，依次进行低真空阶段的缩聚反应和高真空阶段的缩聚反应，制得改性聚酯。
  5. 根据权利要求4所述的高均匀性有色聚酯工业丝的制备方法，其特征在于，所述改性聚酯制备的具体步骤为：
    (1)对苯二甲酸二元醇酯的制备：
    将对苯二甲酸与含支链的二元醇配成浆料加入反应器中，在浓硫酸的催化作用下，进行酯化反应，酯化反应在氮气氛围中加压反应，加压压力为常压～0.3MPa，温度为180～240℃，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；得到对苯二甲酸二元醇酯；
    (2)对苯二甲酸乙二醇酯的制备：
    将对苯二甲酸和乙二醇配成浆料后加入反应器中，进行酯化反应，酯化反应在氮气氛围中加压反应，加压压力为常压～0.3MPa，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，得到对苯二甲酸乙二醇酯；
    (3)改性聚酯的制备：
    在步骤(2)中的酯化反应结束后，加入步骤(1)中制备的对苯二甲酸二元醇酯，搅拌混合15-20分钟，在催化剂和稳定剂的作用下，在负压的条件下开始低真空阶段的缩聚反应，该阶段压力由常压平稳抽至绝对压力500Pa以下，温度控制在260～270℃，反应时间为30～50分钟；然后继续抽真空，进行高真空阶段的缩聚反应，使反应压力降至绝对压力小于100Pa，反应温度控制在275～280℃，反应时间50～90分钟，制得改性聚酯；
    再将改性聚酯经切粒得到改性聚酯切片，所得到聚酯切片通过固相缩聚增粘，使聚酯切片的特性粘度提高到1.0～1.2dL/g，即为高粘切片；再经计量、黑色母粒添加、多孔喷丝板挤出、冷却、上油、拉伸、热定型和卷绕，制得高均匀性有色聚酯工业丝；
    所述黑色母粒添加量为所述改性聚酯切片质量的0.01％～0.03％；
    纺丝主要工艺参数为：
    所述挤出的温度为290～320℃；
    所述冷却的风温为20～30℃；
    所述卷绕的速度为2600～3200m/min。
  6. 根据权利要求5所述的一种高均匀性有色聚酯工业丝的制备方法，其特征在于，所述步骤(1)中，对苯二甲酸与含支链的二元醇的摩尔比为1:1.3-1.5；浓硫酸加入量为对苯二甲酸重量的0.3-0.5％；所述浓硫酸 的浓度为50-60wt％；所述步骤(2)中，对苯二甲酸与乙二醇的摩尔比为1:1.2～2.0；所述步骤(3)中，所述对苯二甲酸二元醇酯与对苯二甲酸乙二醇酯的摩尔百分比值为2～5％；所述催化剂为三氧化二锑、乙二醇锑或醋酸锑，催化剂加入量为对苯二甲酸总重量的0.01％～0.05％；所述稳定剂为磷酸三苯酯、磷酸三甲酯或亚磷酸三甲酯，稳定剂加入量为所述对苯二甲酸总重量的0.01％～0.05％。
  7. 根据权利要求5所述的一种高均匀性有色聚酯工业丝的制备方法，其特征在于，所述含支链的二元醇为2-戊基-1,3丙二醇、2-己基-1,3丙二醇、2-庚基-1,3丙二醇、2-辛基-1,3丙二醇、2-壬基-1,3丙二醇、2-癸基-1,3丙二醇、2-戊基-1,4丁二醇、2-己基-1,4丁二醇、2-庚基-1,4丁二醇、2-辛基-1,4丁二醇、2-壬基-1,4丁二醇、2-癸基-1,4丁二醇、2-戊基-1,5戊二醇、2-己基-1,5戊二醇、2-庚基-1,5戊二醇、2-辛基-1,5戊二醇、2-壬基-1,5戊二醇、2-癸基-1,5戊二醇、2-戊基-1,6己二醇、2-己基-1,6己二醇，2-庚基-1,6己二醇、2-辛基-1,6己二醇、2-壬基-1,6己二醇或2-癸基-1,6己二醇中的一种以上。
  8. 根据权利要求4所述的一种高均匀性有色聚酯工业丝的制备方法，其特征在于，所述多孔喷丝板为圆形喷丝板或椭圆形喷丝板；所述圆形喷丝板的直径与系列椭圆最大的长轴长度的差值大于10mm，所述椭圆形喷丝板与系列椭圆最大的长轴长度的差值大于10mm。
  9. 根据权利要求4所述的一种高均匀性有色聚酯工业丝的制备方法，其特征在于，所述多孔喷丝板上喷丝孔的排列为长轴和/或短轴对称，相邻喷丝孔的间距大于等于喷丝孔的导孔直径加上1.5mm；椭圆的长轴与短轴长度的比值为1.3～1.8。
  10. 根据权利要求4所述的一种高均匀性有色聚酯工业丝的制备方法，其特征在于，所述喷丝孔的导孔直径为1.5～2.5mm；所述喷丝板的喷丝孔数大于等于192，所述喷丝板的喷丝微孔的横截面形状为圆形、正方形、菱形、一字型、三角型、三叶型、中空型或扁平型。
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