WO2017113954A1 - 一种低色差聚酯异收缩复合丝及其制备方法 - Google Patents

一种低色差聚酯异收缩复合丝及其制备方法 Download PDF

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WO2017113954A1
WO2017113954A1 PCT/CN2016/103175 CN2016103175W WO2017113954A1 WO 2017113954 A1 WO2017113954 A1 WO 2017113954A1 CN 2016103175 W CN2016103175 W CN 2016103175W WO 2017113954 A1 WO2017113954 A1 WO 2017113954A1
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polyester
ethylene glycol
low
composite yarn
reaction
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PCT/CN2016/103175
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English (en)
French (fr)
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金管范
邵义伟
张烨
王力军
卓怀智
丁竹君
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江苏恒力化纤股份有限公司
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Priority to EP16880745.1A priority Critical patent/EP3348683B1/en
Priority to US15/744,869 priority patent/US10407538B2/en
Priority to JP2018521122A priority patent/JP6471266B2/ja
Publication of WO2017113954A1 publication Critical patent/WO2017113954A1/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
    • 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
    • C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/13—Organo-metallic 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
    • 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
    • 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
    • D01F6/58—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
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G1/00—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
    • D02G1/18—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by combining fibres, filaments, or yarns, having different shrinkage characteristics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/34—Material containing ester groups
    • D06P3/52—Polyesters
    • D06P3/54—Polyesters using dispersed dyestuffs
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs

Definitions

  • the invention belongs to the technical field of polyester preparation, relates to a low chromatic difference polyester hetero-shrinkage composite yarn and a preparation method thereof, in particular to a polycondensation catalyst using a mixture of ethylene glycol magnesium and ethylene glycol oxime and a polyester chip through water and Low-color difference polyester hetero-shrinkage composite yarn which is brewed and washed under the conditions of 120-130 ° C and 0.2-0.3 MPa and a preparation method thereof.
  • PET Polyethylene terephthalate
  • PET is a kind of polymer with excellent performance. PET is widely used because of its high modulus, high strength, firmness, good shape retention, purity and hygiene, and good barrier properties. In the fields of fiber, bottle packaging, film and sheet, the output is increasing year by year, and the industry status is significantly improved.
  • PET is a symmetrical linear macromolecule.
  • the molecular chain does not contain side chain groups.
  • the regularity is very good. This structure has a high glass transition temperature and needs to be dyed at a very high temperature to promote dye molecules to the inside of the fiber. The spread.
  • 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. Since there is no hydrophilic group in the molecule, the hygroscopicity is poor, which results in difficulty in dyeing polyester.
  • the oligomer in the polyester fiber is a low molecular weight ester or ether, mainly referring to an oligomer having a degree of polymerization of less than 10, diethylene glycol, which is produced as a by-product.
  • the oligomers are divided into linear oligomers and cyclic oligomers, among which cyclic polymers, especially cyclic trimers, are mostly involved, and heteropolymers mainly involve heterogeneous nucleation, spinning processing, dyeing, etc. It has certain adverse effects on the properties of polyester and subsequent processing.
  • the ethylene terephthalate polymer (PET) contains about 3-4% of the oligomer, and the presence of oligomers on the surface of the fiber causes troubles in dyeing and post-processing.
  • the diffusion of the oligomer is most likely to occur during the temperature-increasing and incubation phases of the dyeing.
  • the solubility of the oligomer in water decreases sharply with the decrease in temperature, so that it crystallizes, and the precipitated dye and oligomer adhere to the surface of the fiber and are not easily washed away, thereby giving dyeing and post-processing. It brings a lot of troubles.
  • the accumulated dyes and oligomers adhere to the surface of the fiber, and dye spots, stains, and colored flowers appear. Deposited in the pipes and valves of the dyeing machine, hindering the circulation of the liquid, resulting in difficulty in dyeing.
  • the key to eliminating oligomers is the elimination of oligomeric cyclic trimers and diethylene glycol, on the one hand reducing the production of oligomers during the polymerization process and on the other hand removing them before or during dyeing.
  • the different shrinkage composite yarn is a filament with different potential shrinkage properties, that is, a composite yarn composed of a high shrinkage yarn POY and a low shrinkage yarn FDY, and the main characteristics of the PET different shrinkage blended composite yarn are: high bulkiness and softness. Feeling.
  • the appearance of PET heterotrophic composite filaments is similar to that of ordinary filaments.
  • the filaments having different potential shrinkage properties, that is, the composite yarn composed of the high shrinkage yarn POY and the low shrinkage yarn FDY, are mixed and processed, and the shrinkage effect of the two components is different.
  • the object of the present invention is to provide a low chromaticity polyester hetero-shrinkage composite yarn and a preparation method thereof, which is a polycondensation catalyst.
  • a polyester comprising a mixture of magnesium glycol and ethylene glycol oxime and a low color difference polyester hetero-shrinkage composite yarn and a process for the preparation thereof.
  • the invention adopts a mixture of ethylene glycol magnesium and ethylene glycol ruthenium as a polycondensation catalyst to minimize thermal degradation, and the polyester chips are boiled and washed by water and a solvent at 130 ° C and 0.3 MPa; The effect of polymer and diethylene glycol content on the dyeing of polyester composite yarns.
  • the invention relates to a low chromatic polyester hetero-shrinkage composite yarn, which is obtained by esterification of terephthalic acid and ethylene glycol and polycondensation of a mixture of ethylene glycol and ethylene glycol oxime.
  • the low chromaticity polyester hetero-shrinkage composite yarn is obtained by compounding a polyester POY yarn and a polyester FDY yarn; the polyester POY yarn and the polyester FDY yarn are via a polyester After being melted and spun, the low-chromaticity polyester different shrinkage composite yarn has a breaking strength of ⁇ 1.9 cN/dtex, an elongation at break of 30.0 ⁇ 5.0%, a crimp shrinkage ratio of 2.50 ⁇ 3.0%, and a network degree of 20 ⁇ 5/m; color difference ⁇ E is less than 0.200;
  • the mass percentage of the oligomer is less than 0.5%, and the mass percentage of diethylene glycol is less than 0.5%;
  • the molecular formula of the magnesium glycol is Mg(OCH 2 CH 2 OH) 2 ;
  • the washing means that the pellet after granulation is boiled and washed with water and a solvent at 120 to 130 ° C and 0.2 to 0.3 MPa.
  • a mixture of ethylene glycol and ethylene glycol ruthenium is used as a polycondensation catalyst.
  • Glycolate is a milder type, its thermal degradation coefficient is small, and fewer side reactions are initiated during the reaction, which reduces the number of side reactions during processing. Oligomer production.
  • the main factors causing thermal degradation are high temperature and catalyst. High temperature is the reaction intensity is too high, which leads to accelerated degradation, which produces terminal carboxyl groups and also increases cyclic oligomers.
  • the catalyst is related to the degradation reaction constant of the catalyst during the polycondensation process.
  • the role of the catalyst is not only to catalyze the formation of the main reaction, thereby affecting the rate and yield of the reaction, but also catalyzing thermal degradation and ether bond formation, and increasing the content of cyclic oligomers and diethylene glycol.
  • the low-chromaticity polyester hetero-shrinkage composite yarn as described above has a linear density deviation rate of ⁇ 2.5%, an elongation at break CV value of ⁇ 10.0%, a coefficient of variation CV value of ⁇ 10.0%, an oil content of 1.0 ⁇ 0.2%, and a fineness: 100-150dtex.
  • the invention also provides a preparation method of low color difference polyester hetero-shrinkage composite yarn, a preparation method of low color difference polyester hetero-shrinkage composite yarn, which is esterified with terephthalic acid and ethylene glycol and in ethylene glycol
  • the mixture of magnesium and ethylene glycol ruthenium is condensed to obtain polyester, and then diced to obtain polyester chips, and then the polyester chips are washed to obtain polyester; the polyester is spun according to POY process and FDY process respectively.
  • the silk is then plied and twisted, recombined through the network, and finally wound to form a different shrinkage composite yarn.
  • the main process is:
  • Ethylene glycol is added to the single chamber electrolyzer, the supporting electrolyte is magnesium chloride, the magnesium metal block is anode, the cathode is graphite; the direct current is 6 to 10 VV, the cathode current density is 150 to 200 mA, and the electrolysis is 50 to 60 °C. 10 to 12 hours, after the completion of the electrolysis, the electrode was taken out to obtain a white suspension; the mixture was filtered under reduced pressure, and the white solid was washed with anhydrous ethanol, and dried to obtain the magnesium succinate;
  • esterification reaction Using terephthalic acid and ethylene glycol as raw materials, adding an anti-ethering agent, forming a uniform slurry, and then performing an esterification reaction to obtain an esterified product; the esterification reaction is pressurized in a nitrogen atmosphere, and the pressure is controlled at a normal pressure of -0.3 MPa, the temperature is in the range of 250 to 260 ° C, and the amount of the esterified water is more than 90% of the theoretical value is the end point of the esterification reaction;
  • the polycondensation reaction is in a low vacuum stage, a catalyst and a stabilizer are added to the esterification product, and a polycondensation reaction is started under a negative pressure condition.
  • the pressure is smoothly pumped from a normal pressure to an absolute pressure of 500 Pa or less, and the temperature is controlled at 260 to 270 ° C. , the reaction time is 30 to 50 minutes;
  • the catalyst is a mixture of magnesium glycol and ethylene glycol oxime;
  • the polycondensation reaction high vacuum stage after the low vacuum stage of the polycondensation reaction, continue to evacuate, the reaction pressure is reduced 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;
  • the polyester chips are boiled by water and a solvent at 120-130 ° C and 0.2-0.3 MPa for 3-5 hours, and then washed; a polyester is obtained;
  • Air temperature 20 ⁇ 22 ° C;
  • Winding speed 3000 to 4000 m/min.
  • the catalyst is used in an amount of 0.01% to 0.05% by mass of the terephthalic acid.
  • the stabilizer is selected from the group consisting of triphenyl phosphate, trimethyl phosphate and trimethyl phosphite, and the amount of the stabilizer is 0.01% to 0.05% by weight of terephthalic acid.
  • the stabilizer is mainly composed of phosphate ester, and its main function is to capture the free radical generated by the reaction during the polymerization process and reduce the side reaction.
  • the ratio is 1:5-10;
  • the solvent is one of ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether, and a small amount of solvent is added to the water, the solvent is dissolved. It is soluble in water and can also dissolve most low molecular ethers and esters, which is beneficial to improve the washing effect and the reduction of oligomers.
  • washing refers to washing the polyester slice with hot water at 70-80 ° C for 10-15 minutes, then washing with cold water, drying and cooling. .
  • the anti-ether agent reduces the formation of ether under acidic conditions by adding a small amount of NaAc, thereby reducing the activity of ethylene glycol to form diethylene glycol.
  • the object of the present invention is to provide a low chromatic polyester hetero-shrinkage composite yarn, which adopts a milder type of polycondensation catalyst, ethylene glycol magnesium, which causes less side reactions and less heat during processing.
  • Degradation reduces the production of oligomers during processing.
  • the polyester chips are boiled at a temperature of 130 ° C and 0.3 MPa by water and a solvent to facilitate the improvement of the washing effect and the reduction of the oligomer.
  • the reduction of the oligomer makes the polyester fiber dyeing and post-processing heat setting, the amount of oligomer migration from the inside to the inside of the fiber is reduced, the appearance of the stain and the strip is reduced, and the fiber leveling property and the rubbing fastness are ensured.
  • a mixture of ethylene glycol and ethylene glycol ruthenium is used as a polycondensation catalyst.
  • Glycolate is a milder type with a small thermal degradation coefficient, less side reactions during the reaction, and less processing. Production of a terminal carboxyl group and an oligomer.
  • the mass percentage of the oligomer of the polyester chip is less than 0.5%, and the mass percentage of the diethylene glycol is less than 0.5%, which is beneficial to further improve the quality of the fiber.
  • the polyester chips are boiled under water and solvent at 120-130 ° C and 0.2-0.3 MPa to improve the washing effect and the reduction of oligomers.
  • the anti-ether agent reduces the formation of ether under acidic conditions by adding a small amount of NaAc, thereby reducing the activity of ethylene glycol to form diethylene glycol.
  • the hetero-shrinkage composite yarn obtained by the present invention has excellent light-shielding property, excellent dyeing property, high bulkiness and soft hand feeling, and at the same time, since the fiber surface has many wire loops, the auroral defect of the chemical fiber filament material is also eliminated. .
  • the preparation method of the low chromaticity polyester hetero-shrinkage composite yarn of the invention the polyester is respectively spun according to the POY process and the FDY process, and then plied and twisted, and then recombined through the network, and finally wound to form the hetero-shrinkage composite yarn.
  • the fiber is insulated at 70-80 ° C for 10-15 min, the heating rate is 1.0-2.0 ° C/min, the temperature is maintained at 120-130 ° C for 40-60 min, the temperature is lowered, and the cleaning is carried out at 70-80 ° C for 20-30 min.
  • the dyeing was carried out according to the above procedure, and the pre-dyeing solution was separately taken up, and 2 ml of each of the residual liquid was placed in a 10 ml volumetric flask, and 4 ml of acetone was added to fully dissolve the dye. Dilute to the mark with distilled water, and then measure the ⁇ max with a spectrophotometer.
  • the absorbance of the dye before and after dyeing A0, A1 is:
  • K is the absorption coefficient of the measured object
  • S is the scattering coefficient of the measured object
  • R is the reflectance when the measured object is infinitely thick.
  • the SF600X Datacolor colorimeter was used for testing. Each sample was tested 5 times in different areas and its mathematical average was taken.
  • a preparation method of low color difference polyester different shrinkage composite yarn the main processes include:
  • Ethylene glycol is added to the single chamber electrolyzer, the supporting electrolyte is magnesium chloride, the magnesium metal block is anode, the cathode is graphite; the direct current is 6V, the cathode current density is 150mA, and the electrolysis is 10 hours at 50°C.
  • the electrode was taken out to obtain a white suspension; the mixture was filtered under reduced pressure, and the white solid was washed with anhydrous ethanol and dried
  • the esterification reaction is carried out to obtain an esterified product; the esterification reaction is pressurized in a nitrogen atmosphere, the pressure is controlled at a normal pressure, the temperature is at 250 ° C, and the esterified water is distilled to a theoretical value of 91% for esterification. End point of reaction
  • a catalyst and a stabilizer triphenyl phosphate are added to the esterification product, the amount of the catalyst is 0.01% by mass of the terephthalic acid, and the amount of the triphenyl phosphate is 0.01% by weight of the terephthalic acid.
  • the polycondensation reaction was started under pressure, and the pressure was smoothly pumped from atmospheric pressure to an absolute pressure of 498 Pa, the temperature was controlled at 260 ° C, and the reaction time was 30 minutes; the catalyst was a mixture of ethylene glycol and ethylene glycol oxime, ethylene glycol.
  • the mass ratio of magnesium to ethylene glycol is 2:1;
  • the polycondensation reaction is in a high vacuum stage. After the low vacuum phase of the polycondensation reaction, the vacuum is continued to reduce the reaction pressure to absolute. The pressure is 96 Pa, the reaction temperature is controlled at 275 ° C, and the reaction time is 50 minutes; the polyester is obtained, and the polyester chips are obtained by dicing;
  • the polyester chips were boiled in water and the solvent ethylene glycol monoethyl ether at 120 ° C and 0.2 MPa for 3 hours, and then washed, then the polyester chips were washed with 70 ° C hot water for 10 min, then washed with cold water. Drying and cooling for use; obtaining a polyester, a mass ratio of water to a solvent of 100:3, a ratio of polyester chips to water and a solvent, ie a solid to liquid ratio of 1:5.
  • Winding speed 3000 m/min.
  • the low-chromaticity polyester hetero-shrinkage composite yarn has a breaking strength of 1.9 cN/dtex, an elongation at break of 35%, a crimp shrinkage ratio of 5.5%, a network degree of 24/m, and a linear density deviation rate of +2.5%.
  • the elongation at break CV value was 9.8%
  • the coefficient of variation CV was 9.8%
  • the oil content was 1.2%
  • the fineness was 100 dtex.
  • a preparation method of low color difference polyester different shrinkage composite yarn the main processes include:
  • the supporting electrolyte is magnesium chloride
  • the magnesium metal block is an anode
  • the cathode is graphite
  • DC current, initial voltage 10V, cathode current density is 200mA
  • electrolysis at 60 °C for 12 hours after the end of electrolysis, the electrode is taken out to obtain a white suspension
  • filtered under reduced pressure white solid washed with anhydrous ethanol, dried to obtain ethylene Magnesium alkoxide;
  • the esterification reaction is carried out to obtain an esterified product; the esterification reaction is pressurized in a nitrogen atmosphere, the pressure is controlled at 0.3 MPa, the temperature is at 260 ° C, and the esterified water is distilled to a theoretical value of 92% for esterification. End point of reaction
  • a catalyst and a stabilizer trimethyl phosphate are added to the esterification product, the amount of the catalyst is 0.05% of the mass of the terephthalic acid, and the amount of the trimethyl phosphate is 0.05% of the weight of the terephthalic acid.
  • the polycondensation reaction was started under pressure, and the pressure was smoothly pumped from atmospheric pressure to an absolute pressure of 496 Pa, the temperature was controlled at 270 ° C, and the reaction time was 50 minutes; the catalyst was a mixture of ethylene glycol and ethylene glycol oxime, ethylene glycol.
  • the mass ratio of magnesium to ethylene glycol is 3:1;
  • the polycondensation reaction is in a high vacuum stage. After the low vacuum stage of the polycondensation reaction, the vacuum is continued, the reaction pressure is reduced to an absolute pressure of 95 Pa, the reaction temperature is controlled at 280 ° C, and the reaction time is 90 minutes; the polyester is obtained, and the polyester is obtained by pelletizing. slice;
  • polyester chips were boiled with water and the solvent ethylene glycol monopropyl ether at 130 ° C and 0.3 MPa for 5 hours, and then washed, that is, the polyester chips were washed with hot water at 80 ° C for 15 min, and then washed with cold water. Net, dry and cool for use; obtain polyester, water and solvent ratio of mass ratio of 100:4, the ratio of polyester chips to water and solvent, that is, the ratio of solid to liquid is 1:10.
  • Winding speed 4000 m/min.
  • the low-chromaticity polyester hetero-shrinkage composite yarn has a breaking strength of 1.9 cN/dtex, an elongation at break of 25.0%, and a crimp shrinkage ratio.
  • the ratio was -0.5%, the network degree was 15/m, the linear density deviation rate was -2.5%, the elongation at break CV value was 8.9%, the coefficient of variation CV value was 9.7%, the oil content was 0.8%, and the fineness was 105 dtex.
  • a preparation method of low color difference polyester different shrinkage composite yarn the main processes include:
  • Ethylene glycol is added to the single chamber electrolyzer, the supporting electrolyte is magnesium chloride, the magnesium metal block is anode, the cathode is graphite; the direct current is 7V, the cathode current density is 160mA, and the electrolysis is 11 hours at 55°C.
  • the electrode was taken out to obtain a white suspension; the mixture was filtered under reduced pressure, and the white solid was washed with anhydrous ethanol and dried
  • the esterification reaction is carried out to obtain an esterified product; the esterification reaction is pressurized in a nitrogen atmosphere, the pressure is controlled at 0.2 MPa, the temperature is at 255 ° C, and the esterified water is distilled to a theoretical value of 92% for esterification. End point of reaction
  • a catalyst and a stabilizer trimethyl phosphite are added to the esterification product, the amount of the catalyst is 0.02% by mass of the terephthalic acid, and the amount of the dimethyl phosphite is 0.02% by weight of the terephthalic acid.
  • the polycondensation reaction is started under the condition of negative pressure, and the pressure is smoothly pumped from atmospheric pressure to an absolute pressure of 496 Pa, the temperature is controlled at 265 ° C, and the reaction time is 35 minutes; the catalyst is a mixture of ethylene glycol and ethylene glycol oxime, B The mass ratio of diol magnesium to ethylene glycol oxime is 3:1;
  • the polycondensation reaction is in a high vacuum stage. After the low vacuum stage of the polycondensation reaction, the vacuum is continued, the reaction pressure is reduced to an absolute pressure of 98 Pa, the reaction temperature is controlled at 277 ° C, and the reaction time is 60 minutes; the polyester is obtained, and the polyester is obtained by pelletizing.
  • polyester chips were boiled with water and the solvent ethylene glycol monobutyl ether at 125 ° C and 0.2 MPa for 3 hours, and then washed, that is, the polyester chips were washed with hot water at 70 ° C for 15 minutes, and then washed with cold water. Net, dry and cool for use; obtain polyester, water and solvent ratio of mass ratio of 100:4, the ratio of polyester chips to water and solvent, that is, the ratio of solid to liquid is 1:10.
  • Winding speed 3200 m/min.
  • the low-chromaticity polyester hetero-shrinkage composite yarn has a breaking strength of 2.3 cN/dtex, an elongation at break of 26%, a crimp shrinkage of 4.5%, a network degree of 16/m, a linear density deviation of -2.5%, and an elongation at break.
  • the long CV value was 9.1%
  • the coefficient of variation CV value was 9.9%
  • the oil content was 0.9%
  • the fineness was 132 dtex.
  • a preparation method of low color difference polyester different shrinkage composite yarn the main processes include:
  • Ethylene glycol is added to the single chamber electrolyzer, the supporting electrolyte is magnesium chloride, the magnesium metal block is anode, the cathode is graphite; the direct current is 7V, the cathode current density is 170mA, and the electrolysis is 11 hours at 58°C.
  • the electrode was taken out to obtain a white suspension; the mixture was filtered under reduced pressure, and the white solid was washed with anhydrous ethanol and dried
  • the esterification reaction is carried out to obtain an esterified product; the esterification reaction is pressurized in a nitrogen atmosphere, the pressure is controlled at 0.3 MPa, the temperature is at 250 ° C, and the amount of esterified water is 98% of the theoretical value. End of esterification reaction;
  • a catalyst and a stabilizer, triphenyl phosphate are added to the esterification product, the amount of the catalyst is 0.02% of the mass of the terephthalic acid, and the amount of triphenyl phosphate is 0.02% by weight of the terephthalic acid.
  • the polycondensation reaction is started under the condition of negative pressure, and the pressure is smoothly pumped from atmospheric pressure to an absolute pressure of 496 Pa, the temperature is controlled at 264 ° C, and the reaction time is 38 minutes; the catalyst is a mixture of ethylene glycol and ethylene glycol oxime, B The mass ratio of diol magnesium to ethylene glycol oxime is 3:1;
  • the polycondensation reaction is in a high vacuum stage. After the low vacuum stage of the polycondensation reaction, the vacuum is continued to reduce the reaction pressure to an absolute pressure of 99 Pa, the reaction temperature is controlled at 280 ° C, and the reaction time is 90 minutes; the polyester is obtained, and the polyester is obtained by pelletizing. slice;
  • the polyester chips were boiled in water and the solvent ethylene glycol monoethyl ether at 120 ° C and 0.3 MPa for 3 hours, and then washed, then the polyester chips were washed with hot water at 70 ° C for 15 min, then washed with cold water. Drying and cooling for use; obtaining a polyester, the mass ratio of water to the solvent is 100:4, the ratio of the polyester chips to the water and the solvent, that is, the solid-liquid ratio is 1:8.
  • Winding speed 3000 m/min.
  • the low-chromaticity polyester hetero-shrinkage composite yarn has a breaking strength of 2.3 cN/dtex, an elongation at break of 26%, a crimp shrinkage of 5.5%, a network degree of 15/m, and a linear density deviation of -2.5%. Elongation CV value of 9.2%, coefficient of variation CV value 9.3%, oil content 0.8%, fineness: 150 dtex.

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Abstract

本发明涉及一种低色差聚酯异收缩复合丝及其制备方法，所述低色差聚酯异收缩复合丝为聚酯POY丝与聚酯FDY丝复合而得；所述聚酯POY丝与聚酯FDY丝是经由聚酯经溶洗后纺丝而得，所述低色差聚酯异收缩复合丝的断裂强度≥1.9cN/dtex，断裂伸长率为30.0±5.0％，卷曲收缩率为2.50±3.0％，网络度为20±5个/m；色差ΔE小于0.200；本发明中的乙二醇镁比较温和，其热降解系数很小，聚合过程中低聚物的减少，溶洗过程中低聚物进一步减少，使得聚酯纤维染色及后加工热定形中，减少了色斑和条花出现，保证了纤维匀染性和摩擦牢度。异收缩复合丝据有优异的遮光性能、优良的染色性能、高蓬松性和柔软的手感，同时由于该纤维表面有很多的丝圈，因此还消除了化纤丝物的极光缺陷。

Description

一种低色差聚酯异收缩复合丝及其制备方法 技术领域
本发明属聚酯制备技术领域，涉及一种低色差聚酯异收缩复合丝及其制备方法，特别是一种缩聚催化剂采用乙二醇镁和乙二醇锑的混合物以及聚酯切片经水与溶洗剂在120～130℃，0.2～0.3MPa条件下煮泡、洗涤的低色差聚酯异收缩复合丝及其制备方法。
背景技术
聚对苯二甲酸乙二醇酯(PET)是一种性能优良的聚合物，PET以其模量高、强度高、挺括、保形性好、纯净卫生、阻隔性能好等，被广泛应用于纤维、瓶包装、薄膜和片材等领域，产量逐年递增，行业地位显著提升。
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，这种结构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。由于它分子中没有亲水基团，吸湿性很差，这导致涤纶的染色比较困难。涤纶分散染料染色主要高温高压染色法方法
聚酯纤维中的低聚物是一种低分子量的酯或醚，主要是指聚合度小于10的齐聚物、二甘醇，是以副产物的形式产生。其中齐聚物分为线性齐聚物和环状齐聚物，其中以环状聚体特别是环状三聚体居多，齐聚物主要涉及到异相成核、纺丝加工、染色等，对聚酯的性能及后道加工造成一定的不良影响。对苯二甲酸乙二醇酯聚合物(PET)大约含低聚物3-4％，当纤维表面出现低聚物就会给染色和后加工带来麻烦。低聚物的扩散出来最容易发生在染色时的控温升温和保温阶段。当降温时，和染料一样由于低聚物在水中的溶解度随温度降低急剧减小，因此会结晶析出，析出的染料和低聚物附着在纤维表面极不容易洗去，从而给染色及后加工带来很多麻烦，染色过程中，聚集的染料和低聚物粘附在纤维表面，出现染料色点、斑渍、色花等现象。沉积在染色机的管道和阀门中，阻碍液流循环，导致染色困难。消除低聚物关键在于消除齐聚物环状三聚物和二甘醇，一方面是在聚合过程中减少低聚物的产生，另一方面是在染色前或染色中去除。
异收缩复合丝是具有不同潜在收缩性能的长丝，即高收缩丝POY与低收缩丝FDY经混纤加工组成的复合丝，PET异收缩混纤复合丝的主要特点：高膨松性和柔软的手感。PET异收缩复合丝的外现和普通长丝相似。具有不同潜在收缩性能的长丝，即高收缩丝POY与低收缩丝FDY经混纤加工组成的复合丝，由于两组分收缩率的差异，而产生异收缩的效果。
发明内容
本发明的目的是提供一种低色差聚酯异收缩复合丝及其制备方法，是一种缩聚催化剂采 用乙二醇镁和乙二醇锑的混合物的聚酯以及低色差聚酯异收缩复合丝及其制备方法。本发明采用乙二醇镁和乙二醇锑的混合物为缩聚催化剂，将热降解减少到最低，以及聚酯切片经水与溶洗剂在130℃，0.3MPa条件下煮泡、洗涤；减少齐聚物、二甘醇含量对聚酯复合丝染色的的影响。
本发明的一种低色差聚酯异收缩复合丝，为所述聚酯为对苯二甲酸和乙二醇经酯化和在乙二醇镁和乙二醇锑的混合物催化作用下缩聚、造粒和溶洗后纺丝加工制得；所述低色差聚酯异收缩复合丝为聚酯POY丝与聚酯FDY丝复合而得；所述聚酯POY丝与聚酯FDY丝是经由聚酯经溶洗后纺丝而得，所述低色差聚酯异收缩复合丝的断裂强度≥1.9cN/dtex，断裂伸长率为30.0±5.0％，卷曲收缩率为2.50±3.0％，网络度为20±5个/m；色差ΔE小于0.200；
所述产业用聚酯的切片中，齐聚物质量百分比含量小于0.5％，二甘醇的质量百分比含量小于0.5％；
所述乙二醇镁的分子式为Mg(OCH2CH2OH)2；
所述溶洗是指造粒后的切片经水与溶洗剂在120～130℃与0.2～0.3MPa条件下煮泡和洗涤。
在聚酯纤维染色及后加工中，影响表面低聚物析出的因素很多，主要有温度和时间等因素。提高染色温度将加剧低聚物的迁移，特别是当有某些助剂或染料存在时，迁移速度提高更快。染液循环持续的时间越长，低聚物从纤维内向外迁移的量增加，经常冷热循环以及一些助剂、染料的存在会大大加剧低聚物的的移出与沉积。同时热定形的温度和时间对低聚物迁移速度和迁移量有很大影响。对合成纤维染整加工来说热定形是一个极其重要的工序，其主要目的是消除织物上已有的皱痕和提高织物的尺寸稳定性以及改善织物的强力、手感、起毛起球和表面平整等性能。但是，在色织物定形过程中经常发生这样的现象，即热定形后的织物表面容易出现色斑和条花，匀染性和摩擦牢度也显著下降，尤其是对于超细涤纶织物，影响尤为严重，低聚物在热作用下由内向外的迁移是主要原因之一。现有的技术都集中在染色环节来解决低聚物对染色的影响，这只是一种治标的方法，只有从源头上解决才是治本的根本。
采用乙二醇镁与乙二醇锑混合物作为缩聚催化剂，乙二醇镁属于比较温和的一类，其热降解系数很小，在反应过程中引发的副反应较少，减少了在加工过程中低聚物的产生。引起热降解的主要因素是高温和催化剂，高温是反应强度过高，导致降解加速，产生了端羧基，同时也使环状齐聚物增加；催化剂则与催化剂的降解反应常数相关，在缩聚过程中，催化剂的作用不仅在于能催化生成主反应，从而影响反应的速率与产量，同时还能催化热降解和醚键生成，增加环状齐聚物和二甘醇的含量。
如上所述的一种低色差聚酯异收缩复合丝的线密度偏差率±2.5％，断裂伸长CV值≤10.0％，变异系数CV值≤10.0％，含油率为1.0±0.2％，纤度：100-150dtex。
如上所述的一种低色差聚酯异收缩复合丝，所述乙二醇镁和乙二醇锑的混合物中，乙二醇镁与乙二醇锑质量比为2～3:1。
本发明还提供了一种低色差聚酯异收缩复合丝的制备方法，一种低色差聚酯异收缩复合丝的制备方法，为对苯二甲酸和乙二醇经酯化和在乙二醇镁和乙二醇锑的混合物催化作用下缩聚制得聚酯，再经切粒得到聚酯切片，然后将聚酯切片溶洗后即制得聚酯；聚酯分别按POY工艺和FDY工艺纺丝，然后合股并丝，经过网络复合，最后卷绕形成异收缩复合丝。
主要工艺为：
(1)催化剂乙二醇镁的制备：
在单室电解槽内加乙二醇，支持电解质为氯化镁，金属镁块为阳极，阴极为石墨；通直流电，起始电压6～10VV，阴极电流密度为150～200mA，50～60℃时电解10～12小时，电解结束后取出电极，得白色悬浊液；减压过滤，白色固体用无水乙醇洗涤，干燥后得到乙二醇镁；
(2)聚酯的制备，包括酯化反应和缩聚反应：
所述酯化反应：
采用对苯二甲酸和乙二醇作为原料，加入防醚剂，配成均匀浆料后进行酯化反应，得到酯化产物；酯化反应在氮气氛围中加压，压力控制在常压～0.3MPa，温度在250～260℃，酯化水馏出量达到理论值的90％以上为酯化反应终点；
所述缩聚反应：
包括缩聚反应低真空阶段和缩聚反应高真空阶段：
所述缩聚反应低真空阶段，在酯化产物中加入催化剂和稳定剂，在负压的条件下开始缩聚反应，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；所述催化剂为乙二醇镁和乙二醇锑的混合物；
所述缩聚反应高真空阶段，经所述缩聚反应低真空阶段后，继续抽真空，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；
制得聚酯，经切粒得到聚酯切片；
(3)溶洗
所述聚酯切片经水与溶洗剂在120～130℃与0.2～0.3MPa条件下煮泡3-5小时，后经洗涤；得到聚酯；
(4)纺丝加工主要工艺参数：
纺丝温度：280～300℃；
风温：20～22℃；
合股网络压力：3.5～4.5bar；
GR1速度：800～1000m/min；
SR1速度：3000～4200m/min；
GR2速度：3000～400m/min；
HT1温度：90～115℃；
HT2温度：130～140℃；
卷绕速度：3000～4000m/min。
如上所述的一种低色差聚酯异收缩复合丝的制备方法，所述乙二醇与所述对苯二甲酸的摩尔比为1.2～2.0:1。
如上所述的一种低色差聚酯异收缩复合丝的制备方法，所述乙二醇镁和乙二醇锑的混合物中，乙二醇镁与乙二醇锑质量比为2～3:1；所述催化剂用量为所述对苯二甲酸质量的0.01％～0.05％。
如上所述的一种低色差聚酯异收缩复合丝的制备方法，所述稳定剂选自磷酸三苯酯、磷酸三甲酯和亚磷酸三甲酯中的一种，稳定剂用量为所述对苯二甲酸重量的0.01％～0.05％。稳定剂主要以磷酸酯为主，主要作用是在聚合过程中捕捉反应产生的自由基，减少副反应。
如上所述的一种低色差聚酯异收缩复合丝的制备方法，所述水与溶洗剂的质量比例为100:3～4，聚酯切片与水和溶洗剂的比例，即固液比为1:5-10；所述溶洗剂为乙二醇一乙醚、乙二醇一丙醚和乙二醇一丁醚中的一种，在水中加入少量的溶洗剂，溶洗剂溶于水，同时也可溶解大多数低分子的醚和酯，有利于提高洗涤的效果和低聚物的减少。
如上所述的一种低色差聚酯异收缩复合丝的制备方法，所述洗涤是指煮泡后聚酯切片用70～80℃热水洗10～15min，然后用冷水洗净，烘干冷却备用。
如上所述的一种低色差聚酯异收缩复合丝的制备方法，所述防醚剂为醋酸钠和醋酸钙中的一种，防醚剂用量为所述对苯二甲酸重量的0.01％～0.05％。防醚剂通过加入少量NaAc减少在酸性条件下醚的生成，从而降低了乙二醇反应生成二甘醇的活性。
本发明的目的是提供一种低色差聚酯异收缩复合丝，采用较温和的一类缩聚催化剂乙二醇镁，在反应过程中引发的较少副反应较少以及加工过程中的较少热降解，减少了在加工过程中低聚物的产生。聚酯切片经水与溶洗剂在130℃，0.3MPa条件下煮泡有利于提高洗涤的效果和低聚物的减少。低聚物的减少，使得聚酯纤维染色及后加工热定形中，低聚物从纤维内向外迁移的量降低，减少了色斑和条花出现，保证了纤维匀染性和摩擦牢度。
有益效果：
●采用乙二醇镁与乙二醇锑混合物作为缩聚催化剂，乙二醇镁属于比较温和的一类，其热降解系数很小，在反应过程中引发的副反应较少，减少了在加工过程中端羧基和低聚物的产生。
●聚酯切片的齐聚物质量百分比含量小于0.5％，二甘醇的质量百分比含量小于0.5％，有利于进一步提高纤维的品质。
●聚酯切片经水与溶洗剂在120～130℃与0.2～0.3MPa条件下煮泡有利于提高洗涤的效果和低聚物的减少。
●防醚剂通过加入少量NaAc减少在酸性条件下醚的生成，从而降低了乙二醇反应生成二甘醇的活性。
●聚合过程中低聚物的减少，溶洗过程中低聚物进一步减少，使得聚酯纤维染色及后加工热定形中，低聚物从纤维内向外迁移的量降低，减少了色斑和条花出现，保证了纤维匀染性和摩擦牢度。
●本发明所得的异收缩复合丝据有优异的遮光性能、优良的染色性能、高蓬松性和柔软的手感，同时由于该纤维表面有很多的丝圈，因此还消除了化纤丝物的极光缺陷。
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。
本发明的一种低色差聚酯异收缩复合丝的制备方法，聚酯分别按POY工艺和FDY工艺纺丝，然后合股并丝，经过网络复合，最后卷绕形成异收缩复合丝。
1、染料：
分散艳蓝2BLN，5％(o.w.f)
2、染色工艺：
纤维在70～80℃入染保温10～15min，升温速率1.0～2.0℃/min，120～130℃保温40～60min，降温，70～80℃还原清洗20～30min。
3、上染百分率的测定
按上述工艺进行染色，并分别吸取染前液，残留液各2ml于10ml容量瓶中，加入丙酮4ml，使染料充分溶解。用蒸馏水稀释至刻度，再用分光光度计测λmax、时染色前后染料的吸光度A0、A1则：
上染百分率(％)＝(l一A1/A0)×100％
式中：A0---染前液的吸光度
A1---残留液的吸光度
4、染色牢度的测定
按GB3920-83，GB251-64，GB3921-83测试
5、得色量和色差的测定
采用测色配色仪测试。
6、表观颜色深度(K/S)的测定
利用库贝尔卡—蒙克(kubelka-munk)函数计算：K/S＝(1―R)2//2R.式中，K为被测物体的吸收系数；S为被测物体的散射系数；R为被测物体无限厚时的反射率。应用SF600X Datacolor测色配色仪测试，每样品在不同区域测试5次，取其数学平均值。
实施例1
一种低色差聚酯异收缩复合丝的制备方法，主要工艺包括：
(1)催化剂乙二醇镁的制备：
在单室电解槽内加入乙二醇，支持电解质为氯化镁，金属镁块为阳极，阴极为石墨；通直流电，起始电压6V，阴极电流密度为150mA，50℃时电解10小时，电解结束后取出电极，得白色悬浊液；减压过滤，白色固体用无水乙醇洗涤，干燥后得到乙二醇镁；
(2)聚酯的制备，包括酯化反应和缩聚反应：
酯化反应：
采用对苯二甲酸和乙二醇作为原料，乙二醇与对苯二甲酸的摩尔比为1.2:1，加入防醚剂醋酸钠，醋酸钠用量为对苯二甲酸重量的0.01％，配成均匀浆料后进行酯化反应，得到酯化产物；酯化反应在氮气氛围中加压，压力控制在常压，温度在250℃，酯化水馏出量达到理论值的91％为酯化反应终点；
缩聚反应：
包括缩聚反应低真空阶段和缩聚反应高真空阶段：
缩聚反应低真空阶段，在酯化产物中加入催化剂和稳定剂磷酸三苯酯，催化剂用量为对苯二甲酸质量的0.01％，磷酸三苯酯用量为对苯二甲酸重量的0.01％，在负压的条件下开始缩聚反应，该阶段压力由常压平稳抽至绝对压力498Pa，温度控制在260℃，反应时间为30分钟；催化剂为乙二醇镁和乙二醇锑的混合物，乙二醇镁与乙二醇锑质量比为2:1；
缩聚反应高真空阶段，经缩聚反应低真空阶段后，继续抽真空，使反应压力降至绝对 压力96Pa，反应温度控制在275℃，反应时间50分钟；制得聚酯，经切粒得到聚酯切片；
(3)溶洗
聚酯切片经水与溶洗剂乙二醇一乙醚在120℃与0.2MPa条件下煮泡3小时，后经洗涤，即煮泡后聚酯切片用70℃热水洗10min，然后用冷水洗净，烘干冷却备用；得到聚酯，水与溶洗剂的质量比例为100:3，聚酯切片与水和溶洗剂的比例，即固液比为1:5。
(4)纺丝主要工艺参数：
纺丝温度：280℃；
风温：20℃；
合股网络压力：3.5bar；
GR1速度：800m/min；
SR1速度：3000m/min；
GR2速度：3000m/min；
HT1温度：90℃；
HT2温度：130℃；
卷绕速度：3000m/min。
制得低色差聚酯异收缩复合丝的断裂强度为1.9cN/dtex，断裂伸长率为35％，卷曲收缩率为5.5％，网络度为24个/m；线密度偏差率+2.5％，断裂伸长CV值9.8％，变异系数CV值9.8％，含油率为1.2％，纤度：100dtex。
(5)染色
Figure PCTCN2016103175-appb-000001
实施例2
一种低色差聚酯异收缩复合丝的制备方法，主要工艺包括：
(1)催化剂乙二醇镁的制备：
在单室电解槽内加入乙二醇，支持电解质为氯化镁，金属镁块为阳极，阴极为石墨； 通直流电，起始电压10V，阴极电流密度为200mA，60℃时电解12小时，电解结束后取出电极，得白色悬浊液；减压过滤，白色固体用无水乙醇洗涤，干燥后得到乙二醇镁；
(2)聚酯的制备，包括酯化反应和缩聚反应：
酯化反应：
采用对苯二甲酸和乙二醇作为原料，乙二醇与对苯二甲酸的摩尔比为2.0:1，加入防醚剂醋酸钙，醋酸钙用量为对苯二甲酸重量的0.05％，配成均匀浆料后进行酯化反应，得到酯化产物；酯化反应在氮气氛围中加压，压力控制在0.3MPa，温度在260℃，酯化水馏出量达到理论值的92％为酯化反应终点；
缩聚反应：
包括缩聚反应低真空阶段和缩聚反应高真空阶段：
缩聚反应低真空阶段，在酯化产物中加入催化剂和稳定剂磷酸三甲酯，催化剂用量为对苯二甲酸质量的0.05％，磷酸三甲酯用量为对苯二甲酸重量的0.05％，在负压的条件下开始缩聚反应，该阶段压力由常压平稳抽至绝对压力496Pa，温度控制在270℃，反应时间为50分钟；催化剂为乙二醇镁和乙二醇锑的混合物，乙二醇镁与乙二醇锑质量比为3:1；
缩聚反应高真空阶段，经缩聚反应低真空阶段后，继续抽真空，使反应压力降至绝对压力95Pa，反应温度控制在280℃，反应时间90分钟；制得聚酯，经切粒得到聚酯切片；
(3)溶洗
聚酯切片经水与溶洗剂乙二醇一丙醚在130℃与0.3MPa条件下煮泡5小时，后经洗涤，即煮泡后聚酯切片用80℃热水洗15min，然后用冷水洗净，烘干冷却备用；得到聚酯，水与溶洗剂的质量比例为100:4，聚酯切片与水和溶洗剂的比例，即固液比为1:10。
(4)纺丝主要工艺参数：
纺丝温度：300℃；
风温：22℃；
合股网络压力：4.5bar；
GR1速度：1000m/min；
SR1速度：4200m/min；
GR2速度：400m/min；
HT1温度：115℃；
HT2温度：140℃；
卷绕速度：4000m/min。
制得低色差聚酯异收缩复合丝的断裂强度1.9cN/dtex，断裂伸长率为25.0％，卷曲收缩率 为-0.5％，网络度为15个/m；线密度偏差率-2.5％，断裂伸长CV值8.9％，变异系数CV值为9.7％，含油率为0.8％，纤度：105dtex。
(5)染色
Figure PCTCN2016103175-appb-000002
实施例3
一种低色差聚酯异收缩复合丝的制备方法，主要工艺包括：
(1)催化剂乙二醇镁的制备：
在单室电解槽内加入乙二醇，支持电解质为氯化镁，金属镁块为阳极，阴极为石墨；通直流电，起始电压7V，阴极电流密度为160mA，55℃时电解11小时，电解结束后取出电极，得白色悬浊液；减压过滤，白色固体用无水乙醇洗涤，干燥后得到乙二醇镁；
(2)聚酯的制备，包括酯化反应和缩聚反应：
酯化反应：
采用对苯二甲酸和乙二醇作为原料，乙二醇与对苯二甲酸的摩尔比为1.5:1，加入防醚剂醋酸钠，醋酸钠用量为对苯二甲酸重量的0.02％，配成均匀浆料后进行酯化反应，得到酯化产物；酯化反应在氮气氛围中加压，压力控制在0.2MPa，温度在255℃，酯化水馏出量达到理论值的92％为酯化反应终点；
缩聚反应：
包括缩聚反应低真空阶段和缩聚反应高真空阶段：
缩聚反应低真空阶段，在酯化产物中加入催化剂和稳定剂亚磷酸三甲酯，催化剂用量为对苯二甲酸质量的0.02％，亚磷酸三甲酯用量为对苯二甲酸重量的0.02％，在负压的条件下开始缩聚反应，该阶段压力由常压平稳抽至绝对压力496Pa，温度控制在265℃，反应时间为35分钟；催化剂为乙二醇镁和乙二醇锑的混合物，乙二醇镁与乙二醇锑质量比为3:1；
缩聚反应高真空阶段，经缩聚反应低真空阶段后，继续抽真空，使反应压力降至绝对压力98Pa，反应温度控制在277℃，反应时间60分钟；制得聚酯，经切粒得到聚酯切片；
(3)溶洗
聚酯切片经水与溶洗剂乙二醇一丁醚在125℃与0.2MPa条件下煮泡3小时，后经洗涤，即煮泡后聚酯切片用70℃热水洗15min，然后用冷水洗净，烘干冷却备用；得到聚酯，水与溶洗剂的质量比例为100:4，聚酯切片与水和溶洗剂的比例，即固液比为1:10。
(4)纺丝主要工艺参数：
纺丝温度：290℃；
风温：21℃；
合股网络压力：3.8bar；
GR1速度：900m/min；
SR1速度：3500m/min；
GR2速度：3500m/min；
HT1温度：100℃；
HT2温度：135℃；
卷绕速度：3200m/min。
制得低色差聚酯异收缩复合丝的断裂强度2.3cN/dtex，断裂伸长率为26％，卷曲收缩率为4.5％，网络度为16个/m；线密度偏差-2.5％，断裂伸长CV值为9.1％，变异系数CV值9.9％，含油率为0.9％，纤度：132dtex。
(5)染色
Figure PCTCN2016103175-appb-000003
实施例4
一种低色差聚酯异收缩复合丝的制备方法，主要工艺包括：
(1)催化剂乙二醇镁的制备：
在单室电解槽内加入乙二醇，支持电解质为氯化镁，金属镁块为阳极，阴极为石墨；通直流电，起始电压7V，阴极电流密度为170mA，58℃时电解11小时，电解结束后取出电极，得白色悬浊液；减压过滤，白色固体用无水乙醇洗涤，干燥后得到乙二醇镁；
(2)聚酯的制备，包括酯化反应和缩聚反应：
酯化反应：
采用对苯二甲酸和乙二醇作为原料，乙二醇与所述对苯二甲酸的摩尔比为1.8:1，加入防醚剂醋酸钠，醋酸钠用量为对苯二甲酸重量的0.02％，配成均匀浆料后进行酯化反应，得到酯化产物；酯化反应在氮气氛围中加压，压力控制在0.3MPa，温度在250℃，酯化水馏出量达到理论值的98％为酯化反应终点；
缩聚反应：
包括缩聚反应低真空阶段和缩聚反应高真空阶段：
缩聚反应低真空阶段，在酯化产物中加入催化剂和稳定剂磷酸三苯酯，催化剂用量为所述对苯二甲酸质量的0.02％，磷酸三苯酯用量为对苯二甲酸重量的0.02％，在负压的条件下开始缩聚反应，该阶段压力由常压平稳抽至绝对压力496Pa，温度控制在264℃，反应时间为38分钟；催化剂为乙二醇镁和乙二醇锑的混合物，乙二醇镁与乙二醇锑质量比为3:1；
缩聚反应高真空阶段，经缩聚反应低真空阶段后，继续抽真空，使反应压力降至绝对压力99Pa，反应温度控制在280℃，反应时间90分钟；制得聚酯，经切粒得到聚酯切片；
(3)溶洗
聚酯切片经水与溶洗剂乙二醇一乙醚在120℃与0.3MPa条件下煮泡3小时，后经洗涤，即煮泡后聚酯切片用70℃热水洗15min，然后用冷水洗净，烘干冷却备用；得到聚酯，水与溶洗剂的质量比例为100:4，聚酯切片与水和溶洗剂的比例，即固液比为1:8。
(4)纺丝主要工艺参数：
纺丝温度：280℃；
风温：20℃；
合股网络压力：4.5bar；
GR1速度：1000m/min；
SR1速度：3000m/min；
GR2速度：3000m/min；
HT1温度：90℃；
HT2温度：140℃；
卷绕速度：3000m/min。
制得低色差聚酯异收缩复合丝的断裂强度为2.3cN/dtex，断裂伸长率为26％，卷曲收缩率为5.5％，网络度为15个/m；线密度偏差率-2.5％，断裂伸长CV值9.2％，变异系数CV值 9.3％，含油率为0.8％，纤度：150dtex。
(5)染色
Figure PCTCN2016103175-appb-000004

Claims (10)

  1. 一种低色差聚酯异收缩复合丝，其特征是：所述低色差聚酯异收缩复合丝为聚酯POY丝与聚酯FDY丝复合而得；所述聚酯POY丝与聚酯FDY丝是经由聚酯经溶洗后纺丝而得，所述低色差聚酯异收缩复合丝的断裂强度≥1.9cN/dtex，断裂伸长率为30.0±5.0％，卷曲收缩率为2.50±3.0％，网络度为20±5个/m；色差ΔE小于0.200；所述聚酯为对苯二甲酸和乙二醇经酯化和在乙二醇镁和乙二醇锑的混合物催化作用下缩聚，再经切粒得到聚酯切片；
    所述产业用聚酯的切片中，齐聚物质量百分比含量小于0.5％，二甘醇的质量百分比含量小于0.5％；
    所述乙二醇镁的分子式为Mg(OCH2CH2OH)2；
    所述溶洗是指造粒后的切片经水与溶洗剂在120～130℃与0.2～0.3MPa条件下煮泡和洗涤。
  2. 根据权利要求1所述的一种低色差聚酯异收缩复合丝，其特征在于，所述低色差聚酯异收缩复合丝的线密度偏差率±2.5％，断裂伸长CV值≤10.0％，变异系数CV值≤10.0％，含油率为1.0±0.2％，纤度：100-150dtex。
  3. 根据权利要求1所述的一种低色差聚酯异收缩复合丝，其特征在于，所述乙二醇镁和乙二醇锑的混合物中，乙二醇镁与乙二醇锑质量比为2～3:1。
  4. 4.如权利要求1～3中任一项所述的一种低色差聚酯异收缩复合丝的制备方法，其特征是：聚酯分别按POY工艺和FDY工艺纺丝，然后合股并丝，经过网络复合，最后卷绕形成异收缩复合丝。
  5. 根据权利要求4的一种低色差聚酯异收缩复合丝的制备方法，其特征在于，主要工艺包括：
    (1)催化剂乙二醇镁的制备：
    在单室电解槽内加入乙二醇，支持电解质为氯化镁，金属镁块为阳极，阴极为石墨；通直流电，起始电压6～10V，阴极电流密度为150～200mA，50～60℃时电解10～12小时，电解结束后取出电极，得白色悬浊液；减压过滤，白色固体用无水乙醇洗涤，干燥后得到乙二醇镁；
    (2)聚酯的制备，包括酯化反应和缩聚反应：
    所述酯化反应：
    采用对苯二甲酸和乙二醇作为原料，加入防醚剂，配成均匀浆料后进行酯化反应，得到酯化产物；酯化反应在氮气氛围中加压，压力控制在常压～0.3MPa，温度在250～260℃，酯化水馏出量达到理论值的90％以上为酯化反应终点；
    所述缩聚反应：
    包括缩聚反应低真空阶段和缩聚反应高真空阶段：
    所述缩聚反应低真空阶段，在酯化产物中加入催化剂和稳定剂，在负压的条件下开始缩聚反应，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；所述催化剂为乙二醇镁和乙二醇锑的混合物；
    所述缩聚反应高真空阶段，经所述缩聚反应低真空阶段后，继续抽真空，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；
    制得聚酯，经切粒得到聚酯切片；
    (3)溶洗
    所述聚酯切片经水与溶洗剂在120～130℃与0.2～0.3MPa条件下煮泡3-5小时，后经洗涤；得到聚酯；
    (4)纺丝加工主要工艺参数：
    纺丝温度：280～300℃；
    风温：20～22℃；
    合股网络压力：3.5～4.5bar；
    GR1速度：800～1000m/min；
    SR1速度：3000～4200m/min；
    GR2速度：3000～400m/min；
    HT1温度：90～115℃；
    HT2温度：130～140℃；
    卷绕速度：3000～4000m/min。
  6. 根据权利要求4或5所述的一种低色差聚酯异收缩复合丝的制备方法，其特征在于，所述乙二醇与所述对苯二甲酸的摩尔比为1.2～2.0:1。
  7. 根据权利要求5所述的一种低色差聚酯异收缩复合丝的制备方法，其特征在于，所述乙二醇镁和乙二醇锑的混合物中，乙二醇镁与乙二醇锑质量比为2～3:1；所述催化剂用量为所述对苯二甲酸质量的0.01％～0.05％；所述稳定剂选自磷酸三苯酯、磷酸三甲酯和亚磷酸三甲酯中的一种，稳定剂用量为所述对苯二甲酸重量的0.01％～0.05％。
  8. 根据权利要求5所述的一种低色差聚酯异收缩复合丝的制备方法，其特征在于，所述水与溶洗剂的质量比例为100:3～4，聚酯切片与水和溶洗剂的比例，即固液比为1:5～10；所述溶洗剂为乙二醇一乙醚、乙二醇一丙醚和乙二醇一丁醚中的一种。
  9. 根据权利要求5所述的一种低色差聚酯异收缩复合丝的制备方法，其特征在于，所述洗涤是指煮泡后聚酯切片用70～80℃热水洗10～15min，然后用冷水洗净，烘干冷却备用。
  10. 根据权利要求5所述的一种低色差聚酯异收缩复合丝的制备方法，其特征在于，所述防醚剂为醋酸钠和醋酸钙中的一种，防醚剂用量为所述对苯二甲酸重量的0.01％～0.05％。
PCT/CN2016/103175 2015-12-29 2016-10-25 一种低色差聚酯异收缩复合丝及其制备方法 WO2017113954A1 (zh)

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