WO2020134494A1 - 半消光涤纶牵伸丝及其制备方法 - Google Patents

半消光涤纶牵伸丝及其制备方法 Download PDF

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WO2020134494A1
WO2020134494A1 PCT/CN2019/113839 CN2019113839W WO2020134494A1 WO 2020134494 A1 WO2020134494 A1 WO 2020134494A1 CN 2019113839 W CN2019113839 W CN 2019113839W WO 2020134494 A1 WO2020134494 A1 WO 2020134494A1
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Prior art keywords
polyester
semi
modified
temperature
acid
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PCT/CN2019/113839
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English (en)
French (fr)
Inventor
王丽丽
钮臧臧
杨超明
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江苏恒力化纤股份有限公司
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Priority to US17/042,129 priority Critical patent/US11788212B2/en
Priority to JP2021530144A priority patent/JP7053958B2/ja
Publication of WO2020134494A1 publication Critical patent/WO2020134494A1/zh

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • 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
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
    • D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/18—Arsenic, antimony or bismuth
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]

Definitions

  • the invention belongs to the technical field of polyester fibers, and relates to a semi-dull polyester drafting yarn and a preparation method thereof.
  • Polyester fiber has a series of excellent properties such as high breaking strength and elastic modulus, moderate resilience, excellent heat setting, good heat and light resistance, acid resistance, alkali resistance and corrosion resistance, and the fabric has the advantages of wrinkle resistance, ironing and good stiffness. Therefore, polyester fiber is widely used in clothing, home textiles and other fields. With the continuous improvement of the social material level, people have higher and higher demands for sports, leisure, fashion, comfort and healthy fabrics. Stimulated by the huge market benefits, various manufacturers have begun to develop high-sensitivity and high-functionality polyester fiber products. The industry has developed differentiated fibers such as matting, semi-matting, moisture wicking, antibacterial, anti-mosquito, colored and flame retardant, which provide new high-quality fiber raw materials for textile fabrics and home textiles.
  • Polyester has a smooth surface and a certain degree of transparency. Under the irradiation of light, the intensity of the reflected light is very large, which makes the fiber emit a strong luster that is not very comfortable to the human eye, commonly known as aurora. If a small amount of substances with different refractive indexes are added to the fiber to diffuse light in different directions, the gloss of the fiber will be darkened. This treatment is called extinction, and the added substance is called a matting agent.
  • TiO 2 is usually selected as the matting agent, because its refractive index is large (the refractive index of TiO 2 is 2.60, air is 1.00), at the same time, it has good chemical stability, good dispersibility and is insoluble in water. It does not change at high temperature and does not disappear during post-treatment and washing, so it is widely used.
  • polyester fiber has poor dyeing performance.
  • the finished polyester fiber has a partially crystalline supramolecular structure.
  • the molecular chains of the crystalline parts are parallel to each other, mostly in a trans conformation, and the amorphous region is mostly in a cis conformation. The molecular arrangement is quite close, which further increases the polyester fiber. Difficulty of fiber dyeing.
  • PET polyester
  • the purpose of the present invention is to overcome the shortcomings of the poor dyeing performance of the polyester fiber and the slow degradation rate of the polyester filament in the prior art, to provide a semi-dull polyester drawn yarn with excellent dyeing performance and capable of high-efficiency degradation and recycling treatment and a preparation method thereof .
  • modified polyester FDY yarn can be obtained from the modified polyester melt system, that is, semi-dull polyester drafting yarn;
  • the preparation method of the modified polyester is: terephthalic acid, ethylene glycol, main chain silicon-containing diol, fluorine-containing dibasic acid, matting agent and doped modified Bi 2 O 3 powder After mixing evenly, successively carry out esterification reaction and polycondensation reaction;
  • the main chain silicon-containing diol is dimethyl silicon diol, dimethyl diphenyl disiloxane diol or tetramethyl disiloxane diol
  • the fluorine-containing dibasic acid is 2,2-dibasic Fluorine-1,3-malonic acid, 2,2-difluoro-1,4-succinic acid, 2,2-difluoro-1,5-glutaric acid or 2,2,3,3-tetrafluoro -1,4-succinic acid;
  • the content of the matting agent in the modified polyester is 0.20 to 0.25% by weight; the process of doping and modifying Bi 2 O 3 is as follows: first, mix the solution containing Ca 2+ with the solution containing Bi 3+ , and then drop Add the precipitant to the pH value of the mixed solution of 9-10, and finally calcine the precipitated product.
  • the invention improves the dyeing performance and natural degradation performance of the semi-dull polyester drawn yarn by introducing the main chain silicon-containing diol, fluorine-containing dibasic acid and doped modified Bi 2 O 3 powder.
  • the main chain silicon-containing diol is mainly to increase the hollow free volume of polyester, significantly improve the dyeing performance of semi-dull polyester drawn yarn, and the increase in the free volume of the hollow is to some extent beneficial to semi-dull polyester Improvement of the natural degradation performance of the drawn silk.
  • Disperse dyes are a class of dyes with relatively small molecules and no water-soluble groups in structure. Most of them exist in the form of particles with a particle size between several hundred nanometers and one micrometer.
  • the modified polyester of the present invention begins to be dyed, as the temperature continues to increase, since the polyester macromolecular chain contains -Si-O-Si- bonds, the silicon-oxygen bond is longer than the carbon-oxygen bond, and the internal rotation activation energy is low. The molecular chain containing carbon-oxygen bonds begins to move.
  • the temperature of the dyeing bath needs to be increased to 120-130°C, the movement of the macromolecular chain containing silicon-oxygen bonds is greater than that of the molecular chain containing only carbon-oxygen bonds.
  • the free volume of the cavity formed by the large molecular chain containing silicon-oxygen bonds is more efficient than the free volume formed by the molecular chain containing only carbon-oxygen bonds, so the diffusion rate of the particulate dye into the fiber is significantly improved, and the small molecules of the dye are also more It easily penetrates into the interior of the modified polyester macromolecule and has a positive effect on the dyeing of the fiber. It can reduce the dyeing temperature, shorten the dyeing time, reduce energy consumption, and also increase the dyeing rate of the fiber.
  • the special feature of the fluorine-containing dibasic acid introduced in the present invention is that the fluorine atom is on the alpha carbon.
  • the fluorine-containing dibasic acid is introduced in the hydrolysis process, since the fluorine atom is on the alpha carbon, the electron withdrawing ability is strong, making The density of the electron cloud on the CO bond in the polyester is reduced, and the stability of the tetrahedral negative ions is reduced, which is conducive to the nucleophilic addition reaction.
  • the steric hindrance of the fluorine-containing dibasic acid on the ⁇ carbon is less than that of terephthalic acid , Further promote the nucleophilic addition reaction, thus significantly increasing the degradation rate.
  • the invention also significantly improves the natural degradation performance of polyester by doping and modifying Bi 2 O 3 powder.
  • oxygen in the air can penetrate into the polymer through the free volume in the polyester material Inside the ester, an oxygen reduction reaction occurs on the surface of the oxygen reduction catalyst, which breaks the ester bond of the polyester to accelerate the degradation of the polyester, but the further improvement of the degradation efficiency of the pure oxygen reduction catalyst is still limited.
  • the modified polyester of the present invention is doped with modified Bi 2 O 3 powder.
  • the doped Bi Effect of adsorption adsorbed 2 O 3 is monoclinic Bi 2 O 3 doped with an end surface that Bi 2 O 3 to the side surface that adsorption, and the adsorption surface without Bi atoms "steric effect", O 2
  • the chemical adsorption of molecules at the Bi atom position is enhanced, and the catalytic efficiency of oxygen reduction of the catalyst is improved. Therefore, the degradation efficiency of the polyester porous yarn dispersed and modified with Bi 2 O 3 powder during recycling is high, which is conducive to protecting the environment.
  • said solution containing a concentration of Ca 2+ is 2 ⁇ 3wt%, the solvent is water, the solution anion NO 3 -; containing the Bi 3+
  • the solution is a solution of Bi 2 O 3 with a concentration of 20-25% by weight, and the solvent is nitric acid; the precipitant is ammonia with a concentration of 2 mol/L;
  • the calcination procedure as follows: First, the temperature was raised to 400 deg.] C incubation 2 ⁇ 3h, then warmed to 700 °C for heat 1 ⁇ 2h, and finally cooling in air; Bi 2 O 3 was pulverized in an average particle obtained after doping Powder with a diameter of less than 0.5 microns.
  • calcium is dissolved into the Bi 2 O 3 crystal lattice during the calcination process, so that the catalyst body phase forms more defects, so that it is in a highly dispersed state on the surface of the solid solution, thereby destroying the crystal surface structure of Bi 2 O 3 .
  • cooling rate is too slow, the dispersion of particles in the solid phase is slow, and independent crystals will be formed, which will affect the destruction of the crystal structure of Bi 2 O 3. Cooling in the air is not conducive to the formation of crystals and is conducive to the destruction of Bi 2 O 3 crystal structure.
  • the preparation steps of the modified polyester are as follows:
  • esterification reaction is carried out under pressure in a nitrogen atmosphere.
  • the pressure is from normal pressure to 0.3 MPa.
  • the temperature of the esterification reaction is 250 to 260°C.
  • the polycondensation reaction in the low-vacuum stage is started under negative pressure.
  • the pressure in this stage is steadily pumped from normal pressure to an absolute pressure of 500 Pa or less within 30 to 50 minutes.
  • the reaction temperature is 250 to 260°C and the reaction time is 30 ⁇ 50min, and then continue to evacuate to carry out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to below 100Pa absolute pressure, the reaction temperature is 270 ⁇ 282°C, and the reaction time is 50 ⁇ 90min.
  • the molar ratio of terephthalic acid to ethylene glycol is 1:1.2 ⁇ 2.0, and the main chain contains silicon-containing glycol and fluorine-containing dibasic acid.
  • the sum of the added amount is 3 to 5 mol% (mole percentage) of the added amount of terephthalic acid.
  • the molar ratio of the main chain silicon-containing glycol to the fluorine-containing dibasic acid is 2 to 3:3 to 5.
  • the added amounts of the doped and modified Bi 2 O 3 powder, catalyst, matting agent and stabilizer are 0.04 ⁇ 0.07wt%, 0.03 ⁇ 0.05wt%, 0.20 ⁇ 0.25wt% of the addition amount of terephthalic acid and 0.01 ⁇ 0.05wt% (mass percentage).
  • the addition amount of silicon-containing diol, fluorine-containing dibasic acid and doped modified Bi 2 O 3 powder in the main chain of the present invention can be adjusted according to the actual application, but the adjustment range should not be too large, and the addition amount is too large. It will affect the performance (mechanical properties) of the fiber and affect the application of the fiber. If the addition amount is too small, the dyeing performance or degradation performance of the fiber is too small. It is difficult to significantly improve the dyeing effect and natural degradation rate of the fiber.
  • the catalyst is antimony trioxide, ethylene glycol antimony or antimony acetate
  • the matting agent is titanium dioxide
  • the stabilizer is triphenyl phosphate and triphosphate Methyl ester or trimethyl phosphite.
  • the number average molecular weight of the modified polyester is 25,000 to 30,000, and the molecular weight distribution index is 1.8 to 2.2.
  • the flow of the FDY process is: metering, spinneret extrusion, cooling, oiling, drawing, heat setting and winding;
  • the parameters of the FDY process are: spinning temperature 285-295°C, cooling temperature 17-22°C, network pressure 0.20-0.30MPa, one-roll speed 2300-2700m/min, one-roll temperature 80-90°C, two-roll speed 4200 ⁇ 4500m/min, second roller temperature 125 ⁇ 140°C, winding speed 4130 ⁇ 4420m/min.
  • the invention also provides a semi-dull polyester drafting yarn prepared by using the preparation method of the semi-dull polyester drafting yarn as described above, which is a modified polyester FDY yarn;
  • the molecular chain of the modified polyester includes a terephthalic acid segment, an ethylene glycol segment, a main chain silicon-containing glycol segment and a fluorine-containing dibasic acid segment;
  • the modified polyester is dispersed with a matting agent and doped modified Bi 2 O 3 powder, and the content of the matting agent is 0.20-0.25 wt%.
  • the semi-dull polyester drawn yarn has a monofilament fineness of 0.7 to 3.0 dtex, a breaking strength ⁇ 3.5 cN/dtex, an elongation at break of 32.0 ⁇ 4.0%, and a network degree of 13 ⁇ 2 pcs/m, linear density deviation rate ⁇ 1.0%, breaking strength CV value ⁇ 5.0%, breaking elongation CV value ⁇ 9.0%, boiling water shrinkage rate 6.5 ⁇ 0.5%; the main chain silicon-containing glycol chain of the present invention Compared with the prior art, the quality and quality of the fiber of the segment, the fluorine-containing dibasic acid segment and the dispersed and doped modified Bi 2 O 3 powder in the segment are not reduced, and the modified fiber still has good mechanics Performance and spinnability.
  • the difference between the contrast sample and the semi-dull polyester drafting yarn of the present invention is only that its material is ordinary polyester;
  • the semi-dull polyester drawn yarn was placed under the condition of temperature 25°C and relative humidity 65% for 60 months, its intrinsic viscosity decreased by 18 to 26%. Compared with the conventional polyester fiber, the natural degradation rate of the semi-dull polyester drawn yarn of the present invention is significantly increased.
  • the combination of the fluorine-containing dibasic acid and the doped modified Bi 2 O 3 powder can significantly increase the natural degradation rate of the polyester fiber.
  • the present invention modifies the polyester by the main chain silicon-containing diol, which effectively improves the dyeing performance of the polyester fiber. At the same time, it also cooperates with the fluorine-containing dibasic acid and the doped modified Bi 2 O 3 powder Further modification of the polyester, on the basis of the improvement of the dyeing effect, has realized the accelerated degradation of the polyester, which effectively solves the problem of polyester fiber recycling.
  • the main chain silicon-containing diol of the present invention is dimethyl silicon diol, dimethyl diphenyl disiloxane diol or tetramethyl disiloxane diol, and the structural formulas are as follows:
  • the rigidity of the polymer chain depends on the size of the rotating barrier in the molecular chain.
  • the structure of the main chain is different. Among them, the bond angle and bond length are different or the bonding method is different. The rigidity is also different. After the alcohol, the polymer main chain contains -Si-O-Si- bonds, the silicon-oxygen bond gap is large, and the internal rotation activation energy is low, which is conducive to the free rotation of the atoms.
  • the Si atoms on the polymer main chain and- CH 3 is connected, -CH 3 is perpendicular to the plane where Si-O-Si atoms are located, and because the Si-C bond is longer than the CC bond, the three H in -CH 3 are in an open state, the three in -CH 3 A stretched H atom can rotate freely, making the distance between adjacent Si-O molecular segments larger, and the inert methyl group of the outer chain hinders the access of the polymer, so the polymer material is very compliant and the void free volume Compared with the polymer material without introducing a silicon-containing diol in the main chain, when the Si atom on the main chain of the polymer is connected to the long-chain branched substituent, the main increase is the free volume of the slit.
  • the effect of improving the permeability and diffusivity of small molecules is limited.
  • the molecular chains are prone to entanglement, which is not conducive to the increase of free volume.
  • the introduction of silicon-containing glycols also increases the void free volume of the modified polyester.
  • the increase of the free volume of the cavity will make it easier for water or other molecules such as dyes to penetrate into the interior of the modified polyester macromolecule, which will have a positive effect on the dyeing of the modified polyester, which can reduce the dyeing temperature, shorten the dyeing time, and reduce Energy consumption, but also improve the fiber dyeing rate.
  • the hydrolysis degradation process of polyester under alkaline conditions is a nucleophilic addition-elimination process.
  • OH - attacks the C atom of the ester carbonyl RCOOR ⁇
  • a nucleophilic addition reaction occurs, forming an intermediate ( That is, the negative ions of tetrahedron)
  • the negative ions of tetrahedron can eliminate OR ⁇ to obtain carboxylic acid RCOOH, which breaks the ester bond, and at the same time OR ⁇ combines with H + to obtain alcohol HOR ⁇ .
  • the invention significantly improves the degradation rate of polyester by introducing a fluorine-containing dibasic acid with a special structure into the polyester molecular chain.
  • the special feature of the fluorine-containing dibasic acid is that the fluorine atom is on the alpha carbon, which is introduced during the hydrolysis process.
  • the fluorine-containing dibasic acid since the fluorine atom is on the alpha carbon, the electron withdrawing ability is strong, so that the electron cloud density on the CO bond in the polyester is reduced, and the stability of the tetrahedral negative ion is reduced, which is beneficial to nucleophilic addition.
  • the steric hindrance of the fluorinated dibasic acid on the ⁇ carbon is smaller than that of terephthalic acid, which further promotes the nucleophilic addition reaction, thus significantly increasing the degradation rate.
  • the degradation rate of the polyester will not be significantly increased, because the presence of electron withdrawing groups on the ⁇ carbon only affects It is limited to the adjacent carbon and has little effect on the CO bond in the ester bond, so it has little effect on the nucleophilic addition reaction of the OH - attack ester carbonyl group.
  • polyester is exposed to the air for a long time, when the polyester contains a certain amount of oxygen reduction catalyst, the oxygen in the air can penetrate into the polymer through the free volume in the polyester material (narrow free volume and/or void free volume) Inside the ester, oxygen is adsorbed on the surface of the oxygen reduction catalyst. Oxygen gradually migrates to the surface of the oxygen reduction catalyst inside the polyester. After reaching a certain oxygen concentration gradient, the adsorbed oxygen is formed. An oxygen reduction reaction (oxygen ionization) occurs on the surface of the oxygen reduction catalyst. During a reaction, oxygen is partially reduced to peroxide.
  • oxygen reduction reaction oxygen ionization
  • the oxygen molecule adsorbed by the oxygen reduction catalyst is combined with an ester bond in a polyester to form RCOOOR ⁇ on the catalyst surface, and then a proton is combined to break the oxygen-oxygen bond. , Generate an RCOOH, break the ester bond, and OR ⁇ and H + combine to obtain alcohol HOR ⁇ , thereby accelerating the degradation of polyester.
  • the method of the invention realizes the doping of calcium oxide and bismuth trioxide through the method of solution blending, co-precipitation and calcination, thereby affecting the oxygen reduction catalytic process of bismuth trioxide, and improving the degradation rate of the polyester.
  • the closer the doped ion radius is to the doped ion radius the more favorable is the formation of oxygen vacancies, and the more favorable is the conduction of oxygen ions.
  • Ca 2+ doped with the same radius as Bi 3+ is selected. (The ionic radius of Bi 3+ and Ca 2+ are both 0.103 nm) Doping it can increase the conduction rate of oxygen ions, and thus increase the degree of oxygen reduction reaction.
  • the effect of doping on bismuth trioxide is as follows:
  • the doping method of the present invention can destroy the crystal surface structure of Bi 2 O 3 and increase its specific surface area, thereby increasing the oxygen adsorption capacity per unit mass of Bi 2 O 3 ;
  • the doping method can change the adsorption method of Bi 2 O 3 and the mechanism of oxygen reduction reaction.
  • the adsorption method is terminal adsorption on the surface of monoclinic Bi 2 O 3.
  • O atoms are in different monoclinic Bi 2 O 3 crystals During surface adsorption, it will be affected by the “steric hindrance effect” of Bi atoms on the surface.
  • O 2 molecules are adsorbed on the Bi atom through weak physical adsorption or weak chemical adsorption, and on different monoclinic Bi 2 O 3 crystal planes.
  • the degraded polyester in the prior art all starts from the surface of the polyester, and the present invention provides a new way of degrading from the inside of the polyester by mixing the oxygen reduction catalyst into the polyester, and the degradation efficiency is high.
  • the increase in the free volume of the void (the main chain silicon-containing diol) will also cooperate with the fluorine-containing dibasic acid and the doped modified Bi 2 O 3 powder to improve the natural degradation performance of the semi-dull polyester drawn yarn
  • the increase in the free volume of the cavity reduces the difficulty of the penetration of water and air molecules into the modified polyester macromolecule, which increases more reactants for the degradation reaction and promotes the degradation reaction to a certain extent.
  • the semi-dull polyester drawn yarn of the present invention has excellent dyeing performance, good mechanical properties, is easily degraded and recycled and the quality is not reduced, and has a very good application prospect;
  • the addition of silicon-containing diol in the main chain makes the void free volume of the modified polyester larger, making it easy for small molecules such as dye, air or water to enter Inside the fiber, it has a positive effect on the dyeing and natural degradation of the modified polyester.
  • the addition of fluorine-containing dibasic acid and doped modified Bi 2 O 3 powder further increases its natural degradation rate, which is beneficial to Environmental protection.
  • the preparation method of semi-dull polyester drawn yarn is as follows:
  • the polycondensation reaction in the low-vacuum stage is started under negative pressure.
  • the pressure in this stage is steadily pumped from normal pressure to an absolute pressure of 490 Pa, the reaction temperature is 272 °C, the reaction time is 35 minutes, and then continue to pump Vacuum, the polycondensation reaction in the high vacuum stage is carried out, the reaction pressure is further reduced to an absolute pressure of 100Pa, the reaction temperature is 270 °C, the reaction time is 50min, the number average molecular weight of the prepared modified polyester is 30,000, and the molecular weight distribution index is 2.0;
  • Modified polyester melt is prepared by metering, spinneret extrusion, cooling, oiling, stretching, heat setting and winding to obtain modified polyester FDY yarn, that is, semi-dull polyester draft yarn, FDY process
  • the parameters are: spinning temperature 290°C, cooling temperature 22°C, network pressure 0.26MPa, one-roller speed 2300m/min, one-roller temperature 85°C, two-roller speed 4500m/min, second-roller temperature 140°C, winding speed 4420m/ min.
  • the final semi-dull polyester drawn yarn was modified polyester FDY yarn, the monofilament fineness was 0.7dtex, the breaking strength was 3.6cN/dtex, the breaking elongation was 32.0%, and the network degree was 13 pieces/m.
  • the linear density deviation rate is 0.95%, the breaking strength CV value is 4.45%, the breaking elongation CV value is 8.8%, and the boiling water shrinkage rate is 6.0%;
  • the dyeing rate of modified polyester FDY yarn under the temperature condition of 120°C is 87.5%, the K/S value is 24.22, the color fastness to soaping reaches 5 grades, the dry rubbing fastness reaches 5 grades, and the wet rubbing fastness Level 5;
  • a method for preparing semi-dull polyester drawn yarn the steps are basically the same as in Example 1, except that the polyester is not modified, the monofilament fineness of the prepared semi-dull polyester drawn yarn is 0.7dtex, and the breaking strength 3.5cN/dtex, elongation at break 33.0%, network degree 13/m, linear density deviation rate 0.95%, breaking strength CV value 4.50%, breaking elongation CV value 8.8%, boiling water shrinkage 6.2%; after 60 months at 25°C and 65% relative humidity, its intrinsic viscosity decreased by 4.2%; under the same test conditions as in Example 1, it was at a temperature of 130°C
  • the dyeing rate is 85.6%
  • the K/S value is 21.28
  • the color fastness to soaping is 4 grades
  • the dry rubbing fastness is 4 to 5 grades
  • the wet rubbing fastness is 3 to 4 grades. It can be seen from the comparison between the two that the present invention greatly improves the dyeing performance and natural degradation performance of the polyester fiber by modifying the polyester, and
  • a preparation method of semi-dull polyester drawn yarn the preparation steps are basically the same as those in Example 1, except that in step (1), 1,6-hexanediol is used instead of dimethyl silicon glycol
  • the semi-dull polyester drawn yarn has a monofilament fineness of 0.7dtex, a breaking strength of 3.4cN/dtex, an elongation at break of 35.0%, a network degree of 13 pieces/m, a linear density deviation rate of 0.95%, and a breaking strength CV value It was 4.30%, the CV value of elongation at break was 8.8%, the shrinkage of boiling water was 6.5%, the intrinsic viscosity decreased by 16.7% after being left under the conditions of 25°C and 65% relative humidity for 60 months; Under the same test conditions, the dyeing rate at a temperature of 130°C is 84.8%, the K/S value is 20.56, the color fastness to soaping is 4 to 5 and the wet rubbing fastness is 4; Both are lower than the present invention.
  • Example 1 Compared with Example 1, it can be found that the introduction of silicon-containing diol in the main chain makes the polymer main chain contain -Si-O-Si- bonds, which makes the gap between silicon and oxygen bonds larger, and the internal rotation activation energy is lower, which is beneficial to The atoms rotate freely, thereby increasing the free volume of the cavity. Compared with the long-chain branched substituents, it is more conducive to improving the dyeing performance and natural degradation performance of the fiber.
  • a method for preparing a semi-dull polyester drafting yarn the preparation steps are basically the same as in Example 1, except that, in step (2), the doped and modified Bi 2 O 3 powder is not added to produce the semi-dull polyester
  • the monofilament fineness of the drawn yarn is 0.7dtex
  • the breaking strength is 3.5cN/dtex
  • the breaking elongation is 34.0%
  • the network degree is 13 pieces/m
  • the linear density deviation rate is 0.95%
  • the breaking strength CV value is 4.20%
  • the CV value of elongation at break is 8.8%
  • the shrinkage of boiling water is 6.4%
  • its dyeing rate at a temperature of 130°C is 87.2%
  • K/S value It is 23.98
  • the color fastness to soaping is 4 to 5
  • the dry rubbing fastness is 4
  • the wet rubbing fastness is 4 which are lower than the present invention.
  • its intrinsic viscosity decreased by 13.7%.
  • Comparing Example 1 with Comparative Example 3 it can be found that it is precisely due to the addition of doped modified Bi 2 O 3 powder that the natural degradation rate of the semi-dull polyester drawn yarn of the present invention is compared to ordinary polyester fibers It has been greatly improved, and the degradation rate can be further accelerated by adjusting the degradation conditions, thereby facilitating the recycling of the fiber. At the same time, the addition of modified Bi 2 O 3 powder has little effect on the other properties of the fiber, and Does not affect its processing performance and mechanical properties.
  • a preparation method of semi-dull polyester drafting yarn the preparation steps are basically the same as in Example 1, except that in step (1), 3,3-difluoroglutaric acid is used instead of 2,2-difluoro-1 ,3-malonic acid, the monofilament fineness of the prepared semi-dull polyester drawn yarn is 0.7dtex, the breaking strength is 3.3cN/dtex, the breaking elongation is 35.0%, the network degree is 13 pieces/m, the linear density The deviation rate was 0.95%, the breaking strength CV value was 4.00%, the breaking elongation CV value was 8.8%, and the boiling water shrinkage rate was 6.5%.
  • Example 1 Compared with Example 1, it can be found that the fluorine-containing dibasic acid with a fluorine atom in the alpha carbon is more conducive to improving the natural degradation performance of the fiber than the fluorine-containing dibasic acid with the fluorine atom in the beta carbon because of the presence on the beta carbon
  • the electron-withdrawing group is generated, the effect is limited to the adjacent carbon, and the effect on the CO bond in the ester bond is very small. Therefore, the effect of the nucleophilic addition reaction of the OH - attack ester carbonyl group is small, and It has little effect on the natural degradation process of fibers.
  • the preparation method of semi-dull polyester drawn yarn is as follows:
  • the polycondensation reaction in the low-vacuum stage is started under negative pressure.
  • the pressure in this stage is smoothly pumped from normal pressure to an absolute pressure of 420 Pa, the reaction temperature is 270 °C, the reaction time is 40 minutes, and then continue to pump Vacuum, the polycondensation reaction in the high vacuum stage is carried out, the reaction pressure is further reduced to an absolute pressure of 95Pa, the reaction temperature is 271 °C, the reaction time is 55min, the prepared modified polyester has a number average molecular weight of 28000 and a molecular weight distribution index of 2.0;
  • Modified polyester melt is prepared by metering, spinneret extrusion, cooling, oiling, stretching, heat setting and winding to obtain modified polyester FDY yarn, that is, semi-dull polyester draft yarn, FDY process
  • the parameters are: spinning temperature 285°C, cooling temperature 20°C, network pressure 0.24MPa, one-roller speed 2700m/min, one-roller temperature 90°C, two-roller speed 4300m/min, second-roller temperature 125°C, winding speed 4130m/ min.
  • the final semi-dull polyester drawn yarn was modified polyester FDY yarn, its monofilament fineness was 1.5dtex, breaking strength was 3.5cN/dtex, breaking elongation was 28.0%, and network degree was 11 pieces/m.
  • the linear density deviation rate is 0.9%, the breaking strength CV value is 4.9%, the breaking elongation CV value is 8.8%, and the boiling water shrinkage rate is 7.0%;
  • the dyeing rate of modified polyester FDY yarn at 120°C is 91.8%, the K/S value is 22.17, the color fastness to soaping reaches grade 5, the dry rubbing fastness to grade 5, wet rubbing fastness Level 6;
  • the preparation method of semi-dull polyester drawn yarn is as follows:
  • the polycondensation reaction in the low-vacuum stage starts under negative pressure.
  • the pressure in this stage is smoothly pumped from normal pressure to an absolute pressure of 500 Pa within 45 minutes, the reaction temperature is 280° C., the reaction time is 30 minutes, and then the pumping continues Vacuum, the polycondensation reaction in the high vacuum stage is carried out, the reaction pressure is further reduced to an absolute pressure of 96Pa, the reaction temperature is 273 °C, the reaction time is 60min, the number average molecular weight of the prepared modified polyester is 25000, the molecular weight distribution index is 2.2;
  • Modified polyester melt is prepared by metering, spinneret extrusion, cooling, oiling, stretching, heat setting and winding to obtain modified polyester FDY yarn, that is, semi-dull polyester draft yarn, FDY process
  • the parameters are: spinning temperature 285°C, cooling temperature 17°C, network pressure 0.30MPa, one roll speed 2400m/min, one roll temperature 83°C, two roll speed 4500m/min, second roll temperature 125°C, winding speed 4130m/ min.
  • the final semi-dull polyester drawn yarn is modified polyester FDY yarn, its monofilament fineness is 2.0dtex, breaking strength is 3.6cN/dtex, breaking elongation is 36.0%, network degree is 15/m, The linear density deviation rate is 0.95%, the breaking strength CV value is 4.4%, the breaking elongation CV value is 8.6%, and the boiling water shrinkage rate is 6.5%;
  • the dyeing rate of modified polyester FDY yarn at a temperature of 120°C is 87.5%, the K/S value is 22.17, the color fastness to soaping reaches grade 5, the dry rubbing fastness to grade 5, wet rubbing fastness Level 5;
  • the preparation method of semi-dull polyester drawn yarn is as follows:
  • the pressure is 0.1 MPa
  • the temperature of the esterification reaction is 250 °C
  • the esterification reaction The end of the esterification reaction when the distillate of water reaches 95% of the theoretical value, in which the molar ratio of phthalic acid and ethylene glycol is 1:1.6, dimethylsilyl glycol and 2,2,3,3-tetrafluoro-
  • the polycondensation reaction in the low-vacuum stage is started under negative pressure.
  • the pressure in this stage is smoothly pumped from normal pressure to an absolute pressure of 440Pa, the reaction temperature is 278°C, the reaction time is 40min, and then the pumping is continued.
  • Vacuum the polycondensation reaction in the high vacuum stage is carried out, the reaction pressure is further reduced to an absolute pressure of 99Pa, the reaction temperature is 273 °C, the reaction time is 75min, the number average molecular weight of the prepared modified polyester is 25000, the molecular weight distribution index is 1.8;
  • Modified polyester melt is prepared by metering, spinneret extrusion, cooling, oiling, stretching, heat setting and winding to obtain modified polyester FDY yarn, that is, semi-dull polyester draft yarn, FDY process
  • the parameters are: spinning temperature 295°C, cooling temperature 17°C, network pressure 0.20MPa, one-roller speed 2600m/min, one-roller temperature 90°C, two-roller speed 4200m/min, second-roller temperature 125°C, winding speed 4360m/ min.
  • the final semi-dull polyester drawn yarn was modified polyester FDY yarn, its monofilament fineness was 3.0dtex, breaking strength was 3.5cN/dtex, breaking elongation was 32.0%, and network degree was 12/m.
  • the linear density deviation rate is 1.0%
  • the breaking strength CV value is 4.9%
  • the breaking elongation CV value is 9.0%
  • the boiling water shrinkage rate is 6.8%;
  • the dyeing rate of the modified polyester FDY yarn at a temperature of 120°C is 89.63%, the K/S value is 25.56, the color fastness to soaping reaches grade 5, the dry rubbing fastness to grade 5, wet rubbing fastness Level 5;
  • the preparation method of semi-dull polyester drawn yarn is as follows:
  • the polycondensation reaction in the low-vacuum stage is started under negative pressure.
  • the pressure in this stage is pumped smoothly from normal pressure to an absolute pressure of 490 Pa, the reaction temperature is 282 °C, the reaction time is 35 min, and then the pumping is continued.
  • Vacuum the polycondensation reaction in the high vacuum stage is carried out, the reaction pressure is further reduced to an absolute pressure of 100Pa, the reaction temperature is 274°C, the reaction time is 80min, the number average molecular weight of the prepared modified polyester is 30,000, and the molecular weight distribution index is 1.8;
  • Modified polyester melt is prepared by metering, spinneret extrusion, cooling, oiling, stretching, heat setting and winding to obtain modified polyester FDY yarn, that is, semi-dull polyester draft yarn, FDY process
  • the parameters are: spinning temperature 292°C, cooling temperature 22°C, network pressure 0.20MPa, one-roll speed 2300m/min, one-roll temperature 80°C, two-roll speed 4200m/min, two-roll temperature 125°C, winding speed 4420m/ min.
  • the final semi-dull polyester drawn yarn was modified polyester FDY yarn, its monofilament fineness was 1.6dtex, breaking strength was 3.7cN/dtex, breaking elongation was 31.0%, and the degree of network was 15/m.
  • the linear density deviation rate is 0.92%, the breaking strength CV value is 5.0%, the breaking elongation CV value is 8.4%, and the boiling water shrinkage rate is 7.0%;
  • the dyeing rate of the modified polyester FDY yarn at a temperature of 120°C is 89.20%, the K/S value is 23.44, the color fastness to soaping reaches grade 5, the dry rubbing fastness to grade 5, wet rubbing fastness Level 6;
  • the preparation method of semi-dull polyester drawn yarn is as follows:
  • the polycondensation reaction in the low-vacuum stage starts under negative pressure.
  • the pressure in this stage is smoothly pumped from normal pressure to an absolute pressure of 450 Pa within 35 minutes, the reaction temperature is 270°C, and the reaction time is 50 minutes.
  • Vacuum the polycondensation reaction in the high vacuum stage is carried out, the reaction pressure is further reduced to an absolute pressure of 100Pa, the reaction temperature is 275 °C, the reaction time is 85min, the number average molecular weight of the prepared modified polyester is 27800, the molecular weight distribution index is 1.8;
  • Modified polyester melt is prepared by metering, spinneret extrusion, cooling, oiling, stretching, heat setting and winding to obtain modified polyester FDY yarn, that is, semi-dull polyester draft yarn, FDY process
  • the parameters are: spinning temperature 295°C, cooling temperature 18°C, network pressure 0.20MPa, one-roller speed 2300m/min, one-roller temperature 80°C, two-roller speed 4400m/min, second-roller temperature 130°C, winding speed 4420m/ min.
  • the final semi-dull polyester drawn yarn was modified polyester FDY yarn, the monofilament fineness was 2.5dtex, the breaking strength was 3.5cN/dtex, the breaking elongation was 33.0%, and the network degree was 11 pieces/m.
  • the linear density deviation rate is 1.0%
  • the breaking strength CV value is 5.0%
  • the breaking elongation CV value is 8.2%
  • the boiling water shrinkage rate is 6.5%;
  • the dyeing rate of the modified polyester FDY yarn at a temperature of 120°C is 91.8%, the K/S value is 25.56, the color fastness to soaping reaches grade 5, the dry rubbing fastness to grade 5, wet rubbing fastness Level 6;
  • the preparation method of semi-dull polyester drawn yarn is as follows:
  • the esterification reaction is carried out under pressure in a nitrogen atmosphere, the pressure is 0.3MPa, the temperature of the esterification reaction is 260°C, when the water in the esterification reaction When the distillation amount reaches 99% of the theoretical value, it is the end point of the esterification reaction, in which the molar ratio of phthalic acid and ethylene glycol is 1:1.3, tetramethyldisiloxanediol and 2,2-difluoro-1, The sum of the addition amount of 5-glutaric acid is 5mol% of the addition amount of terephthalic acid, and the molar ratio of tetramethyldisiloxane diol and 2,2-difluoro
  • the polycondensation reaction in the low-vacuum stage is started under negative pressure.
  • the pressure in this stage is smoothly pumped from normal pressure to an absolute pressure of 500 Pa within 45 minutes, the reaction temperature is 280° C., the reaction time is 50 minutes, and then the pumping continues Vacuum, the polycondensation reaction in the high vacuum stage is carried out, the reaction pressure is further reduced to an absolute pressure of 90Pa, the reaction temperature is 277°C, the reaction time is 90min, the prepared modified polyester has a number average molecular weight of 30,000 and a molecular weight distribution index of 2.2;
  • Modified polyester melt is prepared by metering, spinneret extrusion, cooling, oiling, stretching, heat setting and winding to obtain modified polyester FDY yarn, that is, semi-dull polyester draft yarn, FDY process
  • the parameters are: spinning temperature 295°C, cooling temperature 22°C, network pressure 0.30MPa, one-roll speed 2700m/min, one-roll temperature 86°C, two-roll speed 4500m/min, second-roll temperature 135°C, winding speed 4130m/ min.
  • the final semi-dull polyester drawn yarn was modified polyester FDY yarn, the monofilament fineness was 1.2dtex, the breaking strength was 3.5cN/dtex, the breaking elongation was 32.0%, and the network degree was 13/m.
  • the linear density deviation rate is 0.88%, the breaking strength CV value is 4.5%, the breaking elongation CV value is 9.0%, and the boiling water shrinkage rate is 7.0%;
  • the dyeing rate of modified polyester FDY yarn at a temperature of 120°C is 87.5%, the K/S value is 23.55, the color fastness to soaping reaches grade 5, the dry rubbing fastness to grade 5, wet rubbing fastness Level 6;

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Abstract

本发明涉及一种半消光涤纶牵伸丝及其制备方法，制备方法为：按FDY工艺由改性聚酯熔体制得半消光涤纶牵伸丝；改性聚酯的制备方法为：将对苯二甲酸、乙二醇、主链含硅的二元醇、含氟二元酸、消光剂和掺杂改性的Bi2O3粉体混合均匀后先后进行酯化反应和缩聚反应，含氟二元酸为2,2-二氟-1,3-丙二酸、2,2-二氟-1,4-丁二酸、2,2-二氟-1,5-戊二酸或2,2,3,3-四氟-1,4-丁二酸。制得产品在120℃的温度条件下的上染率为87.5～91.8％，在温度为25℃且相对湿度为65％的条件下放置60个月后，其特性粘度下降18～26％。本发明的制备方法工艺简单，制得的产品的染色及降解性能好。

Description

半消光涤纶牵伸丝及其制备方法 技术领域
本发明属于聚酯纤维技术领域，涉及一种半消光涤纶牵伸丝及其制备方法。
背景技术
聚酯纤维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，且织物具有抗皱免烫及挺括性好等优点，因此聚酯纤维广泛应用于服装、家纺等领域。随着社会物质水平的不断提高，人们对运动、休闲、时尚、舒适和健康的织物的要求越来越高。在巨大的市场效益刺激下，各个生产厂家纷纷开始开发高感性和高功能性的聚酯纤维产品。行业中开发出了消光、半消光、吸湿排汗、抗菌、防蚊、有色以及阻燃等差别化纤维，为纺织面料及家纺等产品提供了新的优质的纤维原料。
涤纶由于表面光滑，有一定的透明度，在光线的照射下，其反射光线的强度很大，使纤维发出人的肉眼看起来不太舒服的强烈光泽，俗称极光。如果在纤维内添加少量折射率不同的物质，使光线向不同方向进行漫反射，纤维光泽就会变暗，这种处理方式称为消光，所加物质称为消光剂。涤纶生产中通常选择TiO 2作为消光剂，这是因为它的折射率较大(TiO 2的折射率为2.60，空气为1.00)，同时化学稳定性好、分散性好且又不溶于水，在高温中不起变化，在后处理及洗涤时不会消失，因而得到广泛使用。
虽然以上方法能够制得半消光涤纶纤维，但由于涤纶属于疏水性纤维，其分子上不含有亲水性基团，其分子结构中缺少像纤维素或蛋白质纤维那样的能和染料发生结合的活性基团，涤纶纤维的染色性能不佳。此外，涤纶纤维成品为部分结晶的超分子结构，其结晶部分分子链相互平行，大多呈反式构象，而无定形区则多呈顺式构象，其分子排列相当紧密，这进一步增大了涤纶纤维的上染难度。目前常规涤纶(PET)纤维一般选用分散染料在高温(130℃)高压下进行染色，只有在高温高压下进行染色才能保证纤维的上染率，而高温高压对设备的要求较高，能耗较大，同时由于上染难度大，其染色所需时间较长，导致该工艺的成本较高。同时随着PET产业的快速发展，虽然PET不会直接对环境造成危害，但由于其使用后的废品数目巨大且对大气和微生物试剂的抵抗性很强，PET废弃物已成为全球性的环境污染有机物。
因此，研究一种染色性能优异且能够高效率降解回收处理的半消光涤纶牵伸丝的制备方法具有十分重要的意义。
发明内容
本发明的目的是克服现有技术中涤纶纤维染色性能差以及服用涤纶长丝降解速率慢的缺陷，提供一种染色性能优异且能够高效率降解回收处理的半消光涤纶牵伸丝及其制备方法。
为了达到上述目的，本发明采用的技术方案如下：
半消光涤纶牵伸丝的制备方法，按FDY工艺由改性聚酯熔体制得改性聚酯FDY丝，即得半消光涤纶牵伸丝；
所述改性聚酯的制备方法为：将对苯二甲酸、乙二醇、主链含硅的二元醇、含氟二元酸、消光剂和掺杂改性的Bi 2O 3粉体混合均匀后先后进行酯化反应和缩聚反应；
主链含硅的二元醇为二甲基硅二醇、二甲基二苯基二硅氧烷二醇或四甲基二硅氧烷二醇，含氟二元酸为2,2-二氟-1,3-丙二酸、2,2-二氟-1,4-丁二酸、2,2-二氟-1,5-戊二酸或2,2,3,3-四氟-1,4-丁二酸；
所述改性聚酯中消光剂的含量为0.20～0.25wt％；Bi 2O 3掺杂改性的过程为：首先将含Ca 2+的溶液与含Bi 3+的溶液混合均匀，然后滴加沉淀剂至混合液的pH值为9～10，最后煅烧沉淀产物。
本发明通过引入主链含硅的二元醇、含氟二元酸和掺杂改性的Bi 2O 3粉体，改善半消光涤纶牵伸丝的染色性能及自然降解性能。
其中，主链含硅的二元醇主要是通过增大聚酯的空洞自由体积，显著提高半消光涤纶牵伸丝的染色性能，同时空洞自由体积的增大在一定程度上有利于半消光涤纶牵伸丝的自然降解性能的提高。
分散染料是一类分子比较小且结构上不带水溶性基团的染料，其大多以颗粒形式存在，粒径在几百纳米到一微米之间。本发明改性聚酯开始染色时，随着温度的不断提高，由于聚酯大分子链中含有-Si-O-Si-键，硅氧键较碳氧键长，内旋转活化能较低，先于含碳氧键的分子链开始运动，当染浴温度需提高到120～130℃，含有硅氧键的大分 子链运动的剧烈程度大于只含碳氧键分子链，同时由于空洞自由体积更大，含有硅氧键的大分子链形成的空洞自由体积比只含碳氧键分子链形成的自由体积效率更高，因此颗粒状染料向纤维内部的扩散速率提升显著，染料小分子也更容易渗透到改性聚酯大分子内部，对纤维的染色等产生积极的影响，可降低染色温度，缩短染色的时间，减少能耗，同时也提高了纤维的上染率。
本发明引入的含氟二元酸的特殊之处在于氟原子在α碳上，当在水解过程中引入该含氟二元酸时，由于氟原子在α碳上，吸电子能力较强，使得聚酯中C-O键上的电子云密度降低，四面体的负离子的稳定性下降，有利于亲核加成反应的进行，同时由于α碳上含氟二元酸的空间位阻小于对苯二甲酸，进一步促进了亲核加成反应的进行，因而显著提高了降解速率。
本发明还通过对Bi 2O 3粉体进行掺杂改性显著提高了聚酯的自然降解性能，聚酯中含氧还原催化剂时，空气中的氧气能够通过聚酯材质中的自由体积渗入聚酯内部，在氧还原催化剂表面发生氧还原反应，使聚酯的酯键断裂从而加速聚酯降解，但纯氧还原催化剂的降解效率的进一步提高仍然受到限制。本发明的改性聚酯中分散有掺杂改性的Bi 2O 3粉体，与仅将氧化钙与三氧化二铋物理共混制得的混合物相比，氧化钙掺杂Bi 2O 3能够破坏Bi 2O 3的晶面结构，一方面，掺杂后的Bi 2O 3的比表面积增大，能够提高单位质量Bi 2O 3的氧气吸附量，另一方面，掺杂后的Bi 2O 3的吸附方式由单斜Bi 2O 3表面的端式吸附改为掺杂Bi 2O 3表面的侧式吸附，且吸附不受表面Bi原子的“空间位阻效应”影响，O 2分子在Bi原子位的化学吸附增强，催化剂的氧还原催化效率提高，因此分散掺杂改性的Bi 2O 3粉体的涤纶多孔丝回收处理时的降解效率高，有利于保护环境。
作为优选的技术方案：
如上所述的半消光涤纶牵伸丝的制备方法，所述含Ca 2+的溶液的浓度为2～3wt％，溶剂为水，溶液中的阴离子为NO 3 -；所述含Bi 3+的溶液为浓度20～25wt％的Bi 2O 3的溶液，溶剂为硝酸；所述沉淀剂为浓度2mol/L的氨水；
沉淀开始时，混合液中Ca 2+与Bi 3+的摩尔比为5～8:100；本发明通过在Bi 2O 3中引入金属离子Ca 2+(Bi 2O 3为主催化剂)，提高氧离子的传导速率，进而提高氧还原反应的程度，如摩尔比过大，会影响Bi 2O 3的性能；如摩尔比过小，对氧离子的传导速率的提高不明显；
所述煅烧前对沉淀产物进行洗涤和干燥，干燥的温度为105～110℃，时间为2～3h；
所述煅烧的过程为：首先升温至400℃后保温2～3h，然后升温至700℃后保温1～2h，最后在空气中冷却；Bi 2O 3在掺杂改性后进行粉碎得到平均粒径小于0.5微米的粉体。本发明在煅烧过程中将钙溶入Bi 2O 3晶格内部，使得催化剂体相形成更多的缺陷，使其在固溶体表面呈高度分散状态，进而破坏Bi 2O 3的晶面结构。冷却速度过慢，固相中质点的分散速度则较慢，就会形成独立的结晶物，影响破坏Bi 2O 3的晶面结构，在空气中冷却，不利于形成晶体，有利于破坏Bi 2O 3的晶面结构。
如上所述的半消光涤纶牵伸丝的制备方法，所述改性聚酯的制备步骤如下：
(1)酯化反应；
将对苯二甲酸、乙二醇、主链含硅的二元醇和含氟二元酸配成浆料，加入掺杂改性的Bi 2O 3粉体、催化剂、消光剂和稳定剂混合均匀后，在氮气氛围中加压进行酯化反应，加压压力为常压～0.3MPa，酯化反应的温度为250～260℃，当酯化反应中的水馏出量达到理论值的90％以上时为酯化反应终点；
(2)缩聚反应；
酯化反应结束后，在负压条件下开始低真空阶段的缩聚反应，该阶段压力在30～50min内由常压平稳抽至绝对压力500Pa以下，反应温度为250～260℃，反应时间为30～50min，然后继续抽真空，进行高真空阶段的缩聚反应，使反应压力进一步降至绝对压力100Pa以下，反应温度为270～282℃，反应时间为50～90min。
如上所述的半消光涤纶牵伸丝的制备方法，所述对苯二甲酸与乙二醇的摩尔比为1:1.2～2.0，所述主链含硅的二元醇和含氟二元酸的加入量之和为对苯二甲酸加入量的3～5mol％(摩尔百分比)，所述主链含硅的二元醇与含氟二元酸的摩尔比为2～3:3～5，所述掺杂改性的Bi 2O 3粉体、催化剂、消光剂和稳定剂的加入量分别为对苯二甲酸加入量的0.04～0.07wt％、0.03～0.05wt％、0.20～0.25wt％和0.01～0.05wt％(质量百分比)。本发明主链含硅的二元醇、含氟二元酸和掺杂改性的Bi 2O 3粉体的加入量可根据实际应用进行调整，但调整幅度不宜过大，加入量过大，会对纤维的性能(力学性能)产生影响，影响纤维的应用，加入量过小，对纤维的染色性能或降解性能影响过小，难以显著提升纤维的染色效果以及自然降解速率。
如上所述的半消光涤纶牵伸丝的制备方法，所述催化剂为三氧化二锑、乙二醇锑或醋酸锑，所述消光剂为二氧 化钛，所述稳定剂为磷酸三苯酯、磷酸三甲酯或亚磷酸三甲酯。
如上所述的半消光涤纶牵伸丝的制备方法，改性聚酯的数均分子量为25000～30000，分子量分布指数为1.8～2.2。
如上所述的半消光涤纶牵伸丝的制备方法，所述FDY工艺的流程为：计量、喷丝板挤出、冷却、上油、拉伸、热定型和卷绕；
所述FDY工艺的参数为：纺丝温度285～295℃，冷却温度17～22℃，网络压力0.20～0.30MPa，一辊速度2300～2700m/min，一辊温度80～90℃，二辊速度4200～4500m/min，二辊温度125～140℃，卷绕速度4130～4420m/min。
本发明还提供一种采用如上所述的半消光涤纶牵伸丝的制备方法制得的半消光涤纶牵伸丝，为改性聚酯FDY丝；
所述改性聚酯的分子链包括对苯二甲酸链段、乙二醇链段、主链含硅的二元醇链段和含氟二元酸链段；
所述改性聚酯中分散有消光剂和掺杂改性的Bi 2O 3粉体，消光剂的含量为0.20～0.25wt％。
作为优选的技术方案：
如上所述的半消光涤纶牵伸丝，半消光涤纶牵伸丝的单丝纤度为0.7～3.0dtex，断裂强度≥3.5cN/dtex，断裂伸长率为32.0±4.0％，网络度为13±2个/m，线密度偏差率≤1.0％，断裂强度CV值≤5.0％，断裂伸长CV值≤9.0％，沸水收缩率为6.5±0.5％；本发明主链含硅的二元醇链段、含氟二元酸链段以及链段中分散掺杂改性的Bi 2O 3粉体的纤维的品质和质量相比于现有技术未降低，改性后的纤维仍具有良好的力学性能和可纺性等。
如上所述的半消光涤纶牵伸丝，半消光涤纶牵伸丝在120℃的温度条件下的上染率为87.5～91.8％，K/S值为22.17～25.56，耐皂洗色牢度(涤沾色和棉沾色)达到5级，干摩擦牢度达到5级，湿摩擦牢度大于4级；在其他测试条件相同的情况下，对比样在130℃的温度条件下的上染率为85.6％，K/S值为21.28，耐皂洗色牢度小于5级，涤沾色为4～5级，棉沾色为4级，干摩擦牢度为4～5级，湿摩擦牢度为3～4级，对比样与本发明的半消光涤纶牵伸丝的区别仅在于其材质为普通聚酯；
半消光涤纶牵伸丝在温度为25℃且相对湿度为65％的条件下放置60个月后，其特性粘度下降18～26％。本发明的半消光涤纶牵伸丝相比于常规涤纶自然降解速率显著增加，含氟二元酸以及掺杂改性的Bi 2O 3粉体相互配合能够显著提升涤纶纤维的自然降解速率。
发明机理：
本发明通过主链含硅的二元醇对聚酯进行改性，有效提高了涤纶纤维的染色性能，同时还通过含氟二元酸以及掺杂改性的Bi 2O 3粉体的相互配合对聚酯进行进一步改性，在染色效果提升的基础上，又实现了聚酯的加速降解，有效解决了涤纶纤维回收利用的问题。
本发明的主链含硅的二元醇为二甲基硅二醇、二甲基二苯基二硅氧烷二醇或四甲基二硅氧烷二醇，结构式分别如下：
Figure PCTCN2019113839-appb-000001
高分子链的刚性决定于分子链内旋转势垒的大小，主链结构不同，其中键角和键长不等或键接方式不同，刚性也各不相同，本发明引入主链含硅的二元醇后，高分子主链上含有-Si-O-Si-键，硅氧键间隙较大，内旋转活化能较低，有利于原子自由旋转，同时高分子主链上的Si原子与-CH 3连接，-CH 3垂直于Si-O-Si原子所在的平面，由于Si-C键比C-C键键长，导致-CH 3中的三个H呈撑开状态，-CH 3中的三个撑开的H原子可以自由旋转而使相邻的Si-O分子链段间距离变大，此外侧链的惰性甲基又阻碍了高分子的接近，因而高分子材料非常柔顺，空洞自由体积相对于未引入主链含硅的二元醇的高分子材料增大明显；而当高分子主链上的Si原子与长支链取代基连接时，主要增大的是狭缝自由体积，增大幅度较小，对小分子的渗透率和扩散性的提升效果有限，同时由于长支链取代基的刚性较小，分子链之间容易发生缠结，不利于自由体积的增大，主链含硅的二元醇的引入也同样使得改性聚酯的空洞自由体积增大。空洞自由体积的增大将使水或其它分子如染料等更容易渗透到改性聚酯大分子内部，对改性聚酯的 染色等产生积极的影响，可降低染色温度，缩短染色的时间，减少能耗，同时也提高了纤维的上染率。
另外，聚酯在碱性条件下的水解降解过程为亲核加成-消除过程，在水解反应开始时，OH -进攻酯羰基RCOOR`的C原子，发生亲核加成反应，形成中间体(即四面体的负离子)，四面体的负离子可以消除OR`得到羧酸RCOOH，使酯键断裂，同时OR`与H +结合得到醇HOR`。然而，由于在水解过程中形成的四面体的负离子结构比较拥挤，空间位阻大，不利于亲核加成反应的进行，因此聚酯的降解速率较慢。本发明通过在聚酯分子链中引入特殊结构的含氟二元酸显著提高了聚酯的降解速率，含氟二元酸的特殊之处在于氟原子在α碳上，当在水解过程中引入该含氟二元酸时，由于氟原子在α碳上，吸电子能力较强，使得聚酯中C-O键上的的电子云密度降低，四面体的负离子的稳定性下降，有利于亲核加成反应的进行，同时由于α碳上含氟二元酸的空间位阻小于对苯二甲酸，进一步促进了亲核加成反应的进行，因而显著提高了降解速率。如在聚酯分子链中引入氟原子在β碳的含氟二元酸，则不会显著提高聚酯的降解速率，这是因为在β碳上存在吸电子基团时，所产生的影响仅局限于相邻碳上，而对酯键中C-O键产生的影响很小，因而对于OH -进攻酯羰基发生亲核加成的反应影响较小。
而且由于聚酯长期暴露在空气中，当聚酯中含有一定量的氧还原催化剂时，空气中的氧气能够通过聚酯材质中的自由体积(窄缝自由体积和/或空洞自由体积)渗入聚酯内部，氧还原催化剂表面吸附氧气，氧气逐渐迁移到聚酯内部的氧还原催化剂表面，达到一定氧浓度梯度后形成吸附氧，在氧还原催化剂表面发生氧还原反应(氧离子化)，在这一反应过程中，氧气被部分还原为过氧化物，氧还原催化剂吸附后的氧气分子与一个聚酯中的酯键结合并在催化剂表面形成RCOOOR`，后再结合一个质子并断开氧氧键，生成一个RCOOH，使酯键断裂，同时OR`与H +结合得到醇HOR`，从而加速了聚酯降解。
本发明通过先溶液共混再共沉淀再煅烧的方法实现了氧化钙与三氧化二铋的掺杂，进而对三氧化二铋的氧还原催化过程产生影响，提升了聚酯的降解速率。在一定程度上，掺杂离子半径越接近被掺杂的离子半径，越有利于氧空位的形成，越有利于氧离子的传导，本发明选择掺杂与Bi 3+离子半径相同的Ca 2+(Bi 3+和Ca 2+的离子半径均为0.103nm)对其进行掺杂，这能够提高氧离子的传导速率，进而提高氧还原反应的程度。掺杂对三氧化二铋的影响如下：
一方面，采用本发明的掺杂方式能够破坏Bi 2O 3的晶面结构，增大了其比表面积，进而提高了单位质量Bi 2O 3的氧气吸附量；另一方面，采用本发明的掺杂方式能够改变Bi 2O 3的吸附方式和氧还原反应机制，掺杂改性前，吸附方式为单斜Bi 2O 3表面的端式吸附，O原子在不同单斜Bi 2O 3晶面吸附时，都会受到表面Bi原子的“空间位阻效应”影响，O 2分子通过强度较弱的物理吸附或弱化学吸附在Bi原子位吸附，且在不同单斜Bi 2O 3晶面O 2分子都还原为过氧化物，掺杂改性后，吸附方式为掺杂Bi 2O 3表面的侧式吸附，其不受“空间位阻效应”影响，增强了O 2分子在Bi原子位的化学吸附，还能促进O 2分子的O-O键断裂，即可以促进O 2分子还原生成过氧化物，提高了氧还原催化效率进而提高了聚酯降解速率。如仅将氧化钙与三氧化二铋物理共混，氧化钙不会影响三氧化二铋的晶面结构，也不会改变其吸附方式和氧还原反应机制，因而不会提高氧还原催化效率，也会不提高聚酯降解速率。
由于聚酯内部氧还原催化剂的存在，氧气能够在聚酯内部长时间的停留，能够对聚酯中最薄弱的酯基进行氧化反应，加速了聚酯降解的程度。现有技术的降解聚酯均是从聚酯表面开始的，而本发明通过将氧还原催化剂混入聚酯，提供了一种从聚酯内部降解的新思路，且降解效率高。
此外，空洞自由体积的增大(主链含硅的二元醇)还将与含氟二元酸以及掺杂改性的Bi 2O 3粉体协同提高半消光涤纶牵伸丝的自然降解性能，空洞自由体积的增大降低了水及空气分子渗透到改性聚酯大分子内部的难度，为降解反应提高了更多的反应物，一定程度上促进了降解反应。
有益效果：
(1)本发明的半消光涤纶牵伸丝，染色性能优良，机械性能好，容易降解回收利用且品质未降低，有着很好的应用前景；
(2)本发明的半消光涤纶牵伸丝的制备方法，主链含硅的二元醇的添加使改性聚酯的空洞自由体积较大，使得染料、空气或水等小分子很容易进入纤维内部，对改性聚酯的染色及自然降解等产生积极的影响，此外，含氟二元酸以及掺杂改性的Bi 2O 3粉体的添加进一步提高了其自然降解速率，有利于环境保护。
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
半消光涤纶牵伸丝的制备方法，步骤如下：
(1)制备改性聚酯；
(1.1)制备掺杂改性的Bi 2O 3粉体；
(a)将浓度为2.5wt％的Ca(NO 3) 2水溶液与浓度22wt％的Bi 2O 3的溶液混合均匀，Bi 2O 3的溶液的溶剂为硝酸，混合液中Ca 2+与Bi 3+的摩尔比为7:100；
(b)滴加浓度2mol/L的氨水至混合液的pH值为10得到沉淀产物，对沉淀产物进行洗涤和干燥，干燥的温度为105℃，时间为2.5h；
(c)将干燥产物升温至400℃后保温2.5h，然后升温至700℃后保温1.5h，最后在空气中冷却后粉碎得到平均粒径为0.45微米的掺杂改性的Bi 2O 3粉体；
(1.2)酯化反应；
将对苯二甲酸、乙二醇、二甲基硅二醇和2,2-二氟-1,3-丙二酸配成浆料，加入掺杂改性的Bi 2O 3粉体、三氧化二锑、二氧化钛和磷酸三苯酯混合均匀后，在氮气氛围中加压进行酯化反应，加压压力为0.3MPa，酯化反应的温度为250℃，当酯化反应中的水馏出量达到理论值的95时为酯化反应终点，其中苯二甲酸与乙二醇的摩尔比为1:1.2，二甲基硅二醇和2,2-二氟-1,3-丙二酸的加入量之和为对苯二甲酸加入量的3mol％，二甲基硅二醇和2,2-二氟-1,3-丙二酸的摩尔比为2:3，掺杂改性的Bi 2O 3粉体、三氧化二锑、二氧化钛和磷酸三苯酯的加入量分别为对苯二甲酸加入量的0.05wt％、0.03wt％、0.22wt％和0.02wt％；
(1.3)缩聚反应；
酯化反应结束后，在负压条件下开始低真空阶段的缩聚反应，该阶段压力在30min内由常压平稳抽至绝对压力为490Pa，反应温度为272℃，反应时间为35min，然后继续抽真空，进行高真空阶段的缩聚反应，使反应压力进一步降至绝对压力为100Pa，反应温度为270℃，反应时间为50min，制得的改性聚酯的数均分子量为30000，分子量分布指数为2.0；
(2)制备半消光涤纶牵伸丝；
将改性聚酯熔体经计量、喷丝板挤出、冷却、上油、拉伸、热定型和卷绕制得改性聚酯FDY丝，即得半消光涤纶牵伸丝，FDY工艺的参数为：纺丝温度290℃，冷却温度22℃，网络压力0.26MPa，一辊速度2300m/min，一辊温度85℃，二辊速度4500m/min，二辊温度140℃，卷绕速度4420m/min。
最终制得的半消光涤纶牵伸丝为改性聚酯FDY丝，其单丝纤度为0.7dtex，断裂强度为3.6cN/dtex，断裂伸长率为32.0％，网络度为13个/m，线密度偏差率为0.95％，断裂强度CV值为4.45％，断裂伸长CV值为8.8％，沸水收缩率为6.0％；
改性聚酯FDY丝在120℃的温度条件下的上染率为87.5％，K/S值为24.22，耐皂洗色牢度达到5级，干摩擦牢度达到5级，湿摩擦牢度为5级；
改性聚酯FDY丝在温度为25℃且相对湿度为65％的条件下放置60个月后，其特性粘度下降26％。
对比例1
一种半消光涤纶牵伸丝的制备方法，步骤与实施例1基本一致，不同之处在于不对聚酯进行改性，制得的半消光涤纶牵伸丝的单丝纤度为0.7dtex，断裂强度为3.5cN/dtex，断裂伸长率为33.0％，网络度为13个/m，线密度偏差率为0.95％，断裂强度CV值为4.50％，断裂伸长CV值为8.8％，沸水收缩率为6.2％；在25℃且相对湿度为65％的条件下放置60个月后，其特性粘度下降4.2％；在与实施例1其他测试条件相同的情况下，其在130℃的温度条件下的上染率为85.6％，K/S值为21.28，耐皂洗色牢度为4级，干摩擦牢度为4～5级，湿摩擦牢度为3～4级。两者对比可知，本发明通过对聚酯进行改性，大大提高了聚酯纤维的染色性能及自然降解性能且力学性能不受影响。
对比例2
一种半消光涤纶牵伸丝的制备方法，制备步骤与实施例1基本一致，不同之处在于，步骤(1)中采用1,6-己二醇替代二甲基硅二醇，制得的半消光涤纶牵伸丝的单丝纤度为0.7dtex，断裂强度为3.4cN/dtex，断裂伸长率为35.0％，网络度为13个/m，线密度偏差率为0.95％，断裂强度CV值为4.30％，断裂伸长CV值为8.8％，沸水收缩率为6.5％， 25℃且相对湿度为65％的条件下放置60个月后，其特性粘度下降16.7％；在与实施例1其他测试条件相同的情况下，其在130℃的温度条件下的上染率为84.8％，K/S值为20.56，耐皂洗色牢度为4～5级，湿摩擦牢度为4级，均低于本发明。
与实施例1对比可以发现，主链含硅的二元醇引入使得高分子主链上含有-Si-O-Si-键，使得硅氧键间隙较大，内旋转活化能较低，有利于原子自由旋转，从而增大了空洞自由体积，相对于长支链取代基更有利于提升纤维的染色性能及自然降解性能。
对比例3
一种半消光涤纶牵伸丝的制备方法，制备步骤与实施例1基本一致，不同之处在于，步骤(2)中不添加掺杂改性的Bi 2O 3粉，制得的半消光涤纶牵伸丝的单丝纤度为0.7dtex，断裂强度为3.5cN/dtex，断裂伸长率为34.0％，网络度为13个/m，线密度偏差率为0.95％，断裂强度CV值为4.20％，断裂伸长CV值为8.8％，沸水收缩率为6.4％；在与实施例1其他测试条件相同的情况下，其在130℃的温度条件下的上染率为87.2％，K/S值为23.98，耐皂洗色牢度为4～5级，干摩擦牢度为4级，湿摩擦牢度为4级，均低于本发明。在与实施例1相同测试条件下，其特性粘度下降13.7％。
将实施例1与对比例3相对比可以发现，正是由于添加了掺杂改性的Bi 2O 3粉体，本发明的半消光涤纶牵伸丝的自然降解速率相比于普通聚酯纤维有了极大地提升，通过对降解条件进行调整还可进一步加快其降解速率，进而方便纤维的回收利用，同时掺杂改性的Bi 2O 3粉体的添加对纤维其他性能影响较小，并不影响其加工性能及机械性能。
对比例4
一种半消光涤纶牵伸丝的制备方法，制备步骤与实施例1基本一致，不同之处在于，步骤(1)中采用3,3-二氟戊二酸替代2,2-二氟-1,3-丙二酸，制得的半消光涤纶牵伸丝的单丝纤度为0.7dtex，断裂强度为3.3cN/dtex，断裂伸长率为35.0％，网络度为13个/m，线密度偏差率为0.95％，断裂强度CV值为4.00％，断裂伸长CV值为8.8％，沸水收缩率为6.5％。，25℃且相对湿度为65％的条件下放置60个月后，其特性粘度下降12.8％；在与实施例1其他测试条件相同的情况下，其在130℃的温度条件下的上染率为86.97％，K/S值为24.05，耐皂洗色牢度为4～5级，干摩擦牢度为4级，湿摩擦牢度为4级，均低于本发明。
与实施例1对比可以发现，氟原子在α碳的含氟二元酸相对于氟原子在β碳的含氟二元酸更有利于提升纤维的自然降解性能，这是因为在β碳上存在吸电子基团时，所产生的影响仅局限于相邻碳上，而对酯键中C-O键产生的影响很小，因而对于OH -进攻酯羰基发生亲核加成的反应影响较小，进而对纤维的自然降解过程影响较小。
实施例2
半消光涤纶牵伸丝的制备方法，步骤如下：
(1)制备改性聚酯；
(1.1)制备掺杂改性的Bi 2O 3粉体；
(a)将浓度为2wt％的Ca(NO 3) 2水溶液与浓度20wt％的Bi 2O 3的溶液混合均匀，Bi 2O 3的溶液的溶剂为硝酸，混合液中Ca 2+与Bi 3+的摩尔比为5:100；
(b)滴加浓度2mol/L的氨水至混合液的pH值为9得到沉淀产物，对沉淀产物进行洗涤和干燥，干燥的温度为105℃，时间为2h；
(c)将干燥产物升温至400℃后保温2h，然后升温至700℃后保温1h，最后在空气中冷却后粉碎得到平均粒径为0.4微米的掺杂改性的Bi 2O 3粉体；
(1.2)酯化反应；
将对苯二甲酸、乙二醇、二甲基二苯基二硅氧烷二醇和2,2-二氟-1,4-丁二酸配成浆料，加入掺杂改性的Bi 2O 3粉体、三氧化二锑、二氧化钛和磷酸三甲酯混合均匀后，在氮气氛围中加压进行酯化反应，加压压力为0.2MPa，酯化反应的温度为252℃，当酯化反应中的水馏出量达到理论值的90％时为酯化反应终点，其中苯二甲酸与乙二醇的摩尔比为1:1.5，二甲基二苯基二硅氧烷二醇和2,2-二氟-1,4-丁二酸的加入量之和为对苯二甲酸加入量的3.2mol％，二甲基二苯基二硅氧烷二醇和2,2-二氟-1,4-丁二酸的摩尔比为2:5，掺杂改性的Bi 2O 3粉体、三氧化二锑、二氧化钛和磷酸三甲酯的加入量分别为对苯二甲酸加入量的0.04wt％、0.04wt％、0.20wt％和0.04wt％；
(1.3)缩聚反应；
酯化反应结束后，在负压条件下开始低真空阶段的缩聚反应，该阶段压力在35min内由常压平稳抽至绝对压力为420Pa，反应温度为270℃，反应时间为40min，然后继续抽真空，进行高真空阶段的缩聚反应，使反应压力进一步降至绝对压力为95Pa，反应温度为271℃，反应时间为55min，制得的改性聚酯的数均分子量为28000，分子量分布指数为2.0；
(2)制备半消光涤纶牵伸丝；
将改性聚酯熔体经计量、喷丝板挤出、冷却、上油、拉伸、热定型和卷绕制得改性聚酯FDY丝，即得半消光涤纶牵伸丝，FDY工艺的参数为：纺丝温度285℃，冷却温度20℃，网络压力0.24MPa，一辊速度2700m/min，一辊温度90℃，二辊速度4300m/min，二辊温度125℃，卷绕速度4130m/min。
最终制得的半消光涤纶牵伸丝为改性聚酯FDY丝，其单丝纤度为1.5dtex，断裂强度为3.5cN/dtex，断裂伸长率为28.0％，网络度为11个/m，线密度偏差率为0.9％，断裂强度CV值为4.9％，断裂伸长CV值为8.8％，沸水收缩率为7.0％；
改性聚酯FDY丝在120℃的温度条件下的上染率为91.8％，K/S值为22.17，耐皂洗色牢度达到5级，干摩擦牢度达到5级，湿摩擦牢度为6级；
改性聚酯FDY丝在温度为25℃且相对湿度为65％的条件下放置60个月后，其特性粘度下降20％。
实施例3
半消光涤纶牵伸丝的制备方法，步骤如下：
(1)制备改性聚酯；
(1.1)制备掺杂改性的Bi 2O 3粉体；
(a)将浓度为3wt％的Ca(NO 3) 2水溶液与浓度25wt％的Bi 2O 3的溶液混合均匀，Bi 2O 3的溶液的溶剂为硝酸，混合液中Ca 2+与Bi 3+的摩尔比为8:100；
(b)滴加浓度2mol/L的氨水至混合液的pH值为9得到沉淀产物，对沉淀产物进行洗涤和干燥，干燥的温度为110℃，时间为3h；
(c)将干燥产物升温至400℃后保温3h，然后升温至700℃后保温2h，最后在空气中冷却后粉碎得到平均粒径为0.4微米的掺杂改性的Bi 2O 3粉体；
(1.2)酯化反应；
将对苯二甲酸、乙二醇、四甲基二硅氧烷二醇和2,2-二氟-1,5-戊二酸配成浆料，加入掺杂改性的Bi 2O 3粉体、乙二醇锑、二氧化钛和亚磷酸三甲酯混合均匀后，在氮气氛围中加压进行酯化反应，加压压力为0.1MPa，酯化反应的温度为255℃，当酯化反应中的水馏出量达到理论值的92％时为酯化反应终点，其中苯二甲酸与乙二醇的摩尔比为1:1.3，四甲基二硅氧烷二醇和2,2-二氟-1,5-戊二酸的加入量之和为对苯二甲酸加入量的3.5mol％，四甲基二硅氧烷二醇和2,2-二氟-1,5-戊二酸的摩尔比为2.5:3，掺杂改性的Bi 2O 3粉体、乙二醇锑、二氧化钛和亚磷酸三甲酯的加入量分别为对苯二甲酸加入量的0.04wt％、0.05wt％、0.24wt％和0.01wt％；
(1.3)缩聚反应；
酯化反应结束后，在负压条件下开始低真空阶段的缩聚反应，该阶段压力在45min内由常压平稳抽至绝对压力为500Pa，反应温度为280℃，反应时间为30min，然后继续抽真空，进行高真空阶段的缩聚反应，使反应压力进一步降至绝对压力为96Pa，反应温度为273℃，反应时间为60min，制得的改性聚酯的数均分子量为25000，分子量分布指数为2.2；
(2)制备半消光涤纶牵伸丝；
将改性聚酯熔体经计量、喷丝板挤出、冷却、上油、拉伸、热定型和卷绕制得改性聚酯FDY丝，即得半消光涤纶牵伸丝，FDY工艺的参数为：纺丝温度285℃，冷却温度17℃，网络压力0.30MPa，一辊速度2400m/min，一辊温度83℃，二辊速度4500m/min，二辊温度125℃，卷绕速度4130m/min。
最终制得的半消光涤纶牵伸丝为改性聚酯FDY丝，其单丝纤度为2.0dtex，断裂强度为3.6cN/dtex，断裂伸长率为36.0％，网络度为15个/m，线密度偏差率为0.95％，断裂强度CV值为4.4％，断裂伸长CV值为8.6％，沸水收缩率为6.5％；
改性聚酯FDY丝在120℃的温度条件下的上染率为87.5％，K/S值为22.17，耐皂洗色牢度达到5级，干摩擦牢度达到5级，湿摩擦牢度为5级；
改性聚酯FDY丝在温度为25℃且相对湿度为65％的条件下放置60个月后，其特性粘度下降18％。
实施例4
半消光涤纶牵伸丝的制备方法，步骤如下：
(1)制备改性聚酯；
(1.1)制备掺杂改性的Bi 2O 3粉体；
(a)将浓度为2.5wt％的Ca(NO 3) 2水溶液与浓度25wt％的Bi 2O 3的溶液混合均匀，Bi 2O 3的溶液的溶剂为硝酸，混合液中Ca 2+与Bi 3+的摩尔比为8:100；
(b)滴加浓度2mol/L的氨水至混合液的pH值为10得到沉淀产物，对沉淀产物进行洗涤和干燥，干燥的温度为110℃，时间为3h；
(c)将干燥产物升温至400℃后保温2.5h，然后升温至700℃后保温2h，最后在空气中冷却后粉碎得到平均粒径为0.4微米的掺杂改性的Bi 2O 3粉体；
(1.2)酯化反应；
将对苯二甲酸、乙二醇、二甲基硅二醇和2,2,3,3-四氟-1,4-丁二酸配成浆料，加入掺杂改性的Bi 2O 3粉体、乙二醇锑、二氧化钛和磷酸三苯酯混合均匀后，在氮气氛围中加压进行酯化反应，加压压力为0.1MPa，酯化反应的温度为250℃，当酯化反应中的水馏出量达到理论值的95％时为酯化反应终点，其中苯二甲酸与乙二醇的摩尔比为1:1.6，二甲基硅二醇和2,2,3,3-四氟-1,4-丁二酸的加入量之和为对苯二甲酸加入量的4mol％，二甲基硅二醇和2,2,3,3-四氟-1,4-丁二酸的摩尔比为2.2:4，掺杂改性的Bi 2O 3粉体、乙二醇锑、二氧化钛和磷酸三苯酯的加入量分别为对苯二甲酸加入量的0.07wt％、0.04wt％、0.25wt％和0.03wt％；
(1.3)缩聚反应；
酯化反应结束后，在负压条件下开始低真空阶段的缩聚反应，该阶段压力在40min内由常压平稳抽至绝对压力为440Pa，反应温度为278℃，反应时间为40min，然后继续抽真空，进行高真空阶段的缩聚反应，使反应压力进一步降至绝对压力为99Pa，反应温度为273℃，反应时间为75min，制得的改性聚酯的数均分子量为25000，分子量分布指数为1.8；
(2)制备半消光涤纶牵伸丝；
将改性聚酯熔体经计量、喷丝板挤出、冷却、上油、拉伸、热定型和卷绕制得改性聚酯FDY丝，即得半消光涤纶牵伸丝，FDY工艺的参数为：纺丝温度295℃，冷却温度17℃，网络压力0.20MPa，一辊速度2600m/min，一辊温度90℃，二辊速度4200m/min，二辊温度125℃，卷绕速度4360m/min。
最终制得的半消光涤纶牵伸丝为改性聚酯FDY丝，其单丝纤度为3.0dtex，断裂强度为3.5cN/dtex，断裂伸长率为32.0％，网络度为12个/m，线密度偏差率为1.0％，断裂强度CV值为4.9％，断裂伸长CV值为9.0％，沸水收缩率为6.8％；
改性聚酯FDY丝在120℃的温度条件下的上染率为89.63％，K/S值为25.56，耐皂洗色牢度达到5级，干摩擦牢度达到5级，湿摩擦牢度为5级；
改性聚酯FDY丝在温度为25℃且相对湿度为65％的条件下放置60个月后，其特性粘度下降18％。
实施例5
半消光涤纶牵伸丝的制备方法，步骤如下：
(1)制备改性聚酯；
(1.1)制备掺杂改性的Bi 2O 3粉体；
(a)将浓度为2.5wt％的Ca(NO 3) 2水溶液与浓度24wt％的Bi 2O 3的溶液混合均匀，Bi 2O 3的溶液的溶剂为硝酸，混合液中Ca 2+与Bi 3+的摩尔比为6:100；
(b)滴加浓度2mol/L的氨水至混合液的pH值为10得到沉淀产物，对沉淀产物进行洗涤和干燥，干燥的温度为107℃，时间为2.5h；
(c)将干燥产物升温至400℃后保温2.5h，然后升温至700℃后保温2h，最后在空气中冷却后粉碎得到平均粒径为0.45微米的掺杂改性的Bi 2O 3粉体；
(1.2)酯化反应；
将对苯二甲酸、乙二醇、二甲基二苯基二硅氧烷二醇和2,2-二氟-1,3-丙二酸配成浆料，加入掺杂改性的Bi 2O 3 粉体、醋酸锑、二氧化钛和磷酸三甲酯混合均匀后，在氮气氛围中加压进行酯化反应，加压压力为常压，酯化反应的温度为260℃，当酯化反应中的水馏出量达到理论值的91％时为酯化反应终点，其中苯二甲酸与乙二醇的摩尔比为1:1.8，二甲基二苯基二硅氧烷二醇和2,2-二氟-1,3-丙二酸的加入量之和为对苯二甲酸加入量的4.0mol％，二甲基二苯基二硅氧烷二醇和2,2-二氟-1,3-丙二酸的摩尔比为3:4，掺杂改性的Bi 2O 3粉体、醋酸锑、二氧化钛和磷酸三甲酯的加入量分别为对苯二甲酸加入量的0.05wt％、0.03wt％、0.25wt％和0.01wt％；
(1.3)缩聚反应；
酯化反应结束后，在负压条件下开始低真空阶段的缩聚反应，该阶段压力在50min内由常压平稳抽至绝对压力为490Pa，反应温度为282℃，反应时间为35min，然后继续抽真空，进行高真空阶段的缩聚反应，使反应压力进一步降至绝对压力为100Pa，反应温度为274℃，反应时间为80min，制得的改性聚酯的数均分子量为30000，分子量分布指数为1.8；
(2)制备半消光涤纶牵伸丝；
将改性聚酯熔体经计量、喷丝板挤出、冷却、上油、拉伸、热定型和卷绕制得改性聚酯FDY丝，即得半消光涤纶牵伸丝，FDY工艺的参数为：纺丝温度292℃，冷却温度22℃，网络压力0.20MPa，一辊速度2300m/min，一辊温度80℃，二辊速度4200m/min，二辊温度125℃，卷绕速度4420m/min。
最终制得的半消光涤纶牵伸丝为改性聚酯FDY丝，其单丝纤度为1.6dtex，断裂强度为3.7cN/dtex，断裂伸长率为31.0％，网络度为15个/m，线密度偏差率为0.92％，断裂强度CV值为5.0％，断裂伸长CV值为8.4％，沸水收缩率为7.0％；
改性聚酯FDY丝在120℃的温度条件下的上染率为89.20％，K/S值为23.44，耐皂洗色牢度达到5级，干摩擦牢度达到5级，湿摩擦牢度为6级；
改性聚酯FDY丝在温度为25℃且相对湿度为65％的条件下放置60个月后，其特性粘度下降21％。
实施例6
半消光涤纶牵伸丝的制备方法，步骤如下：
(1)制备改性聚酯；
(1.1)制备掺杂改性的Bi 2O 3粉体；
(a)将浓度为3wt％的Ca(NO 3) 2水溶液与浓度24wt％的Bi 2O 3的溶液混合均匀，Bi 2O 3的溶液的溶剂为硝酸，混合液中Ca 2+与Bi 3+的摩尔比为7:100；
(b)滴加浓度2mol/L的氨水至混合液的pH值为10得到沉淀产物，对沉淀产物进行洗涤和干燥，干燥的温度为110℃，时间为2.5h；
(c)将干燥产物升温至400℃后保温3h，然后升温至700℃后保温1.5h，最后在空气中冷却后粉碎得到平均粒径为0.45微米的掺杂改性的Bi 2O 3粉体；
(1.2)酯化反应；
将对苯二甲酸、乙二醇、四甲基二硅氧烷二醇和2,2-二氟-1,4-丁二酸配成浆料，加入掺杂改性的Bi 2O 3粉体、醋酸锑、二氧化钛和亚磷酸三甲酯混合均匀后，在氮气氛围中加压进行酯化反应，加压压力为常压，酯化反应的温度为254℃，当酯化反应中的水馏出量达到理论值的94％时为酯化反应终点，其中苯二甲酸与乙二醇的摩尔比为1:2.0，四甲基二硅氧烷二醇和2,2-二氟-1,4-丁二酸的加入量之和为对苯二甲酸加入量的4.5mol％，四甲基二硅氧烷二醇和2,2-二氟-1,4-丁二酸的摩尔比为3:5，掺杂改性的Bi 2O 3粉体、醋酸锑、二氧化钛和亚磷酸三甲酯的加入量分别为对苯二甲酸加入量的0.07wt％、0.04wt％、0.20wt％和0.05wt％；
(1.3)缩聚反应；
酯化反应结束后，在负压条件下开始低真空阶段的缩聚反应，该阶段压力在35min内由常压平稳抽至绝对压力为450Pa，反应温度为270℃，反应时间为50min，然后继续抽真空，进行高真空阶段的缩聚反应，使反应压力进一步降至绝对压力为100Pa，反应温度为275℃，反应时间为85min，制得的改性聚酯的数均分子量为27800，分子量分布指数为1.8；
(2)制备半消光涤纶牵伸丝；
将改性聚酯熔体经计量、喷丝板挤出、冷却、上油、拉伸、热定型和卷绕制得改性聚酯FDY丝，即得半消光涤纶牵伸丝，FDY工艺的参数为：纺丝温度295℃，冷却温度18℃，网络压力0.20MPa，一辊速度2300m/min，一 辊温度80℃，二辊速度4400m/min，二辊温度130℃，卷绕速度4420m/min。
最终制得的半消光涤纶牵伸丝为改性聚酯FDY丝，其单丝纤度为2.5dtex，断裂强度为3.5cN/dtex，断裂伸长率为33.0％，网络度为11个/m，线密度偏差率为1.0％，断裂强度CV值为5.0％，断裂伸长CV值为8.2％，沸水收缩率为6.5％；
改性聚酯FDY丝在120℃的温度条件下的上染率为91.8％，K/S值为25.56，耐皂洗色牢度达到5级，干摩擦牢度达到5级，湿摩擦牢度为6级；
改性聚酯FDY丝在温度为25℃且相对湿度为65％的条件下放置60个月后，其特性粘度下降22％。
实施例7
半消光涤纶牵伸丝的制备方法，步骤如下：
(1)制备改性聚酯；
(1.1)制备掺杂改性的Bi 2O 3粉体；
(a)将浓度为2.5wt％的Ca(NO 3) 2水溶液与浓度25wt％的Bi 2O 3的溶液混合均匀，Bi 2O 3的溶液的溶剂为硝酸，混合液中Ca 2+与Bi 3+的摩尔比为8:100；
(b)滴加浓度2mol/L的氨水至混合液的pH值为10得到沉淀产物，对沉淀产物进行洗涤和干燥，干燥的温度为110℃，时间为3h；
(c)将干燥产物升温至400℃后保温3h，然后升温至700℃后保温2h，最后在空气中冷却后粉碎得到平均粒径为0.45微米的掺杂改性的Bi 2O 3粉体；
(1.2)酯化反应；
将对苯二甲酸、乙二醇、四甲基二硅氧烷二醇和2,2-二氟-1,5-戊二酸配成浆料，加入掺杂改性的Bi 2O 3粉体、三氧化二锑、二氧化钛和磷酸三甲酯混合均匀后，在氮气氛围中加压进行酯化反应，加压压力为0.3MPa，酯化反应的温度为260℃，当酯化反应中的水馏出量达到理论值的99％时为酯化反应终点，其中苯二甲酸与乙二醇的摩尔比为1:1.3，四甲基二硅氧烷二醇和2,2-二氟-1,5-戊二酸的加入量之和为对苯二甲酸加入量的5mol％，四甲基二硅氧烷二醇和2,2-二氟-1,5-戊二酸的摩尔比为2.5:3，掺杂改性的Bi 2O 3粉体、三氧化二锑、二氧化钛和磷酸三甲酯的加入量分别为对苯二甲酸加入量的0.06wt％、0.04wt％、0.21wt％和0.01wt％；
(1.3)缩聚反应；
酯化反应结束后，在负压条件下开始低真空阶段的缩聚反应，该阶段压力在45min内由常压平稳抽至绝对压力为500Pa，反应温度为280℃，反应时间为50min，然后继续抽真空，进行高真空阶段的缩聚反应，使反应压力进一步降至绝对压力为90Pa，反应温度为277℃，反应时间为90min，制得的改性聚酯的数均分子量为30000，分子量分布指数为2.2；
(2)制备半消光涤纶牵伸丝；
将改性聚酯熔体经计量、喷丝板挤出、冷却、上油、拉伸、热定型和卷绕制得改性聚酯FDY丝，即得半消光涤纶牵伸丝，FDY工艺的参数为：纺丝温度295℃，冷却温度22℃，网络压力0.30MPa，一辊速度2700m/min，一辊温度86℃，二辊速度4500m/min，二辊温度135℃，卷绕速度4130m/min。
最终制得的半消光涤纶牵伸丝为改性聚酯FDY丝，其单丝纤度为1.2dtex，断裂强度为3.5cN/dtex，断裂伸长率为32.0％，网络度为13个/m，线密度偏差率为0.88％，断裂强度CV值为4.5％，断裂伸长CV值为9.0％，沸水收缩率为7.0％；
改性聚酯FDY丝在120℃的温度条件下的上染率为87.5％，K/S值为23.55，耐皂洗色牢度达到5级，干摩擦牢度达到5级，湿摩擦牢度为6级；
改性聚酯FDY丝在温度为25℃且相对湿度为65％的条件下放置60个月后，其特性粘度下降26％。

Claims (10)

  1. 半消光涤纶牵伸丝的制备方法，其特征是：按FDY工艺由改性聚酯熔体制得改性聚酯FDY丝，即得半消光涤纶牵伸丝；
    所述改性聚酯的制备方法为：将对苯二甲酸、乙二醇、主链含硅的二元醇、含氟二元酸、消光剂和掺杂改性的Bi 2O 3粉体混合均匀后先后进行酯化反应和缩聚反应；
    主链含硅的二元醇为二甲基硅二醇、二甲基二苯基二硅氧烷二醇或四甲基二硅氧烷二醇，含氟二元酸为2,2-二氟-1,3-丙二酸、2,2-二氟-1,4-丁二酸、2,2-二氟-1,5-戊二酸或2,2,3,3-四氟-1,4-丁二酸；
    所述改性聚酯中消光剂的含量为0.20～0.25wt％；Bi 2O 3掺杂改性的过程为：首先将含Ca 2+的溶液与含Bi 3+的溶液混合均匀，然后滴加沉淀剂至混合液的pH值为9～10，最后煅烧沉淀产物。
  2. 根据权利要求1所述的半消光涤纶牵伸丝的制备方法，其特征在于，所述含Ca 2+的溶液的浓度为2～3wt％，溶剂为水，溶液中的阴离子为NO 3 -；所述含Bi 3+的溶液为浓度20～25wt％的Bi 2O 3的溶液，溶剂为硝酸；所述沉淀剂为浓度2mol/L的氨水；
    沉淀开始时，混合液中Ca 2+与Bi 3+的摩尔比为5～8:100；
    所述煅烧前对沉淀产物进行洗涤和干燥，干燥的温度为105～110℃，时间为2～3h；
    所述煅烧的过程为：首先升温至400℃后保温2～3h，然后升温至700℃后保温1～2h，最后在空气中冷却；Bi 2O 3在掺杂改性后进行粉碎得到平均粒径小于0.5微米的粉体。
  3. 根据权利要求2所述的半消光涤纶牵伸丝的制备方法，其特征在于，所述改性聚酯的制备步骤如下：
    (1)酯化反应；
    将对苯二甲酸、乙二醇、主链含硅的二元醇和含氟二元酸配成浆料，加入掺杂改性的Bi 2O 3粉体、催化剂、消光剂和稳定剂混合均匀后，在氮气氛围中加压进行酯化反应，加压压力为常压～0.3MPa，酯化反应的温度为250～260℃，当酯化反应中的水馏出量达到理论值的90％以上时为酯化反应终点；
    (2)缩聚反应；
    酯化反应结束后，在负压条件下开始低真空阶段的缩聚反应，该阶段压力在30～50min内由常压平稳抽至绝对压力500Pa以下，反应温度为250～260℃，反应时间为30～50min，然后继续抽真空，进行高真空阶段的缩聚反应，使反应压力进一步降至绝对压力100Pa以下，反应温度为270～282℃，反应时间为50～90min。
  4. 根据权利要求3所述的半消光涤纶牵伸丝的制备方法，其特征在于，所述对苯二甲酸与乙二醇的摩尔比为1:1.2～2.0，所述主链含硅的二元醇和含氟二元酸的加入量之和为对苯二甲酸加入量的3～5mol％，所述主链含硅的二元醇与含氟二元酸的摩尔比为2～3:3～5，所述掺杂改性的Bi 2O 3粉体、催化剂、消光剂和稳定剂的加入量分别为对苯二甲酸加入量的0.04～0.07wt％、0.03～0.05wt％、0.20～0.25wt％和0.01～0.05wt％。
  5. 根据权利要求4所述的半消光涤纶牵伸丝的制备方法，其特征在于，所述催化剂为三氧化二锑、乙二醇锑或醋酸锑，所述消光剂为二氧化钛，所述稳定剂为磷酸三苯酯、磷酸三甲酯或亚磷酸三甲酯。
  6. 根据权利要求5所述的半消光涤纶牵伸丝的制备方法，其特征在于，改性聚酯的数均分子量为25000～30000，分子量分布指数为1.8～2.2。
  7. 根据权利要求1所述的半消光涤纶牵伸丝的制备方法，其特征在于，所述FDY工艺的流程为：计量、喷丝板挤出、冷却、上油、拉伸、热定型和卷绕；
    所述FDY工艺的参数为：纺丝温度285～295℃，冷却温度17～22℃，网络压力0.20～0.30MPa，一辊速度2300～2700m/min，一辊温度80～90℃，二辊速度4200～4500m/min，二辊温度125～140℃，卷绕速度4130～4420m/min。
  8. 采用如权利要求1～7任一项所述的半消光涤纶牵伸丝的制备方法制得的半消光涤纶牵伸丝，其特征是：为改性聚酯FDY丝；
    所述改性聚酯的分子链包括对苯二甲酸链段、乙二醇链段、主链含硅的二元醇链段和含氟二元酸链段；
    所述改性聚酯中分散有消光剂和掺杂改性的Bi 2O 3粉体，消光剂的含量为0.20～0.25wt％。
  9. 根据权利要求8所述的半消光涤纶牵伸丝，其特征在于，半消光涤纶牵伸丝 的单丝纤度为0.7～3.0dtex，断裂强度≥3.5cN/dtex，断裂伸长率为32.0±4.0％，网络度为13±2个/m，线密度偏差率≤1.0％，断裂强度CV值≤5.0％，断裂伸长CV值≤9.0％，沸水收缩率为6.5±0.5％。
  10. 根据权利要求8所述的半消光涤纶牵伸丝，其特征在于，半消光涤纶牵伸丝在120℃的温度条件下的上染率为87.5～91.8％，K/S值为22.17～25.56，耐皂洗色牢度达到5级，干摩擦牢度达到5级，湿摩擦牢度大于4级；
    半消光涤纶牵伸丝在温度为25℃且相对湿度为65％的条件下放置60个月后，其特性粘度下降18～26％。
PCT/CN2019/113839 2018-12-27 2019-10-29 半消光涤纶牵伸丝及其制备方法 WO2020134494A1 (zh)

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