WO2018077126A1 - 一种聚酯 - Google Patents

一种聚酯 Download PDF

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Publication number
WO2018077126A1
WO2018077126A1 PCT/CN2017/107220 CN2017107220W WO2018077126A1 WO 2018077126 A1 WO2018077126 A1 WO 2018077126A1 CN 2017107220 W CN2017107220 W CN 2017107220W WO 2018077126 A1 WO2018077126 A1 WO 2018077126A1
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Prior art keywords
polyester
amount
weight
semi
hindered phenolic
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PCT/CN2017/107220
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English (en)
French (fr)
Inventor
成娟
柏立军
陈彬彬
旦浩一
中川顺一
田中陽一郎
Original Assignee
东丽纤维研究所（中国）有限公司
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Application filed by 东丽纤维研究所（中国）有限公司 filed Critical 东丽纤维研究所（中国）有限公司
Priority to CN201780050617.6A priority Critical patent/CN109563257B/zh
Priority to JP2019521413A priority patent/JP6988891B2/ja
Priority to KR1020197011786A priority patent/KR102356959B1/ko
Publication of WO2018077126A1 publication Critical patent/WO2018077126A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • 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
    • 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
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • D01F6/88—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

Definitions

  • the present invention relates to a polyester excellent in hygroscopicity.
  • Polyester has a wide range of applications in the fields of fibers, films, and plastics due to its excellent properties.
  • the hydrophobicity is strong.
  • the polyester fiber has poor water absorption and hygroscopicity, which greatly limits the application of the polyester fiber in a hygroscopic environment.
  • the polyester fiber has a sultry feeling due to poor hygroscopicity, so the polyester fiber is particularly unsuitable for use in summer clothing.
  • the surface of the fiber is modified to mainly make the surface of the fiber porous, and the capillary principle is used to improve the hygroscopicity of the fiber.
  • Modification of the fiber surface can also be achieved by methods such as discharge treatment, photo-graft modification, and low-temperature plasma treatment.
  • discharge treatment photo-graft modification
  • low-temperature plasma treatment low-temperature plasma treatment.
  • the fiber obtained by these methods is made into a woven fabric, it does not have a good effect in reducing the steaming feeling in a sweating state, and the like, and there is no feeling of cooling of natural fibers such as cotton or hemp.
  • there is a method of coating a hydrophilic film on the surface of the fiber but this method often has the disadvantage of poor affinity between the fiber and the film, and poor durability after washing.
  • polyester fibers it is also possible to improve the moisture absorption properties of the fibers by chemically grafting the polyester fibers. For example, after graft copolymerization of acrylic acid and methacrylic acid to a polyethylene terephthalate (PET) fiber of 15%, a sodium ion exchange treatment is performed to obtain a moisture absorption rate equivalent to that of cotton.
  • PET polyethylene terephthalate
  • a sodium ion exchange treatment is performed to obtain a moisture absorption rate equivalent to that of cotton.
  • the moisture absorption rate of the fiber is very slow, and the basic properties of the polyester fiber are greatly lost, and there is basically no application value, so there has been no industrial production.
  • high molecular weight polyether compounds are also used to improve hygroscopicity, but high molecular weight polyether compounds are not completely copolymerized with the polyester matrix, and most of them are present in the polyester in the state of the separated phase, which causes the polymer.
  • the coarse phase is formed to form an unstable phase-separated structure.
  • the discharge is spun and the discharge of the gold portion is unstable during the spinning, resulting in a fine fiber spot, a large stain, and a hairiness.
  • Special PEG is copolymerized with PET to improve the moisture absorption properties of PET in Japanese Patent Laid-Open No. 2007-70467.
  • An object of the present invention is to provide a polyester excellent in hygroscopicity, and the fiber obtained by the polyester spinning has excellent heat-resistant water properties and oxidation-resistant heat-generating properties.
  • a polyester which is a polymer formed by using an aromatic dicarboxylic acid or a derivative thereof and an aliphatic diol as a main constituent component, and polyethylene glycol as a copolymer component, wherein the polyethylene glycol is a polyethylene glycol.
  • the number average molecular weight is from 2,000 to 30,000 g/mol
  • the copolymerization ratio is from 25 to 55% by weight
  • the polyester contains a semi-hindered phenolic antioxidant as shown in Formula 1.
  • R1 is a group formed by one or a combination of hydrocarbon, oxygen, nitrogen; and R2 is a group formed by one or a combination of hydrogen, hydrocarbon, oxygen, nitrogen.
  • the content of the semi-hindered phenolic antioxidant is preferably from 1.0 to 8.0% by weight based on the total weight of the polyester.
  • the semi-hindered phenolic antioxidant is preferably an antioxidant 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylbenzene) as shown in Formula 2.
  • the copolymerization ratio of the polyethylene glycol is preferably 35 to 55 wt%.
  • the aliphatic diol is preferably ethylene glycol or 1,4-butanediol; and when the aliphatic diol is preferably ethylene glycol, the number average molecular weight of the polyethylene glycol is preferably from 4,000 to 30,000 g/mol.
  • the polyethylene glycol has a high copolymerization rate
  • the polyester sheet is excellent in hygroscopicity
  • the difference in moisture absorption rate before and after dyeing of the polyester fiber is small.
  • the polyester has good heat resistance, excellent anti-yellowing property and high application value.
  • the polyester of the present invention is a polyether ester obtained by copolymerizing an aromatic dicarboxylic acid or a derivative thereof and an aliphatic diol as a main monomer, and polyethylene glycol is a copolymerized component, and has good heat resistance. Sexual and mechanical properties.
  • the aromatic dicarboxylic acid or a derivative thereof may specifically be exemplified by terephthalic acid, isophthalic acid, phthalic acid, sodium isophthalate-5-sulfonate, isophthalic acid- Lithium 5-sulfonate, phosphorus compound of 5-(tetraalkyl)-isophthalate sulfonate, 4,4'-biphenyl dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, etc., but not limited to the above, Among them, teric acid is preferred.
  • the aliphatic diol may specifically be exemplified by ethylene glycol, 1,3-propanediol, 1,4-butanediol, hexanediol, cyclohexane hexanediol, diethylene glycol, and hexa Methyl glycol, neopentyl glycol, etc., but not limited to the above.
  • ethylene glycol, propylene glycol, and 1,4-butanediol are preferred for use in production and use. From the viewpoint of heat resistance and mechanical properties, ethylene glycol is more preferable; from the viewpoint of crystallinity, 1,4-butanediol is more preferable.
  • the number average molecular weight of the polyethylene glycol of the copolymer component of the polyester of the present invention can be appropriately selected within the range in which the polyester has crystallinity.
  • the copolymerization ratio of the polyethylene glycol in the polyester of the present invention is 25 to 55 wt%. When the copolymerization ratio of polyethylene glycol is less than 25% by weight, the discharge property of the polyester is poor; when the copolymerization ratio of polyethylene glycol is more than 55 wt%, the physical properties of the fiber formed of the obtained polyester are lowered. Since the copolymerization ratio of the polyethylene glycol is generally between 25 and 35 wt%, the resulting polyester has a general discharge property. Therefore, in order to obtain a polyester having a better discharge property, the copolymerization ratio of the polyethylene glycol in the present invention is preferably 35 to ⁇ . 55wt%.
  • the preferred range varies depending on the composition of the polyester.
  • the aliphatic diol of the polyester component is ethylene glycol
  • the polymerization temperature is too high, so that the polymerization is too high.
  • the degradation of ethylene glycol is severe, and the moisture absorption rate of the final polyester or even the finished fiber will decrease.
  • the aliphatic diol which is a constituent component of the polyester is 1,4-butanediol
  • the degradation of polyethylene glycol is relatively less serious due to the lower polymerization temperature than in the case of using ethylene glycol as described above.
  • the hygroscopicity of the polyester and the hygroscopicity even after the fiber is formed can also be improved.
  • the number average molecular weight of the polyethylene glycol is preferably 4,000 to 30,000 g/mol, and the copolymerization ratio of the polyethylene glycol is preferably 35 to 55 wt%.
  • the polyester has high hygroscopicity and can be obtained by spinning alone or by composite spinning to obtain fibers excellent in hygroscopicity.
  • the number average molecular weight of the polyethylene glycol is 30,000 g/mol or less, the polycondensation reactivity is high, and the unreacted polyethylene glycol is reduced, and the dissolution in hot water during hot water treatment such as dyeing can be suppressed.
  • the hygroscopicity after the treatment can be maintained.
  • the number average molecular weight of the polyethylene glycol is preferably 25,000 g/mol or less, and more preferably 20,000 g/mol or less.
  • the polyester has high hygroscopicity, and fibers which are excellent in hygroscopicity can be obtained by individual spinning or composite spinning.
  • the copolymerization ratio of polyethylene glycol is 55 wt% or less, the occurrence of yarn breakage and hairiness is reduced after the polyester is spun, and the engineering passability is good, and the stain is formed when a fiber structure such as a woven fabric or a knitted fabric is formed. The hairiness is reduced and the quality is excellent.
  • the number average molecular weight of the polyethylene glycol is preferably 2,000 to 30,000 g/mol, and the copolymerization ratio of the polyethylene glycol is preferably 35 to 55 wt%.
  • the polyester has high hygroscopicity, and fibers which are excellent in hygroscopicity can be obtained by individual spinning or composite spinning. At the same time, it is possible to suppress a decrease in crystallinity of the polyester.
  • the number average molecular weight of the polyethylene glycol is 2,000 g/mol or more
  • the decrease in the crystallinity of the polyester and the decrease in the extrapolation melting initiation temperature can be suppressed, and the occurrence of the yarn and the hairiness due to the elongation and the false twisting process is reduced.
  • the project has good passability, and when the fiber structure such as woven fabric and knitted fabric is formed, the generation of stains and hairiness is reduced, and the quality is excellent.
  • the number average molecular weight of the polyethylene glycol is 30,000 g/mol or less, the polycondensation reactivity is high, and the unreacted polyethylene glycol is reduced, and the dissolution in hot water during hot water treatment such as dyeing can be suppressed.
  • the hygroscopicity after the treatment can be maintained.
  • the number average molecular weight of the polyethylene glycol is preferably 27,000 g/mol or less, more preferably 25,000 g/mol or less, and most preferably 20,000 g/mol or less.
  • the polyester has high hygroscopicity, and fibers which are excellent in hygroscopicity can be obtained by individual spinning or composite spinning.
  • the copolymerization ratio of polyethylene glycol is 55 wt% or less, the elongation of the yarn and the hairiness of the false twisting project are reduced, and the engineering passability is good, and the fiber structure is formed when a fabric such as a woven fabric or a knitted fabric is formed. The hairiness is reduced and the quality is excellent.
  • the antioxidant dose of the hindered phenol to be added is generally small, so that the yellowing problem does not occur; however, when the copolymerization ratio of polyethylene glycol is higher than 25 wt% The problem of yellowing will be more serious.
  • the present invention uses a semi-hindered phenolic antioxidant as shown in Formula 1, even if there is an ether bond radical formed by thermal oxidative decomposition, since the phenolic hydroxyl group of the semi-hindered phenolic antioxidant is ortho-methyl, the steric effect is compared. Small, ether-bonded free radicals will attack the meta-position of the semi-hindered phenolic antioxidant phenolic hydroxyl group and will not form yellow anthraquinones.
  • R1 is a group formed by one or a combination of hydrocarbon, oxygen, nitrogen; and R2 is a group formed by one or a combination of hydrogen, hydrocarbon, oxygen, nitrogen.
  • the semi-hindered phenolic antioxidant of the present invention is preferably 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy Ethyl]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, or 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethyl Benzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, the amount of addition varies according to the amount of polyethylene glycol, the final hindered phenol in the polyester
  • the content of the antioxidant is preferably 1.0 to 8.0% by weight.
  • the content of the semi-hindered phenolic antioxidant is too low, the oxidation resistance of the polyester after forming the fiber is poor, and the hygroscopicity of the polyester fiber after the oxidative decomposition of the polyethylene glycol is lowered; if the content of the semi-hindered phenolic antioxidant is too high, The polyester fiber is yellowed due to the decomposition of the antioxidant itself.
  • the polyester is moisture absorption rate
  • the moisture absorption rate difference (?MR) according to the present invention means a value measured in accordance with the method described in the specification.
  • the polyester is separately spun by a conventional spinning method or is conjugated with other component polymers to obtain fibers excellent in hygroscopicity.
  • the fiber obtained by the conventional single or composite spinning method has a fiber color L value of 6 or less, preferably 4, after hot water treatment at 130 ° C. the following.
  • the hue yellowing value ⁇ YI is 10.0 or less, preferably 8.0 or less, and more preferably 7.5 or less.
  • ⁇ YI is 7.5 or less
  • the nitrogen-oxygen fastness is 4 to 5
  • ⁇ YI is 7.5 or more
  • the nitrogen-oxygen fastness is 4 steps.
  • a compound containing a titanium element or a lanthanum element may be added as a catalyst. Since the catalytic activity of the titanium-containing catalyst is high, the side reaction is easily promoted, and the color tone stability of the final polyester fiber is affected. Therefore, when the titanium-containing catalyst is selected, the amount of the titanium-containing catalyst is preferably controlled to be 10 to 150 ppm equivalent to the polyester based on the titanium element. Within the scope. When a compound of a ruthenium element is used as a catalyst, the amount thereof is in the range of 150 to 300 ppm corresponding to the polyester based on the ruthenium element.
  • auxiliary modifiers can also be added.
  • the auxiliary modifier may specifically be exemplified by other types of antioxidants, phase solvents, plasticizers, ultraviolet absorbers, fluorescent whitening agents, antibacterial agents, nucleating agents, heat stabilizers, antistatic agents, matting agents, Defoamers, dyes, pigments, perfumes and the like, but are not limited to the above.
  • the above auxiliary additives may be used singly or in combination.
  • the extrapolated melting onset temperature of the polyester of the present invention is above 180 °C.
  • the extrapolated melting onset temperature of the polyester of the present invention means a value calculated in accordance with the method described in the specification. When a plurality of melting peaks are observed, the melting peak having the lowest temperature is calculated.
  • the polyester has an extrapolated melting initiation temperature of 180 ° C or more, the polyester is formed into a fiber, and the occurrence of yarn breakage and hairiness is reduced, and the engineering passability is good, and the dyeing and hairiness are generated when a fiber structure such as a woven fabric or a knitted fabric is formed. It is less and has excellent quality.
  • the polyester of the present invention is a fiber obtained by spinning alone or by composite spinning with other components by a conventional spinning method, and a pseudofilament yarn or a fiber structure formed therefrom is excellent in hygroscopicity. Therefore, it can be used for applications requiring comfort and quality. For example, general clothing use, sports clothing use, bedding use, interior decoration use, and use of materials, etc., are not limited to the above list.
  • the polyester and the fiber were used as samples, and dried at 60 ° C for 30 minutes in hot air, and then allowed to stand in a constant temperature and humidity machine LHU-123 manufactured by ESPEC at a temperature of 20 ° C and a humidity of 65% RH for 24 hours to measure the weight of the polymer. (W1); and then allowed to stand in a constant temperature and humidity machine at a temperature of 30 ° C and a humidity of 90% RH for 24 hours, and the weight of the polymer was determined to be (W2). Then, it was dried by hot air at 105 ° C for 2 hours, and the weight of the polymer after absolute drying was measured as (W3).
  • the moisture absorption rate MR1 (%) after standing for 24 hours from the dry state to 20 ° C and a humidity of 65% RH was calculated from the weights W1 and W3 of the polymer, and the weight of the polymer was used according to the following formula.
  • W2 and W3 calculated the moisture absorption rate MR2 (%) after leaving the dry state to 30 ° C and a humidity of 90% RH for 24 hours, and then calculated the moisture absorption rate difference ( ⁇ MR) according to the following formula. Furthermore, one sample was measured five times, and the average value was taken as the moisture absorption rate difference ( ⁇ MR).
  • Hygroscopic rate difference ( ⁇ MR) (%) MR2-MR1.
  • the polyester obtained in the examples was subjected to hot water treatment at 130 ° C for 20 minutes by spinning separately or by spinning a fiber formed by spinning separately with other components by a conventional method, and the obtained sample was subjected to a color difference meter (USTC). -datacolor)
  • the L value was measured as L2
  • the L value before hot water treatment was measured as L1
  • L2-L1 was the hot water treatment yellowing value.
  • the polyester obtained in the examples was separately spun by a conventional method or a fiber formed by composite spinning with other components as a test sample, and a NOx gas generating agent (85% phosphoric acid and 2% of argon) was placed in a closed container.
  • a NOx gas generating agent 85% phosphoric acid and 2% of argon
  • the aqueous solution of nitric acid then the sample and the blue standard dyeing are arranged in the container.
  • the blue standard dyeing cloth fades to the standard gray board No. 3
  • the blue standard dyeing cloth is replaced, and when the color reaches the standard gray board again 3
  • the sample is taken out, washed twice, and dried.
  • the yellowing value was measured by a Datacolor 650 spectrophotometer.
  • Copolymerization ratio of polyethylene glycol (peak area of H in ether bond / number of H in ether bond * molecular weight of structural unit of polyether compound) / [(peak area of H in ether bond / H in ether bond) Number * structural unit molecular weight of the polyether compound) + (peak area of H in isophthalic acid containing sodium sulfonate / 3 * molecular weight of ester formed by isophthalic acid containing sodium sulfonate) + H in PTA Peak area / molecular weight of 4*PET + peak area of H of EG unit structure in polyester / molecular weight of 4*EG unit structure].
  • a 50 mg sample was weighed into a bottle, sealed with 1 mL of ammonia water, and heated at 120 ° C for 3 hours. After cooling, the sample was pulverized and heated at 120 ° C for an additional 2 hours. After cooling, 1.5 ml of distilled water and 1.5 mL of 6 M hydrochloric acid were added, and the volume was adjusted with a 5 ML volumetric flask. After centripetal separation (3500 rpm ⁇ 10 minutes), filtration was carried out with a 0.45 ⁇ m sieve, and the obtained filtrate was subjected to GPC test. This sample was subjected to GPC test (Alliance 2690 manufactured by Waters) under the following conditions. The molecular weight below 1800 cannot be separated from the impurity, and the number average molecular weight is determined in addition to this;
  • Detector RI-8020 manufactured by Japan's "East ⁇ ", sensitivity 128x
  • Pillar TSKge1G3000PWXL I manufactured by Japan's "East ⁇ "
  • Standard material polyethylene glycol ("Mn ⁇ 106 ⁇ 10 1000 g/mol" manufactured by ⁇ ).
  • Pretreatment 8g of polyester was taken and treated with 150 ml of solvent toluene for 35 minutes; after treatment, it was cooled to 100 degrees, then pour into the telecentric separation tube; next to the telecentric separation, take the upper layer of the liquid with a 0.45 ⁇ m filter for filtration; then dilute with methanol, telecentric separation to take the upper layer of liquid; finally add the internal standard, with 0.45 The filter of ⁇ m was filtered and measured by HPLC.
  • HPLC determination mobile phase A/B: methanol/water (12%); flow rate: 1.3 ml/min; column temperature: 40 degrees; ultraviolet wavelength: 284 nm; time: 15 min.
  • the core component, the sheath component polymer, and the fiber obtained in the example were used as a sample, and the extrapolation melting onset temperature was measured using a Q2000 type differential scanning calorimeter (DSC) manufactured by TA Instruments.
  • DSC differential scanning calorimeter
  • the temperature change range was ⁇ 1 ° C, and the temperature was changed for 60 seconds, and then the temperature was raised to measure TMDSC.
  • the extrapolated melting onset temperature was calculated from the melting peak observed during the second temperature rise in accordance with the standard of JISK7121:1987 (method of measuring the transition temperature of plastic). One sample was measured three times, and the average value was used as the extrapolation melting onset temperature. Further, when a plurality of melting peaks are observed, the extrapolated melting onset temperature is calculated from the melting peak on the lowest temperature side.
  • PEG 8300 polyethylene glycol having a number average molecular weight of 8300 g/mol, abbreviated as PEG 8300
  • PEG 8300 polyethylene glycol having a number average molecular weight of 8300 g/mol, abbreviated as PEG 8300
  • the amount of stabilizer trimethyl phosphate 250ppm after 5 minutes, began to increase the pressure under reduced pressure, reached a final temperature of 285 ° C, the final pressure, adding to the reaction system of 1.0 wt% of semi-hindered phenolic antioxidant relative to the total amount of final polyester 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H - Triketone (CN1790), after stirring for 10 minutes, nitrogen gas was introduced into the reaction system to return to normal pressure, and the polycondensation reaction was stopped to obtain a copolyester.
  • PEG 8300 polyethylene
  • polyester chips obtained above were melt-spun, and the spinning speed was 3 Km/min to obtain pre-oriented yarns. Then, the obtained pre-oriented yarn was subjected to false twist processing under the following conditions: a first hot box temperature of 180 ° C, a second hot box temperature of normal temperature, and a stretching ratio of 1.7, to obtain a highly hygroscopic polyester fiber.
  • the specific properties of polyester and fiber are shown in Table 1.
  • the amount of PEG 8300 added was 40% by weight, and the amount of the semi-hindered phenolic antioxidant CN1790 was 1.1% by weight. The rest are the same as in the first embodiment. See Table 1 for details.
  • the addition amount of PEG 11000 (number average molecular weight 11000 g/mol) was 35 wt%, and the amount of the semi-hindered phenol antioxidant CN1790 was 1.0 wt%. The rest are the same as in the first embodiment. See Table 1 for details.
  • the addition amount of PEG 20000 (number average molecular weight 20,000 g/mol) was 35 wt%, and the amount of the semi-hindered phenol antioxidant CN1790 was 1.0 wt%. The rest are the same as in the first embodiment. See Table 1 for details.
  • the addition amount of PEG30000 (number average molecular weight 30000 g/mol) was 35 wt%, and the amount of the semi-hindered phenol antioxidant CN1790 was 1.0 wt%. The rest are the same as in the first embodiment. See Table 1 for details.
  • the addition amount of PEG8300 was 35 wt%, and the amount of the semi-hindered phenol antioxidant CN1790 was 3.0 wt%. The rest are the same as in the first embodiment. See Table 1 for details.
  • the addition amount of PEG8300 was 35 wt%, and the amount of the semi-hindered phenol antioxidant CN1790 was 5.0 wt%. The rest are the same as in the first embodiment. See Table 1 for details.
  • PEG8300 is added in an amount of 35 wt%, semi-hindered phenolic antioxidant semi-hindered phenolic antioxidant 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-) Methylphenyl)propanoyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane (AO80) was added in an amount of 1.6% by weight. The rest are the same as in the first embodiment. See Table 1 for details.
  • the addition amount of PEG8300 was 35 wt%, and the amount of the semi-hindered phenol antioxidant AO80 was 4.7 wt%. The rest are the same as in the first embodiment. See Table 1 for details.
  • the addition amount of PEG8300 was 35 wt%, and the amount of the semi-hindered phenol antioxidant AO80 was 8.0 wt%. The rest are the same as in the first embodiment. See Table 1 for details.
  • the amount of PEG 8300 added was 30% by weight, and the amount of the semi-hindered phenolic antioxidant CN1790 was 1.0% by weight. The rest are the same as in the first embodiment. See Table 1 for details.
  • the addition amount of PEG8300 was 27% by weight, and the amount of the semi-hindered phenolic antioxidant CN1790 was 10.0% by weight. The rest are the same as in the first embodiment. See Table 1 for details.
  • the tetrabutyl phthalate catalyst was 900 ppm, and the stabilizer trimethyl phosphate was added to the total amount of the final polyester, 250 ppm. After 5 minutes, the pressure was raised to a temperature of 250 ° C and the final pressure was added to the reaction system.
  • polyester is 1.3% by weight of the semi-hindered phenolic antioxidant 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5- Triazine-2,4,6-(1H,3H,5H)-trione (CN1790), after stirring for 10 minutes, nitrogen gas was introduced into the reaction system to return to normal pressure, and the polycondensation reaction was stopped to obtain a copolyester.
  • semi-hindered phenolic antioxidant 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5- Triazine-2,4,6-(1H,3H,5H)-trione
  • polyester chips obtained above were melt-spun, and the spinning speed was 3 Km/min to obtain pre-oriented yarns. Then, the obtained pre-oriented yarn was subjected to false twist processing under the following conditions: a first hot box temperature of 180 ° C, a second hot box temperature of normal temperature, and a stretching ratio of 1.7, to obtain a highly hygroscopic polyester fiber.
  • the specific properties of polyester and fiber are shown in Table 2.
  • the amount of PEG 3400 added was 55 wt%, and the amount of the semi-hindered phenolic antioxidant CN1790 was 1.4 wt%.
  • the rest is the same as in Example 13. See Table 2 for details.
  • the amount of PEG 3400 added was 58% by weight, and the amount of the semi-hindered phenolic antioxidant CN1790 was 1.8% by weight. The rest is the same as in Example 13. See Table 2 for details.
  • the amount of PEG 11000 added was 55 wt%, and the amount of antioxidant CN1790 added was 1.4 wt%. The rest is the same as in Example 13. See Table 2 for details.
  • the amount of PEG 20000 added was 55 wt%, and the amount of the semi-hindered phenolic antioxidant CN 1790 was 1.4 wt%.
  • the rest is the same as in Example 13. See Table 2 for details.
  • the addition amount of PEG3400 was 55 wt%, and the amount of the semi-hindered phenolic antioxidant CN1790 was 4.2 wt%, and the rest was the same as in Example 13. See Table 2 for details.
  • the addition amount of PEG3400 was 55 wt%, and the amount of the semi-hindered phenolic antioxidant CN1790 was 8.0 wt%, and the rest was the same as in Example 13. See Table 2 for details.
  • PEG3400 is added in an amount of 55 wt%, a semi-hindered phenolic antioxidant 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propene
  • the amount of the acyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane (AO80) was 2.2% by weight. The rest is the same as in Example 13. See Table 2 for details.
  • the amount of PEG 3400 added was 55 wt%, and the amount of the semi-hindered phenol antioxidant AO80 was 6.6 wt%.
  • the rest is the same as in Example 13. See Table 2 for details.
  • the amount of PEG 3400 added was 55 wt%, and the amount of the semi-hindered phenolic antioxidant AO-80 was 8.0 wt%.
  • the rest is the same as in Example 13. See Table 2 for details.
  • the amount of PEG 3400 added was 50% by weight, and the amount of the semi-hindered phenolic antioxidant CN1790 was 10.0% by weight. The rest is the same as in Example 13. See Table 2 for details.
  • PEG 8300 polyethylene glycol having a number average molecular weight of 8300 g/mol, abbreviated as PEG 8300
  • PEG 8300 polyethylene glycol having a number average molecular weight of 8300 g/mol, abbreviated as PEG 8300
  • the amount of stabilizer trimethyl phosphate 250ppm after 5 minutes, began to increase the pressure under reduced pressure, reached a final temperature of 285 ° C, the final pressure, adding to the reaction system of 1.0 wt% of semi-hindered phenolic antioxidant relative to the total amount of final polyester 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H - Triketone (CN1790), after stirring for 10 minutes, nitrogen gas was introduced into the reaction system to return to normal pressure, and the polycondensation reaction was stopped to obtain a copolyester.
  • PEG 8300 polyethylene
  • the ratio is supplied to the screw type composite spinning machine to be melted separately, and the spunlace temperature is 285 ° C and the discharge amount is 36 g / min.
  • the island-type composite spinning spun gold (24 islands in one discharge hole) is spun. article.
  • the spun yarn is cooled under cold air with a wind temperature of 20 ° C and a wind speed of 20 m / min.
  • the oil feed device is subjected to oil-contracting, and the first section of the roller is rotated at 2,500 m/min, and the first section of the roller is passed.
  • the second stage roller of the same turning speed is taken up to obtain an unstretched yarn of 144 dtex-36f.
  • an extension false twisting machine tilting section: friction disk type, heater part: contact type
  • the obtained unstretched yarn was subjected to extension false twisting at a heater temperature of 170 ° C and a magnification of 1.7 times to obtain 84 dtex. -36f fake silk.
  • the evaluation results of the fiber properties, the fabric properties, and the engineering passability of the obtained fibers are shown in Table 3.
  • the number of broken wires at the time of false twist is 0, and the engineering passability is extremely good.
  • the hygroscopicity after the hot water treatment is not substantially lowered, and the hygroscopicity after the hot water treatment is also good.
  • the level of dyeing and quality have reached the qualified level. See Table 3 for details.
  • the semi-hindered phenolic antioxidant CN1790 was added in an amount of 3.0% by weight, the same as in Example 24. See Table 3 for details.
  • the amount of the semi-hindered phenolic antioxidant CN1790 was 5.0% by weight, and the rest was the same as in Example 24. See Table 3 for details.
  • the addition amount of PEG8300 was 45 wt%, and the amount of the semi-hindered phenolic antioxidant CN1790 was 5.0 wt%, and the rest was the same as in Example 24. See Table 3 for details.
  • the addition amount of PEG8300 was 55 wt%, and the amount of the semi-hindered phenolic antioxidant CN1790 was 5.0 wt%, and the rest was the same as in Example 24. See Table 3 for details.
  • Example 30 The amount of the semi-hindered phenolic antioxidant AO80 was 1.6 wt%, and the rest was the same as in Example 24. See Table 3 for details.
  • Example 30 The amount of the semi-hindered phenolic antioxidant AO80 was 1.6 wt%, and the rest was the same as in Example 24. See Table 3 for details.
  • Example 31 The amount of the semi-hindered phenolic antioxidant AO80 was 4.7 wt%, and the rest was the same as in Example 24. See Table 3 for details.
  • Example 31 The amount of the semi-hindered phenolic antioxidant AO80 was 4.7 wt%, and the rest was the same as in Example 24. See Table 3 for details.
  • Example 32 The amount of the semi-hindered phenolic antioxidant AO80 was 8.0% by weight, and the rest was the same as in Example 24. See Table 3 for details.
  • Example 32 The amount of the semi-hindered phenolic antioxidant AO80 was 8.0% by weight, and the rest was the same as in Example 24. See Table 3 for details.
  • the amount of the semi-hindered phenolic antioxidant CN1790 was 2.0% by weight, and the rest was the same as in Example 24. See Table 3 for details.
  • Example 34 The amount of the semi-hindered phenolic antioxidant AO80 was 4.0% by weight, and the rest was the same as in Example 24. See Table 3 for details.
  • Example 34 The amount of the semi-hindered phenolic antioxidant AO80 was 4.0% by weight, and the rest was the same as in Example 24. See Table 3 for details.
  • Example 35 The amount of the semi-hindered phenolic antioxidant AO80 was 6.0% by weight, and the rest was the same as in Example 24. See Table 3 for details.
  • Example 35 The amount of the semi-hindered phenolic antioxidant AO80 was 6.0% by weight, and the rest was the same as in Example 24. See Table 3 for details.
  • the amount of the semi-hindered phenolic antioxidant CN1790 was 9.0% by weight, and the rest was the same as in Example 24. See Table 3 for details.
  • the amount of the semi-hindered phenolic antioxidant CN1790 was 0.9 wt%, and the rest was the same as in Example 24. See Table 3 for details.
  • the tetrabutyl phthalate catalyst was 900 ppm, and the stabilizer trimethyl phosphate was added to the total amount of the final polyester, 250 ppm. After 5 minutes, the pressure was raised to a temperature of 250 ° C and the final pressure was added to the reaction system.
  • polyester is 1.3% by weight of the semi-hindered phenolic antioxidant 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5- Triazine-2,4,6-(1H,3H,5H)-trione (CN1790), after stirring for 10 minutes, nitrogen gas was introduced into the reaction system to return to normal pressure, and the polycondensation reaction was stopped to obtain a copolyester. The rest is the same as in Example 24. See Table 4 for details.
  • the amount of the semi-hindered phenolic antioxidant CN1790 was 2.4 wt%, and the rest was the same as in Example 37. See Table 4 for details.
  • the amount of the semi-hindered phenolic antioxidant CN1790 was 4.2% by weight, and the rest was the same as in Example 37. See Table 4 for details.
  • the amount of the semi-hindered phenolic antioxidant CN1790 was 8.0% by weight, and the rest was the same as in Example 37. See Table 4 for details.
  • Example 42 The amount of the semi-hindered phenolic antioxidant AO80 added was 2.2% by weight, and the rest was the same as in Example 37. See Table 4 for details.
  • Example 42 The amount of the semi-hindered phenolic antioxidant AO80 added was 2.2% by weight, and the rest was the same as in Example 37. See Table 4 for details.
  • Example 43 The amount of the semi-hindered phenolic antioxidant AO80 was 6.6 wt%, and the rest was the same as in Example 37. See Table 4 for details.
  • Example 43 The amount of the semi-hindered phenolic antioxidant AO80 was 6.6 wt%, and the rest was the same as in Example 37. See Table 4 for details.
  • the addition amount of PEG8300 was 45 wt%, and the amount of the semi-hindered phenol antioxidant AO80 was 6.6 wt%, and the rest was the same as in Example 37. See Table 4 for details.
  • the addition amount of PEG8300 was 55 wt%, and the amount of the semi-hindered phenol antioxidant AO80 was 6.6 wt%, and the rest was the same as in Example 37. See Table 4 for details.
  • the addition amount of PEG8300 was 50% by weight, and the amount of the semi-hindered phenolic antioxidant AO80 was 8.0% by weight, and the rest was the same as in Example 37. See Table 4 for details.
  • the addition amount of PEG8300 was 50% by weight, and the amount of the semi-hindered phenolic antioxidant CN1790 was 2.0% by weight, and the rest was the same as in Example 37. See Table 4 for details.
  • the addition amount of PEG8300 was 50% by weight, and the amount of the semi-hindered phenolic antioxidant CN1790 was 3.0% by weight, and the rest was the same as in Example 37. See Table 4 for details.
  • the addition amount of PEG8300 was 50% by weight, and the amount of the semi-hindered phenolic antioxidant CN1790 was 5.0% by weight, and the rest was the same as in Example 37. See Table 4 for details.
  • the addition amount of PEG8300 was 50% by weight, and the amount of the semi-hindered phenolic antioxidant AO80 was 4.0% by weight, and the rest was the same as in Example 37. See Table 4 for details.
  • the addition amount of PEG8300 was 50% by weight, and the amount of the semi-hindered phenolic antioxidant AO80 was 6.0% by weight, and the rest was the same as in Example 37. See Table 4 for details.
  • the addition amount of PEG8300 was 50% by weight, and the amount of the semi-hindered phenolic antioxidant CN1790 was 9.0% by weight, and the rest was the same as in Example 37. See Table 4 for details.
  • the addition amount of PEG8300 was 12% by weight, and the amount of the semi-hindered phenolic antioxidant CN1790 was 1.0% by weight, and the rest was the same as in Example 1. See Table 5 for details. Since the amount of PEG added is relatively small, the high hygroscopic effect is not obtained.
  • the addition amount of PEG8300 was 20% by weight, and the amount of the semi-hindered phenolic antioxidant CN1790 was 1.0% by weight, and the rest was the same as in Example 1. See Table 5 for details. Since the amount of PEG added is relatively small, the high hygroscopic effect is not obtained.
  • the addition amount of PEG 100000 (number average molecular weight 100,000 g/mol) was 30% by weight, and the amount of the semi-hindered phenolic antioxidant CN1790 was 2.0% by weight, and the rest was the same as in Example 1. See Table 5 for details. Due to the addition of ultra-high molecular weight PEG, the spit rises and the discharge is not easy.
  • the addition amount of PEG3400 was 12% by weight, and the amount of the semi-hindered phenolic antioxidant CN1790 was 0.8% by weight, and the rest was the same as in Example 13. See Table 5 for details. Since the amount of PEG added is relatively small, the high hygroscopic effect is not obtained.
  • the addition amount of PEG3400 was 70% by weight, and the amount of the semi-hindered phenolic antioxidant CN1790 was 4.6% by weight, and the rest was the same as in Example 13. See Table 5 for details.
  • the addition amount of PEG3400 is too high, resulting in a low initial melt initiation temperature of the final polyester.
  • the polyester forms fibers, the occurrence of broken filaments and hairiness increases, and the engineering passability deteriorates to form fiber structures such as fabrics and braids.
  • the body is stained and hairy, the quality is not good.
  • the addition amount of PEG 600 (number average molecular weight: 600 g/mol) was 50% by weight, and the amount of the semi-hindered phenolic antioxidant CN1790 was 3.3% by weight, and the rest was the same as in Example 13. See Table 5 for details.
  • the molecular weight of PEG is low, and a large amount of scattering occurs during the polymerization. Even if it is added in a large amount, the obtained polyester has poor hygroscopicity.
  • the amount of PEG 100000 added was 50% by weight, and the amount of the semi-hindered phenolic antioxidant CN1790 was 3.3% by weight, the same as in Example 13. See Table 5 for details. Due to the addition of ultra-high molecular weight PEG, the spit rises and the discharge is not easy.
  • the addition amount of PEG3400 was 20% by weight, and the amount of the semi-hindered phenolic antioxidant CN1790 was 1.0% by weight, and the rest was the same as in Example 13. See Table 5 for details. Since the amount of PEG added is relatively small, the high hygroscopic effect is not obtained.
  • PEG8300 was added in an amount of 20% by weight, and the hindered phenolic antioxidant (IR1010) was added in an amount of 0.5% by weight, the same as in Example 1. See Table 5 for details. Hindered phenolic antioxidants tend to cause yellowing of the polyester compared to hindered phenolic antioxidants.
  • PEG8300 was added in an amount of 50% by weight, and the hindered phenolic antioxidant IR1010 was added in an amount of 3.0% by weight, the same as in Example 1. See Table 5 for details.
  • a hindered phenolic antioxidant is added in a large amount, although the antioxidant effect is excellent, the fiber is liable to yellow.
  • PEG8300 was added in an amount of 50% by weight, and the hindered phenolic antioxidant IR1010 was added in an amount of 0.5% by weight, the same as in Example 1. See Table 5 for details.
  • the hindered phenolic antioxidant is added in a small amount, the yellowing of the fiber can be suppressed, but the antioxidant effect is lowered.
  • PEG3400 was added in an amount of 20% by weight, and the hindered phenolic antioxidant IR1010 was added in an amount of 0.5% by weight, the same as in Example 13. See Table 5 for details. Hindered phenolic antioxidants tend to cause yellowing of the polyester compared to hindered phenolic antioxidants. In the case of a small amount of PEG added, although only a small amount of hindered phenolic antioxidant IR1010 is required, the polyester yellowing index is within an acceptable range, but the antioxidant effect of the polyester is lowered, and the polyester fiber before and after dyeing is used. The difference in moisture absorption rate difference is large, indicating that the hygroscopicity of the polyester fiber after dyeing is significantly reduced.
  • PEG3400 was added in an amount of 50% by weight, and the hindered phenolic antioxidant IR1010 was added in an amount of 3.0% by weight, the same as in Example 13. See Table 5 for details.
  • a hindered phenolic antioxidant is added in a large amount, although the antioxidant effect is excellent, the fiber is liable to yellow.
  • PEG3400 was added in an amount of 50% by weight, and the hindered phenolic antioxidant IR1010 was added in an amount of 0.5% by weight, the same as in Example 13. See Table 5 for details.
  • the hindered phenolic antioxidant is added in a small amount, the yellowing of the fiber can be suppressed, but the antioxidant effect is lowered.
  • the addition amount of PEG8300 was 22% by weight, and the amount of the semi-hindered phenolic antioxidant CN1790 was 1.0% by weight, and the rest was the same as in Example 1. See Table 5 for details. The addition amount of PEG8300 is not suitable, resulting in poor discharge property.
  • the addition amount of PEG8300 was 25 wt%, and the amount of the semi-hindered phenolic antioxidant CN1790 was 1.0 wt%, and the rest was the same as in Example 1. See Table 5 for details. The addition amount of PEG8300 is not suitable, resulting in poor discharge property.
  • PEG8300 was added in an amount of 50% by weight, and the hindered phenolic antioxidant IR1010 was added in an amount of 3.0% by weight, the same as in Example 24. See Table 6 for details.
  • the antioxidant effect is excellent, the fiber is liable to yellow.
  • PEG8300 was added in an amount of 50% by weight, and the hindered phenolic antioxidant IR1010 was added in an amount of 0.8% by weight, the same as in Example 24. See Table 6 for details.
  • a hindered phenolic antioxidant is added in a small amount, although the yellowing of the fiber can be suppressed, the antioxidant effect is lowered.
  • the addition amount of PEG8300 was 50% by weight, and no antioxidant was added, and the rest was the same as in Example 24. See Table 6 for details. Since no antioxidant is added, the fiber does not yellow, but does not have an antioxidant effect.

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Abstract

本发明公开一种聚酯，所述聚酯是以芳香族二元羧酸或其衍生物与脂肪族二元醇为主要构成成分、聚乙二醇为共聚合成分形成的聚合物，其中聚乙二醇的数均分子量为2000～30000g/mol，共聚合率为25～55wt％。本发明的聚酯，通过常规纺丝方法单独纺丝或与其他组分复合纺丝制得的纤维，及由其形成的假捻丝、纤维构造体的吸湿性优异。因此，可以用于要求舒适性及品质的用途。

Description

一种聚酯 技术领域
本发明涉及一种吸湿性优异的聚酯。
背景技术
聚酯由于其优异的性能，在纤维、薄膜、塑料等领域有着广泛的应用。但是由于聚酯的结构规整，疏水性较强，与棉或麻等天然纤维相比，聚酯纤维的吸水性、吸湿性较差，大大限制了聚酯纤维在要求吸湿性环境下的应用。由聚酯纤维得到的纺织品制成贴身衣物时，由于聚酯纤维的吸湿性差，会给人带来闷热感，因此聚酯纤维特别不适合应用于夏装方面。
为了解决聚酯纤维吸水吸湿性差的问题，本领域技术人员尝试了很多方法。例如对纤维表面进行改性，主要是使纤维表面多孔质化后利用毛细管原理提高纤维的吸湿性。也可以使用放电处理、光接枝改性、低温等离子处理等方法实现纤维表面的改性。但是通过这些方法得到的纤维制成织物后，对于在出汗状态下减少蒸热感等方面没有很好的效果，更不会有棉、麻等天然纤维的清凉感。在这些方法之外，还有在纤维表面包裹亲水性膜的方法，但是这种方法往往存在纤维与膜之间亲和性差、水洗后耐久性不佳的缺点。
也可以通过对聚酯纤维进行化学接枝的方法来提高纤维的吸湿性能。例如：对聚对苯二甲酸乙二醇酯(PET)纤维进行15％程度的丙烯酸及甲基丙烯酸的接枝共聚合后，进行钠离子交换的处理，可以得到与棉同等的吸湿率。可是这种纤维的吸湿速度很慢，而且聚酯纤维的基本性能有很大损失，基本上没有了应用价值，所以也一直没有工业化生产。
另外，也有使用高分子量的聚醚化合物来提高吸湿性的，但是高分子量的聚醚化合物与聚酯基体不完全进行共聚，大部分以分离相的状态存在于聚酯中，这样会导致聚合物熔融滞留时粗大化形成不稳定的相分离结构，聚合反应终了后吐出以及纺丝时口金部吐出不稳定，导致最终纤维的纤度斑、染斑大，以及毛羽的产生。日本专利特开2007-70467中使用特殊的PEG与PET共聚来改善PET的吸湿性能。但是PEG的添加量过少的话，不能带来高的吸湿性，因此需要较高的添加量，其结果就是导致聚酯成纤后失去纤维的基本性能，而且耐热性能、耐热水性能以及耐氧化发热性能大大变差，使用价值变的很低。
发明内容
本发明的目的在于提供一种吸湿性优异的聚酯，由该聚酯纺丝所得到的纤维具有优异的耐热水性能以及耐氧化发热性能。
本发明的技术解决方案如下：
一种聚酯，所述聚酯是以芳香族二元羧酸或其衍生物与脂肪族二元醇为主要构成成分、聚乙二醇为共聚合成分形成的聚合物，其中聚乙二醇的数均分子量为2000～30000g/mol，共聚合率为25～55wt％，并且聚酯中含有如式1所示的半受阻酚类抗氧化剂，
Figure PCTCN2017107220-appb-000001
其中，R1为由碳氢、氧、氮中的一种或者几种结合形成的基团；R2为由氢、碳氢、氧、氮中的一种或者几种结合形成的基团。
所述半受阻酚类抗氧化剂的含有量优选占聚酯总重量的1.0～8.0wt％。
所述半受阻酚类抗氧化剂优选如式2所示的抗氧化剂3,9-双[1,1-二甲基-2-[(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基]乙基]-2,4,8,10-四氧杂螺[5.5]十一烷，或者如式3所示的1，3，5-三(4-叔丁基-3-羟基-2，6-二甲基苄基)-1，3，5-三嗪-2，4，6-(1H，3H，5H)-三酮，
Figure PCTCN2017107220-appb-000002
Figure PCTCN2017107220-appb-000003
所述聚乙二醇的共聚合率优选35～55wt％。
所述脂肪族二元醇优选乙二醇或1，4-丁二醇；当脂肪族二元醇优选乙二醇时，所述聚乙二醇的数均分子量优选4000～30000g/mol。
本发明所述聚酯中聚乙二醇的共聚合率高，聚酯切片的吸湿性优异，且所述聚酯成纤后纤维染色前后的吸湿率差的差值小。同时，聚酯的耐热性好，抗黄变性优良，应用价值高。
具体实施方式
本发明所述聚酯是以芳香族二元羧酸或其衍生物、脂肪族二元醇为主要单体，聚乙二醇为共聚合成分共聚所得到的聚醚酯，具有良好的耐热性及机械特性。
所述芳香族二元羧酸或其衍生物，具体地可以列举的有对苯二甲酸、间苯二甲酸、邻苯二甲酸、间苯二甲酸-5-磺酸钠、间苯二甲酸-5-磺酸锂、5-(四烷基)-间苯二甲酸磺酸磷化合物、4，4’-联苯二元羧酸、2，6-奈二甲酸等，但不限于以上物质，其中优选对苯二甲酸。
所述脂肪族二元醇，具体地可以列举的有乙二醇、1，3-丙二醇、1，4-丁二醇、己二醇、环己烷己二醇、二乙二醇、六亚甲基乙二醇、新戊二醇等，但不限于以上物质。尤其，乙二醇、丙二醇、1，4-丁二醇制造以及使用时取用性良好而优选。从耐热性以及机械特性的角度来看，更优选乙二醇；从结晶性的角度来看，更优选1，4-丁二醇。
本发明所述的聚酯，其共聚合成分聚乙二醇的数均分子量，可以在聚酯具有结晶性的范围内进行适当选择。本发明的聚酯中聚乙二醇的共聚合率为25～55wt％。当聚乙二醇的共聚合率小于25wt％时，聚酯的吐出性差；当聚乙二醇的共聚合率大于55wt％时，所得聚酯形成的纤维的物性下降。由于聚乙二醇的共聚合率在25～35wt％之间时所得聚酯的吐出性一般，因此为了获得更好吐出性的聚酯，本发明优选聚乙二醇的共聚合率为35～55wt％。
优选的范围根据聚酯的组成成分不同而不同。例如，在聚酯的组成成分脂肪族二元醇为乙二醇的场合下，聚酯分子量如果过低的话，由于聚合温度过高，使得聚 乙二醇降解严重，最终聚酯、甚至制成的纤维的吸湿率会下降。同时，当聚酯的构成成分脂肪族二元醇为1，4-丁二醇时，与上述使用乙二醇的场合相比，由于聚合温度低，聚乙二醇降解相对不是很严重，从而聚酯的吸湿性、甚至制成纤维后的吸湿性也能得到提高。
本发明所述脂肪族二元醇为乙二醇的场合，聚乙二醇的数均分子量优选4000～30000g/mol,聚乙二醇的共聚合率优选35～55wt％。聚乙二醇的数均分子量在4000g/mol以上的话，聚酯的吸湿性高，单独纺丝或复合纺丝，都能得到吸湿性优异的纤维。同时，能够抑制聚酯的结晶性的下降及外推熔融起始温度的降低，由于聚酯纺丝后断丝以及毛羽的发生变少，工程通过性良好，形成织物和编物等纤维构造体时染斑及毛羽的产生变少，品质优异。另一方面，聚乙二醇的数均分子量在30000g/mol以下的话，缩聚反应性高，未反应的聚乙二醇减少，能够抑制染色等热水处理时在热水中的溶出，热水处理后的吸湿性能够被维持。聚乙二醇的数均分子量优选25000g/mol以下，更优选为20000g/mol以下。
同时，聚乙二醇的共聚合率在35wt％以上的话，聚酯的吸湿性高，单独纺丝或复合纺丝都能得到吸湿性优异的纤维。另一方面，聚乙二醇的共聚合率在55wt％以下的话，聚酯纺丝后，断丝以及毛羽的发生变少，工程通过性良好，形成织物和编物等纤维构造体时染斑及毛羽的产生变少，品质优异。同时，能够抑制染色等热水处理时聚乙二醇的溶出，热水处理后能够维持纤维的吸湿性。
本发明所述脂肪族二元醇为1，4-丁二醇的场合，聚乙二醇的数均分子量优选2000～30000g/mol，聚乙二醇的共聚合率优选35～55wt％。聚乙二醇的数均分子量在2000g/mol以上的话，聚酯的吸湿性高，单独纺丝或复合纺丝都能得到吸湿性优异的纤维。同时，能够抑制聚酯的结晶性下降。同时，聚乙二醇的数均分子量在2000g/mol以上的话，能够抑制聚酯的结晶性的下降以及外推熔融起始温度的降低，由于延伸以及假捻工程中断丝以及毛羽的发生变少，工程通过性良好，形成织物和编物等纤维构造体时染斑及毛羽的产生变少，品质优异。另一方面，聚乙二醇的数均分子量在30000g/mol以下的话，缩聚反应性高，未反应的聚乙二醇减少，能够抑制染色等热水处理时在热水中的溶出，热水处理后的吸湿性能够维持。聚乙二醇的数均分子量优选27000g/mol以下，更优选25000g/mol以下，最优选20000g/mol以下。同时，聚乙二醇的共聚合率在35wt％以上的话，聚酯的吸湿性高，单独纺丝或复合纺丝都能得到吸湿性优异的纤维。另一方面，聚乙二醇的共聚合率在55wt％以下时，由于延伸以及假捻工程中断丝以及毛羽的发生变少，工程通过性良好，形成织物和编物等纤维构造体时染斑及毛羽的产生变少，品质优异。同时，能够抑制染色等热水处理时在热水中的溶出，热水处理后的吸湿性能够维持。
众所周知，聚酯中大量添加聚醚类化合物时，由于醚键受热氧化分解，导致聚酯形成纤维后吸湿性大幅度下降。故在聚酯的合成过程中，一般会添加受阻酚类抗氧化剂，但是，聚酯制成纤维后，在高温染色过程中，被氧化分解的醚键自由基进攻受阻酚类抗氧化剂酚羟基的对位，生成醌类黄色物质。同样的机理，与NO2作用后也会生成黄色物质，使得纤维氮氧监牢度不合格，影响了纤维的使用性能。当聚乙二醇的共聚率低于25wt％时，添加的受阻酚类抗氧剂量一般比较少，因而不会产生上述黄变问题；但是，当聚乙二醇的共聚率高于25wt％时，黄变问题就会比较严重。本发明使用如式1所示的半受阻酚类抗氧化剂，即使存在被热氧化分解后形成的醚键自由基，由于半受阻酚类抗氧化剂酚羟基邻位上是甲基，位阻效应比较小，醚键自由基将进攻半受阻酚类抗氧剂酚羟基的间位，将不会生成黄色醌类物质，
Figure PCTCN2017107220-appb-000004
其中，R1为由碳氢、氧、氮中的一种或者几种结合形成的基团；R2为由氢、碳氢、氧、氮中的一种或者几种结合形成的基团。
本发明所述半受阻酚类抗氧化剂，优选3,9-双[1,1-二甲基-2-[(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基]乙基]-2,4,8,10-四氧杂螺[5.5]十一烷，或者1，3，5-三(4-叔丁基-3-羟基-2，6-二甲基苄基)-1，3，5-三嗪-2，4，6-(1H，3H，5H)-三酮，添加量根据聚乙二醇的量而改变，最终聚酯中半受阻酚类抗氧化剂的含量优选1.0～8.0wt％。半受阻酚类抗氧化剂的含量太低的话，使得聚酯形成纤维后的抗氧化性能差，聚乙二醇氧化分解后聚酯纤维的吸湿性下降；半受阻酚类抗氧化剂的含量太高的话，由于抗氧剂自身的分解也会使得聚酯纤维发生黄变。
本发明中，所述聚酯为吸湿率
差(△MR)13.0wt％以上的聚醚酯化合物。本发明所述的吸湿率差(△MR)是指按照说明书中所记载的方法测定的值。该聚酯通过常规纺丝方法单独纺丝，或者与其他组分聚合物进行复合纺丝，均能得到吸湿性优异的纤维。
本发明中，所述聚酯通过常规单独或者复合纺丝的方法制得的纤维，在130℃热水处理后，与未热水处理相比，纤维色调L值的变化为6以下，优选4以下。另一方面，纤维经过氮氧监牢度测试后，色调黄变值△YI为10.0以下，优选8.0以下，更优选7.5以下。当△YI为7.5以下时，氮氧监牢度达到4～5级，△YI为7.5以上时，氮氧监牢度为4级。
在上述聚酯合成时，可以添加含钛元素或锑元素的化合物作为催化剂。由于含钛催化剂的催化活性高，容易促进副反应，影响最终聚酯纤维的色调稳定性，因此选用含钛催化剂时其添加量最好控制在以钛元素计相当于聚酯的10～150ppm的范围之内。以锑元素的化合物作为催化剂时，其添加量为以锑元素计相当于聚酯150～300ppm范围内。
在上述聚酯合成时，还可以添加各种各样的辅助改性剂。辅助改性剂，具体地可以列举的有其他类型的抗氧化、相溶剂、可塑剂、紫外线吸收剂、荧光增白剂、抗菌剂、成核剂、热稳定剂、带电防止剂、消光剂、消泡剂、染料、颜料、香料等，但不限于上述物质。上述辅助添加剂可以单独使用，也可以混合使用。
本发明的聚酯的外推熔融起始温度在180℃以上。本发明的聚酯的外推熔融起始温度，是指按照说明书中记载的方法算出的值。在观测到多个熔融峰的场合，从温度最低的融解峰开始算出。聚酯的外推熔融起始温度在180℃以上的话，聚酯形成纤维后，断丝以及毛羽的发生变少，工程通过性良好，形成织物和编物等纤维构造体时染斑及毛羽产生变少，品质优异。
本发明的聚酯，通过常规纺丝方法单独纺丝或与其他组分复合纺丝制得的纤维，及由其形成的假捻丝、纤维构造体的吸湿性优异。因此，可以用于要求舒适性及品质的用途。例如，一般衣料用途、运动衣料用途、寝具用途、室内装饰用途、资材用途等，但并不限于上述列举。
下面，通过具体实施例对本发明作详细地说明。同时，实施例中的各特性值通过以下的方法测试。
A.聚酯以及纤维的吸湿率差(△MR)
将聚酯以及纤维作为样品，先在60℃下热风干燥30分钟后，在温度20℃、湿度65％RH的ESPEC社制恒温恒湿机LHU-123内静置24小时，测定聚合物的重量(W1)；接着在温度30℃、湿度90％RH的恒温恒湿机内静置24小时，测定聚合物的重量为(W2)。然后，在105℃下热风干燥2小时，测定绝干后的聚合物重量为(W3)。根据下记公式用聚合物的重量W1、W3计算出从绝干状态到20℃、湿度65％RH氛围下静置24小时后的吸湿率MR1(％)，根据下记公式用聚合物的重量W2、W3计算出绝干状态到30℃、湿度90％RH氛围下静置24小时后的吸湿率MR2(％)，然后根据下记公式算出吸湿率差(△MR)。并且，1个样品测定5回，取平均值作为吸湿率差(△MR)，
MR1(％)＝{(W1-W3)/W3}×100，
MR2(％)＝{(W2-W3)/W3}×100，
吸湿率差(△MR)(％)＝MR2-MR1。
B.纤维的热水黄变性能
实施例所制得的聚酯，通过常规方法单独纺丝或与其他组分复合纺丝后形成的纤维，在130℃×20分钟的条件下进行热水处理，得到的样品用色差计(USTC-datacolor)进行L值测定为L2，热水处理前的L值测定为L1，L2-L1为热水处理黄变值。
C.纤维的黄变值测试
实施例所制得的聚酯，通过常规方法单独纺丝或与其他组分复合纺丝后形成的纤维作为测试样品，在密闭容器中放入NOx气体发生剂(85％磷酸及2％的亚硝酸水溶液)，然后将试样及蓝色标准染色布置于容器内，当蓝色标准布颜色褪为标准灰度板3号时，更换蓝色标准染色布，当颜色再次达到标准灰度板3号时，将试样取出，并清洗2次，晾干。通过Datacolor 650分光光度仪对黄变值进行测定。
D.聚乙二醇的共聚合率
聚乙二醇的共聚合率：(醚键中H的峰面积/醚键中H的个数*聚醚化合物的结构单元分子量)/[(醚键中H的峰面积/醚键中H的个数*聚醚化合物的结构单元分子量)+(含磺酸钠的间苯二甲酸中H的峰面积/3*含磺酸钠的间苯二甲酸形成的酯的分子量)+PTA中H的峰面积/4*PET的分子量+聚酯中EG单元结构的H的峰面积/4*EG单元结构的分子量]。
E.所含聚乙二醇的数均分子量(Mn)
用瓶子称取50mg试样，加入1mL氨水密封，温度120℃下加热3小时。冷却后，试样经粉碎后在120℃下再加热2小时。冷却后，添加蒸馏水1Ml、6M盐酸1.5mL，用5ML的容量瓶进行定容。远心分离(3500rpm×10分)后，用0.45μm的滤网进行过滤，得到的滤液进行GPC测试。该试样，用以下的条件进行GPC测试(Waters制Alliance2690)。分子量低于1800的与不纯物不能进行分离，除此之外求出数均分子量；
检出器：日本“東ソー”制造的RI-8020、感度128x
柱子：日本“東ソー”制造的TSKge1G3000PWXL I
溶剂：0.1M氯化钠水溶液
注入量：200μm
柱子温度：40℃
标准物质：聚乙二醇(“エーエムアル株式会社”制Mn106～101000g/mol)。
F.半受阻酚类抗氧化剂、受阻酚类抗氧化剂的含有量
前处理：取聚酯8g，用溶剂甲苯150ml进行环流处理35分钟；处理后冷却至 100度，然后倒入远心分离管；接下来进行远心分离，取上层液体用0.45μm的过滤器进行过滤；然后用甲醇进行稀释，远心分离取上层液体；最后添加内标，用0.45μm的过滤器进行过滤后用HPLC进行测定。
HPLC测定：流动相A/B：甲醇/水(12％)；流速：1.3ml/min；柱温：40度；紫外线波长：284nm；时间：15min。
G.外推熔融起始温度
取芯成分、鞘成分的聚合物以及通过实施例得到的纤维作为试样，采用TA Instruments社制的Q2000型差示扫描量热仪(DSC)，测定外推熔融起始温度。首先，在氮气氛围下将5mg的试样以50℃/分的升温速度从0℃升温至280℃，在280℃的状态下保持5分钟消除热历史。然后，从280℃骤冷至0℃，再次以3℃/分的速度从0℃升温至280℃，温度变调幅度为±1℃，温度变调周期60秒后进行升温，进行TMDSC的测定。根据JISK7121：1987(塑料的转变温度的测定方法)9.1的标准，根据第2回升温过程中观测到的融解峰算出外推熔融起始温度。1个样品测定3回，其平均值作为外推熔融起始温度。并且，观测到多个融解峰的场合，根据最低温侧的融解峰算出外推熔融起始温度。
实施例1
将对苯二甲酸10.9Kg与乙二醇4.7Kg投入酯化釜中，搅拌升温至230℃进行酯化反应后移至缩聚釜，加入相对于最终聚酯总量为35wt％的聚乙二醇8300(数均分子量为8300g/mol的聚乙二醇，简写PEG8300)，以锑元素计相对于最终聚酯总量含量为250ppm的三氧化二锑作为聚合催化剂，以及添加相对于最终聚酯总量的稳定剂磷酸三甲酯250ppm，5分钟后开始减压升温，达到最终温度285℃、最终压力后，向反应体系添加相对于最终聚酯总量为1.0wt％的半受阻酚类抗氧化剂1，3，5-三(4-叔丁基-3-羟基-2，6-二甲基苄基)-1，3，5-三嗪-2，4，6-(1H，3H，5H)-三酮(CN1790)，搅拌10分钟后向反应体系里导入氮气回至常压，停止缩聚反应得到共聚酯。
将上述所得到的聚酯切片进行熔融纺丝，纺丝速度为3Km/min得到预取向丝。然后将得到的预取向丝经过假捻加工，加工条件：第一热箱温度为180℃，第二热箱的温度为常温，延伸倍率为1.7，制得高吸湿性聚酯纤维。聚酯以及纤维的具体物性见表1。
实施例2
PEG8300的添加量为40wt％，半受阻酚类抗氧化剂CN1790的添加量为1.1wt％。其余同实施例1。具体见表1。
实施例3
PEG11000(数均分子量11000g/mol)的添加量为35wt％，半受阻酚类抗氧化剂CN1790的添加量为1.0wt％。其余同实施例1。具体见表1。
实施例4
PEG20000(数均分子量20000g/mol)的添加量为35wt％，半受阻酚类抗氧化剂CN1790的添加量为1.0wt％。其余同实施例1。具体见表1。
实施例5
PEG30000(数均分子量30000g/mol)的添加量为35wt％，半受阻酚类抗氧化剂CN1790的添加量为1.0wt％。其余同实施例1。具体见表1。
实施例6
PEG8300的添加量为35wt％，半受阻酚类抗氧化剂CN1790的添加量为3.0wt％。其余同实施例1。具体见表1。
实施例7
PEG8300的添加量为35wt％，半受阻酚类抗氧化剂CN1790的添加量为5.0wt％。其余同实施例1。具体见表1。
实施例8
PEG8300的添加量为35wt％，半受阻酚类抗氧化剂半受阻酚类抗氧化剂3,9-双[1,1-二甲基-2-[(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基]乙基]-2,4,8,10-四氧杂螺[5.5]十一烷(AO80)的添加量为1.6wt％。其余同实施例1。具体见表1。
实施例9
PEG8300的添加量为35wt％，半受阻酚类抗氧化剂AO80的添加量为4.7wt％。其余同实施例1。具体见表1。
实施例10
PEG8300的添加量为35wt％，半受阻酚类抗氧化剂AO80的添加量为8.0wt％。其余同实施例1。具体见表1。
实施例11
PEG8300的添加量为30wt％，半受阻酚类抗氧化剂CN1790的添加量为1.0wt％。其余同实施例1。具体见表1。
实施例12
PEG8300的添加量为27wt％，半受阻酚类抗氧化剂CN1790的添加量为10.0wt％。其余同实施例1。具体见表1。
实施例13
将对苯二甲酸10.9Kg与1，4-丁二醇11.8Kg投入酯化釜中，加入相对于最终聚酯总量的钛酸四丁酯催化剂450ppm，搅拌升温至230℃进行酯化反应后移至缩聚釜，加入相对于最终聚酯总量为45wt％的聚乙二醇3400(数均分子量为3400g/mol的聚乙二醇，简写PEG3400)，添加相对于最终聚酯总量的钛酸四丁酯催化剂900ppm，以及添加相对于最终聚酯总量的稳定剂磷酸三甲酯250ppm，5分钟后开始减压升温，达到最终温度250℃、最终压力后，向反应体系添加相对于最终聚酯总量为1.3wt％的半受阻酚类抗氧化剂1，3，5-三(4-叔丁基-3-羟基-2，6-二甲基苄基)-1，3，5-三嗪-2，4，6-(1H，3H，5H)-三酮(CN1790)，搅拌10分钟后向反应体系里导入氮气回至常压，停止缩聚反应得到共聚酯。
将上述所得到的聚酯切片进行熔融纺丝，纺丝速度为3Km/min得到预取向丝。然后将得到的预取向丝经过假捻加工，加工条件：第一热箱温度为180℃，第二热箱的温度为常温，延伸倍率为1.7，制得高吸湿性聚酯纤维。聚酯以及纤维的具体物性见表2
实施例14
PEG3400的添加量为55wt％，半受阻酚类抗氧化剂CN1790的添加量为1.4wt％。其余同实施例13。具体见表2。
实施例15
PEG3400的添加量为58wt％，半受阻酚类抗氧化剂CN1790的添加量为1.8wt％。其余同实施例13。具体见表2。
实施例16
PEG11000的添加量为55wt％，抗氧化剂CN1790的添加量为1.4wt％。其余同实施例13。具体见表2。
实施例17
PEG20000的添加量为55wt％,半受阻酚类抗氧化剂CN1790的添加量为1.4wt％。 其余同实施例13。具体见表2。
实施例18
PEG3400的添加量为55wt％，半受阻酚类抗氧化剂CN1790的添加量为4.2wt％，其余同实施例13。具体见表2。
实施例19
PEG3400的添加量为55wt％，半受阻酚类抗氧化剂CN1790的添加量为8.0wt％，其余同实施例13。具体见表2。
实施例20
PEG3400的添加量为55wt％，半受阻酚类抗氧化剂3,9-双[1,1-二甲基-2-[(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基]乙基]-2,4,8,10-四氧杂螺[5.5]十一烷(AO80)的添加量为2.2wt％。其余同实施例13。具体见表2。
实施例21
PEG3400的添加量为55wt％，半受阻酚类抗氧化剂AO80的添加量为6.6wt％。其余同实施例13。具体见表2。
实施例22
PEG3400的添加量为55wt％，半受阻酚类抗氧化剂AO-80的添加量为8.0wt％。其余同实施例13。具体见表2。
实施例23
PEG3400的添加量为50wt％，半受阻酚类抗氧化剂CN1790的添加量为10.0wt％。其余同实施例13。具体见表2。
实施例24
将对苯二甲酸10.9Kg与乙二醇4.7Kg投入酯化釜中，搅拌升温至230℃进行酯化反应后移至缩聚釜，加入相对于最终聚酯总量为35wt％的聚乙二醇8300(数均分子量为8300g/mol的聚乙二醇，简写PEG8300)，以锑元素计相对于最终聚酯总量含量为250ppm的三氧化二锑作为聚合催化剂，以及添加相对于最终聚酯总量的稳定剂磷酸三甲酯250ppm，5分钟后开始减压升温，达到最终温度285℃、最终压力后，向反应体系添加相对于最终聚酯总量为1.0wt％的半受阻酚类抗氧化剂1，3，5-三(4-叔丁基-3-羟基-2，6-二甲基苄基)-1，3，5-三嗪-2，4，6-(1H，3H，5H)-三酮(CN1790)，搅拌10分钟后向反应体系里导入氮气回至常压，停止缩聚反应得到共聚酯。
将上述聚酯作为岛成分，以聚对苯二甲酸乙二醇酯(IV＝0.66)作为海成分，分别在150℃条件下真空干燥12小时后，按岛成分20wt％、海成分80wt％的配比向螺杆型复合纺丝机内供给分别进行熔融，在纺丝温度285℃、吐出量为36g/分下用海岛型复合用纺丝口金(一个吐出孔有24个岛)，纺出丝条。纺出的丝条在风温20℃、风速20m/分的冷风下进行冷却，通过给油装置进行给油收束，2500m/分回转的第1段罗拉进行拉伸，通过与第一段罗拉同样的回转速度的第2段罗拉卷取，得到144dtex-36f的未延伸丝。然后，采用延伸假捻机(加捻部：摩擦磁盘式、加热器部：接触式)，将得到的未延伸丝在加热器温度170℃、倍率1.7倍的条件下进行延伸假捻，得到84dtex-36f的假捻丝。
得到的纤维的纤维特性、布帛特性以及工程通过性的评价结果如表3所示。假捻时的断丝回数为0回，工程通过性极其良好。同时，热水处理后吸湿性基本没有降低，热水处理后吸湿性也良好。并且，但是均染性、品质都达到合格水平。具体见表3。
实施例25
半受阻酚类抗氧化剂CN1790的添加量为3.0wt％，其余同实施例24。具体见表3。
实施例26
半受阻酚类抗氧化剂CN1790的添加量为5.0wt％，其余同实施例24。具体见表3。
实施例27
PEG8300的添加量为45wt％，半受阻酚类抗氧化剂CN1790的添加量为5.0wt％，其余同实施例24。具体见表3。
实施例28
PEG8300的添加量为55wt％，半受阻酚类抗氧化剂CN1790的添加量为5.0wt％，其余同实施例24。具体见表3。
实施例29
半受阻酚类抗氧化剂AO80的添加量为1.6wt％，其余同实施例24。具体见表3。实施例30
半受阻酚类抗氧化剂AO80的添加量为4.7wt％，其余同实施例24。具体见表3。实施例31
半受阻酚类抗氧化剂AO80的添加量为8.0wt％，其余同实施例24。具体见表3。实施例32
半受阻酚类抗氧化剂CN1790的添加量为2.0wt％，其余同实施例24。具体见表3。
实施例33
半受阻酚类抗氧化剂AO80的添加量为4.0wt％，其余同实施例24。具体见表3。实施例34
半受阻酚类抗氧化剂AO80的添加量为6.0wt％，其余同实施例24。具体见表3。实施例35
半受阻酚类抗氧化剂CN1790的添加量为9.0wt％，其余同实施例24。具体见表3。
实施例36
半受阻酚类抗氧化剂CN1790的添加量为0.9wt％，其余同实施例24。具体见表3。
实施例37
将对苯二甲酸10.9Kg与1，4-丁二醇11.8Kg投入酯化釜中，加入相对于最终聚酯总量的钛酸四丁酯催化剂450ppm，搅拌升温至230℃进行酯化反应后移至缩聚釜，加入相对于最终聚酯总量为50wt％的聚乙二醇8300(数均分子量为8300g/mol的聚乙二醇，简写PEG8300)，添加相对于最终聚酯总量的钛酸四丁酯催化剂900ppm，以及添加相对于最终聚酯总量的稳定剂磷酸三甲酯250ppm，5分钟后开始减压升温，达到最终温度250℃、最终压力后，向反应体系添加相对于最终聚酯总量为1.3wt％的半受阻酚类抗氧化剂1，3，5-三(4-叔丁基-3-羟基-2，6-二甲基苄基)-1，3，5-三嗪-2，4，6-(1H，3H，5H)-三酮(CN1790)，搅拌10分钟后向反应体系里导入氮气回至常压，停止缩聚反应得到共聚酯。其余同实施例24。具体见表4。
实施例38
半受阻酚类抗氧化剂CN1790的添加量为2.4wt％，其余同实施例37。具体见表4。
实施例39
半受阻酚类抗氧化剂CN1790的添加量为4.2wt％，其余同实施例37。具体见表4。
实施例40
半受阻酚类抗氧化剂CN1790的添加量为8.0wt％，其余同实施例37。具体见表4。
实施例41
半受阻酚类抗氧化剂AO80的添加量为2.2wt％，其余同实施例37。具体见表4。实施例42
半受阻酚类抗氧化剂AO80的添加量为6.6wt％，其余同实施例37。具体见表4。实施例43
PEG8300的添加量为45wt％,半受阻酚类抗氧化剂AO80的添加量为6.6wt％，其余同实施例37。具体见表4。
实施例44
PEG8300的添加量为55wt％,半受阻酚类抗氧化剂AO80的添加量为6.6wt％，其余同实施例37。具体见表4。
实施例45
PEG8300的添加量为50wt％,半受阻酚类抗氧化剂AO80的添加量为8.0wt％，其余同实施例37。具体见表4。
实施例46
PEG8300的添加量为50wt％,半受阻酚类抗氧化剂CN1790的添加量为2.0wt％，其余同实施例37。具体见表4。
实施例47
PEG8300的添加量为50wt％,半受阻酚类抗氧化剂CN1790的添加量为3.0wt％，其余同实施例37。具体见表4。
实施例48
PEG8300的添加量为50wt％,半受阻酚类抗氧化剂CN1790的添加量为5.0wt％，其余同实施例37。具体见表4。
实施例49
PEG8300的添加量为50wt％,半受阻酚类抗氧化剂AO80的添加量为4.0wt％，其余同实施例37。具体见表4。
实施例50
PEG8300的添加量为50wt％,半受阻酚类抗氧化剂AO80的添加量为6.0wt％，其余同实施例37。具体见表4。
实施例51
PEG8300的添加量为50wt％,半受阻酚类抗氧化剂CN1790的添加量为9.0wt％，其余同实施例37。具体见表4。
比较例1
PEG8300的添加量为12wt％，半受阻酚类抗氧化剂CN1790的添加量为1.0wt％，其余同实施例1。具体见表5。由于PEG的添加量比较少，达不到高吸湿性效果。
比较例2
PEG8300的添加量为20wt％，半受阻酚类抗氧化剂CN1790的添加量为1.0wt％，其余同实施例1。具体见表5。由于PEG的添加量比较少，达不到高吸湿性效果。
比较例3
PEG100000(数均分子量100000g/mol)的添加量为30wt％，半受阻酚类抗氧化剂CN1790的添加量为2.0wt％，其余同实施例1。具体见表5。由于添加了超高分子量PEG，发生吐出涨大，不易吐出。
比较例4
PEG3400的添加量为12wt％，半受阻酚类抗氧化剂CN1790的添加量为0.8wt％，其余同实施例13。具体见表5。由于PEG的添加量比较少，达不到高吸湿性效果。
比较例5
PEG3400的添加量为70wt％，半受阻酚类抗氧化剂CN1790的添加量为4.6wt％，其余同实施例13。具体见表5。PEG3400的添加量过高，导致最终聚酯的外推熔融起始温度偏低，聚酯形成纤维后，断丝以及毛羽的发生变多，工程通过性变差，形成织物和编物等纤维构造体时染斑及毛羽产生变多，品质不佳。
比较例6
PEG600(数均分子量600g/mol)的添加量为50wt％，半受阻酚类抗氧化剂CN1790的添加量为3.3wt％，其余同实施例13。具体见表5。PEG的分子量偏低，聚合过程中大量飞散，即使大量添加，所得聚酯的吸湿性差。
比较例7
PEG100000的添加量为50wt％，半受阻酚类抗氧化剂CN1790的添加量为3.3wt％，其余同实施例13。具体见表5。由于添加了超高分子量PEG，发生吐出涨大，不易吐出。
比较例8
PEG3400的添加量为20wt％，半受阻酚类抗氧化剂CN1790的添加量为1.0wt％，其余同实施例13。具体见表5。由于PEG的添加量比较少，达不到高吸湿性效果。
比较例9
PEG8300的添加量为20wt％，受阻酚类抗氧化剂……(IR1010)的添加量为0.5wt％，其余同实施例1。具体见表5。与受阻酚类抗氧化剂相比，受阻酚类抗氧化剂容易导致聚酯黄变。在PEG添加量少的情况下，虽然只需要添加少量的受阻酚类抗氧化剂四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯IR1010，聚酯黄变指数也在可接受范围之内，但是聚酯的抗氧化效果降低，染色前后聚酯纤维的吸湿率差的差值大，说明染色后聚酯纤维的吸湿性下降明显。
比较例10
PEG8300的添加量为50wt％，受阻酚类抗氧化剂IR1010的添加量为3.0wt％，其余同实施例1。具体见表5。受阻酚类抗氧化剂大量添加的场合，虽然抗氧化效果优异，但是纤维容易发生黄变。
比较例11
PEG8300的添加量为50wt％，受阻酚类抗氧化剂IR1010的添加量为0.5wt％，其余同实施例1。具体见表5。受阻酚类抗氧化剂少量添加的场合，虽然可以抑制纤维的黄变，但是抗氧化效果降低。
比较例12
PEG3400的添加量为20wt％，受阻酚类抗氧化剂IR1010的添加量为0.5wt％，其余同实施例13。具体见表5。与受阻酚类抗氧化剂相比，受阻酚类抗氧化剂容易导致聚酯黄变。在PEG添加量少的情况下，虽然只需要添加少量的受阻酚类抗氧化剂IR1010，聚酯黄变指数也在可接受范围之内，但是聚酯的抗氧化效果降低，染色前后聚酯纤维的吸湿率差的差值大，说明染色后聚酯纤维的吸湿性下降明显。
比较例13
PEG3400的添加量为50wt％，受阻酚类抗氧化剂IR1010的添加量为3.0wt％，其余同实施例13。具体见表5。受阻酚类抗氧化剂大量添加的场合，虽然抗氧化效果优异，但是纤维容易发生黄变。
比较例14
PEG3400的添加量为50wt％，受阻酚类抗氧化剂IR1010的添加量为0.5wt％，其余同实施例13。具体见表5。受阻酚类抗氧化剂少量添加的场合，虽然可以抑制纤维的黄变，但是抗氧化效果降低。
实施例15
PEG8300的添加量为22wt％,半受阻酚类抗氧化剂CN1790的添加量为1.0wt％,其余同实施例1。具体见表5。PEG8300的添加量不合适，导致吐出性变差。
实施例16
PEG8300的添加量为25wt％,半受阻酚类抗氧化剂CN1790的添加量为1.0wt％,其余同实施例1。具体见表5。PEG8300的添加量不合适，导致吐出性变差。
比较例17
PEG8300的添加量为50wt％，受阻酚类抗氧化剂IR1010的添加量为3.0wt％,其余同实施例24。具体见表6。复合纺丝的场合，受阻酚类抗氧化剂大量添加时，虽然抗氧化效果优异，但是纤维容易发生黄变。
比较例18
PEG8300的添加量为50wt％，受阻酚类抗氧化剂IR1010的添加量为0.8wt％,其余同实施例24。具体见表6。复合纺丝的场合，受阻酚类抗氧化剂少量添加时，虽然可以抑制纤维的黄变，但是抗氧化效果降低。
比较例19
PEG8300的添加量为50wt％，不添加抗氧化剂，其余同实施例24。具体见表6。由于没有添加抗氧化剂，纤维不会发生黄变，但是不具有抗氧化效果。
Figure PCTCN2017107220-appb-000005
Figure PCTCN2017107220-appb-000006
Figure PCTCN2017107220-appb-000007
Figure PCTCN2017107220-appb-000008
Figure PCTCN2017107220-appb-000009
Figure PCTCN2017107220-appb-000010

Claims (6)

  1. 一种聚酯，其特征在于：所述聚酯是以芳香族二元羧酸或其衍生物与脂肪族二元醇为主要构成成分、聚乙二醇为共聚合成分形成的聚合物，其中聚乙二醇的数均分子量为2000～30000g/mol，共聚合率为25～55wt％，并且聚酯中含有如式1所示的半受阻酚类抗氧化剂，
    Figure PCTCN2017107220-appb-100001
    其中，R1为由碳氢、氧、氮中的一种或者几种结合形成的基团；R2为由氢、碳氢、氧、氮中的一种或者几种结合形成的基团。
  2. 根据权利要求1所述的聚酯，其特征在于：所述半受阻酚类抗氧化剂的含有量占聚酯总重量的1.0wt％～8.0wt％。
  3. 根据权利要求1或2所述的聚酯，其特征在于：所述半受阻酚类抗氧化剂为如式2所示的抗氧化剂3,9-双[1,1-二甲基-2-[(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基]乙基]-2,4,8,10-四氧杂螺[5.5]十一烷，或者如式3所示的1，3，5-三(4-叔丁基-3-羟基-2，6-二甲基苄基)-1，3，5-三嗪-2，4，6-(1H，3H，5H)-三酮，
    Figure PCTCN2017107220-appb-100002
  4. 根据权利要求1或2所述的聚酯，其特征在于：所述聚乙二醇的共聚合率为35～55wt％。
  5. 根据权利要求4所述的聚酯，其特征在于：所述脂肪族二元醇为乙二醇，所述聚乙二醇的数均分子量为4000～30000g/mol。
  6. 根据权利要求4所述的聚酯，其特征在于：所述脂肪族二元醇为1，4-丁二醇。
PCT/CN2017/107220 2016-10-25 2017-10-23 一种聚酯 WO2018077126A1 (zh)

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