CN104619897A - Hygroscopic polyester fiber and manufacturing method thereof - Google Patents
Hygroscopic polyester fiber and manufacturing method thereof Download PDFInfo
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- CN104619897A CN104619897A CN201380045855.XA CN201380045855A CN104619897A CN 104619897 A CN104619897 A CN 104619897A CN 201380045855 A CN201380045855 A CN 201380045855A CN 104619897 A CN104619897 A CN 104619897A
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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
- 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
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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
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
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Abstract
Disclosed are a hygroscopic polyester fiber and manufacturing method thereof, the hygroscopic polyester fiber containing a poly-N-ethenyl lactam hygroscopic component and a phosphorus thermal stabilizer, the poly-N-ethenyl lactam is 3-15% by weight of the polyester fiber, and has a dispersion diameter of less than 200nm; the content of the element P in the phosphorus thermal stabilizer is 50-500ppm by weight of the polyester fiber. When the poly-N-ethenyl lactam is blended with the polyester, a double-screw extruder having an L/D of greater than 45 is used to conduct the blending and spinning at a low temperature to obtain the polyester fiber; the phosphorus thermal stabilizer is added during blending or melt-spinning. The resulting polyester fiber has good and durable hygroscopic property, good fiber color and excellent lightfastness, and can be used for underwear or sport clothing.
Description
Moisture-absorption polyester fiber and preparation method thereof
The invention relates to a hygroscopic polyester fiber and a preparation method thereof. Specifically, a moisture-absorbing polyester fiber which can be used as a material for clothing such as underwear and sportswear can be obtained by adding a moisture-absorbing component and a phosphorus-based heat stabilizer to a polyester. Background
Polyester fibers are typical thermoplastic synthetic fibers, and since their birth, they are widely used in clothing and industry because of their excellent mechanical strength, chemical resistance, heat resistance, and the like.
However, polyester fibers have a very low moisture absorption and desorption property, cannot discharge sweat in a timely manner, and have a sticky feeling when worn in direct contact with the skin or in close proximity to the skin, thereby limiting the development of polyester fibers for underwear.
Examples of methods for improving the moisture absorption of polyester fibers include copolymerizing a moisture absorbing component with a polyester and adding a compound having moisture absorption. For example, a method of copolymerizing a diol having a hydroxyl alkanyl diol in a side chain during a polyester reaction, or a method of copolymerizing a dicarboxylic acid containing a metal sulfonate. However, the hygroscopic polyester fiber obtained by copolymerization has a problem of low strength and weather resistance.
In addition to the above-described method of imparting moisture absorption to the polyester as a fiber raw material to make the fiber have moisture absorption, a moisture-absorbing compound may be chemically attached to the polyester fiber. For example, acrylic acid or methacrylic acid is grafted to the polyester fiber in the fabric in the post-processing process, and the carboxyl group is replaced by alkali metal, thereby improving the hygroscopicity of the polyester fiber. However, hygroscopic compounds adhere to the surface of the fiber, and thus there are problems such as a decrease in strength, poor hand feeling, and poor light resistance during use.
Jp-a 2-99612 discloses a core-sheath type composite fiber having a core portion made of a hygroscopic resin having a moisture absorption rate of 10% or more and a sheath portion made of a general polyester. When the fiber obtained in this way is subjected to heat treatment such as refining or dyeing, the hygroscopic resin in the core portion tends to absorb water and swell, so that cracks are formed on the fiber surface, and the hygroscopic resin has high solubility in water and flows out, so that the hygroscopicity is lost.
A technique of adding polyvinyl pyrrolidone to nylon to improve moisture absorption ability of nylon fibers is disclosed in japanese patent No. hei 8-311326. The addition of polyvinyl pyrrolidone does not have a negative effect on the performance of nylon fibers, but a technique of adding polyvinyl pyrrolidone to polyester and fiberizing the same is not known. Disclosure of Invention
The invention aims to provide a hygroscopic polyester fiber and a preparation method thereof, wherein a hygroscopic substance poly N-vinyl lactam is added into polyester to be dispersed in the polyester, thereby improving the hygroscopicity of the polyester fiber. In addition, a phosphorus-based heat stabilizer is added to the fiber in order to obtain a fiber having excellent color and excellent light fastness.
The technical solution of the invention is as follows:
a hygroscopic polyester fiber contains polyester, poly N-vinyl lactam hygroscopic components and phosphorus heat stabilizer, wherein the poly N-vinyl lactam accounts for 3-15 wt% of the weight of the polyester fiber, and the dispersion diameter is less than 200 nm; the phosphorus-based heat stabilizer is present in an amount of 50-500 ppm in terms of P element based on the weight of the polyester fiber.
In the polyester fiber of the present invention, the content of poly-N-vinyl lactam is 3 to 15wt% relative to the weight of the polyester fiber. When the poly-N-vinyllactam content in the polyester fiber is less than 3wt%, the fiber does not have sufficient hygroscopicity and is poor in practical applicability; when the content of poly-N-vinyllactam in the polyester fiber exceeds 15% by weight, the fiber has a sticky feeling, is uncomfortable to touch, and the physical properties of the fiber are deteriorated. In order to obtain more desirable moisture absorption characteristics for the polyester fiber, the content of poly-N-vinyl lactam is preferably 5 to 12 wt%.
The average dispersion diameter of the poly-N-vinyllactam in the polyester fiber of the present invention is preferably 200nm or less, more preferably 150nm or less. The poly-N-vinyl lactam with the average dispersion diameter of less than 200nm can be well complexed with the polyester fiber, thereby inhibiting the dissolution of the poly-N-vinyl lactam, preventing the reduction of the hygroscopicity of the polyester fiber and improving the moisture absorption durability of the polyester fiber.
The poly-N-vinyl lactam used in the present invention may be, for example, a polymer of N-vinyl lactam such as N-vinyl-2-pyrrolidon, N-vinyl-2-piperidone, or N-vinyl caprolactam. In the present invention, a polymer of N-vinyl-2-pyrrolidone, i.e., polyvinyl-pyrrolidone (PVP), is preferably used as the poly-N-vinyl lactam in terms of small steric hindrance, easy adsorption, and release of water molecules.
In the invention, polyvinyl pyrrolidone with a K value of 15-90 is preferably used. More preferably, the polyvinyl-pyrrolidone with the K value of 20-70 is used. If the K value of the polyvinyl pyrrolidone is too low, the complexing ability of the polyvinyl pyrrolidone and the polyester is not strong, and the polyvinyl pyrrolidone is easily dissolved out in the water cooling process after extrusion, so that the fiber cannot obtain good hygroscopicity. On the other hand, if the K value is too high, the viscosity of the polyester system increases greatly, the kneading and discharging are poor, and the granulation is difficult, resulting in a low production efficiency.
The polyester fiber of the present invention further contains a phosphorus heat stabilizer in an amount of 50 to 500ppm in terms of P element based on the weight of the polyester fiber. In the invention, by adding the phosphorus heat stabilizer, the polyester can be inhibited from thermal degradation and hydrolysis when being blended with the moisture absorption component, the color tone of the obtained polyester fiber is improved, and the light fastness of the polyester fiber is improved.
The phosphorus-based heat stabilizer may be a phosphoric acid, a phosphorous acid, a phosphonic acid, a phosphoric ester, or the like. Specific examples thereof include phosphoric acid, trimethyl phosphate, triethyl phosphate, trisphenol phosphate, phosphorous acid, trimethyl phosphite, methyl phosphoric acid, phenol phosphoric acid, diphenyl phosphoric acid, methyl phosphate, ethyl phenol phosphate, phenol aldehyde diphenyl phosphate, ethyl phosphorylacetate, distearyl pentaerythritol diphosphate, bis (2, 4, 6-tri-t-butylphenyl) pentaerythritol diphosphate, resorcinol bis (di (pentaerythritol)) phosphate, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphate and bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphate.
Acid ester-based compound:
wherein Ri, R2Each independently an aromatic hydrocarbon group which may have a substituent. The aromatic hydrocarbon group is preferably a C6-C10 aromatic hydrocarbon group, which may be, for example, C1-C6 hydrocarbon group, amino group, hydroxyl group, and sulfo group. The R n may be, for example, a phenyl group having an alkyl substituent having 1 to 5 carbon atoms in the meta-position, a p-alkyl phenyl group, an aromatic hydrocarbon group which may be substituted with an amino group, an aromatic hydrocarbon group which may be substituted with a sulfo group, or the like. In the present invention, Ri is preferably one of the groups of formula 2-4 as follows:
the diphosphonate ester compound represented by the above formula 1 is preferably used as a stabilizer because it has a higher effect of improving the color tone of the polyester fiber. Bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate or bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphate among the diphosphate ester compounds represented by the above formula 1 is most preferable because it has a particularly excellent effect of improving the color tone of polyester fibers when used as a stabilizer.
The polyester used in the present invention is not particularly limited, and may be, for example, an aliphatic polyester or an aromatic polyester. Generally, it is composed mainly of a dibasic acid repeating unit and a glycol repeating unit.
The diol repeating units may specifically be one or more of an aliphatic diol or an aromatic diol, such as ethylene glycol, propylene glycol, butylene glycol and isomers thereof, pentane glycol and isomers thereof, a C6-C20 linear or branched aliphatic diol and isomers thereof, a bisphenol a and ethylene oxide-alkyl addition product, polyethylene glycol, polypropylene glycol, polybutylene glycol, cyclobutanediol, cyclopentanediol, cyclohexane diol, benzene dimethanol, naphthalene dimethanol, and the like.
The diacid repeat unit may be a C8-C18 aromatic diacid, such as malonic acid, succinic acid, glutaric acid, adipic acid, C7-C20 alicyclic diacid and isomers thereof, terephthalic acid and esterified derivatives thereof, isophthalic acid and esterified derivatives thereof, other diacid containing a benzene ring, naphthalene diacid or derivatives thereof, or the like.
As the polyester used in the present invention, polyester having a melting point of 200-240 ℃, i.e., polyester having a melting point Tm of 200 ℃ or more and 240 ℃ or less is preferable. Poly-N-vinyl lactam has poor heat resistance at high temperature, and the color tone of the fiber obtained by blending with polyester is easy to turn yellow. Therefore, in order to obtain a polyester fiber having good moisture absorption and excellent color tone, it is necessary to perform processing at as low a temperature as possible. So that this effect can be achieved by selecting a polyester having a low melting point.
The polyester having a melting point of 200-240 ℃ is preferably polyethylene terephthalate-based polyester, polypropylene terephthalate-based polyester, or polybutylene terephthalate-based polyester.
More preferred are polyethylene terephthalate-based polyesters, polypropylene terephthalate-based polyesters, and polybutylene terephthalate-based polyesters which further contain a diol copolymerization unit and/or a diacid copolymerization unit.
The copolymerized diol repeating unit can be aliphatic diol or aromatic diol, preferably one or more of propylene glycol, butylene glycol, bisphenol A and ethylene oxide alkyl addition product.
The copolymerized diacid repeat units can be aliphatic diacids, aromatic diacids, or derivatives thereof. The derivatives may be methyl, ethyl, propyl, etc. of the above dibasic acids, with methyl esters of the dibasic acids being preferred. The aliphatic dibasic acid is preferably a saturated aliphatic dibasic acid with 3-20 carbon atoms, and most preferably one or more of malonic acid, succinic acid, glutaric acid, adipic acid and azelaic acid; the aromatic dibasic acid is preferably isophthalic acid or naphthalenedicarboxylic acid. The copolymerized diacid repeat units of the present invention are most preferably isophthalic acid or isophthalic acid sulfonate units.
Most preferred are polyethylene terephthalate-based polyesters, polypropylene terephthalate-based polyesters, and polybutylene terephthalate-based polyesters which further contain a sulfonate copolymerized unit and/or a polyether copolymerized repeating unit. The sulfonate component of the copolymerization can be one or more of 5-sodium sulfoisophthalate, 5-lithium sulfoisophthalate, 5-calcium sulfoisophthalate, 5-sodium sulfoisophthalate, 5-lithium sulfoisophthalate and 5-calcium sulfoisophthalate.
The copolymerized polyether component can be one or more of polyethylene glycol, polypropylene glycol and polybutylene glycol. The polyethylene terephthalate polyester, polypropylene terephthalate polyester, or polybutylene terephthalate polyester may further contain a polyfunctional copolymerized repeating unit such as trimesic acid, pyromellitic acid, glycerol, or pentaerythritol, without impairing the effect of the present invention.
The polyester can be produced by a polymerization method generally used in industry, that is, first, esterification or transesterification is carried out to obtain a polyester compound having a low molecular weight, and then, further, polycondensation is carried out at a high temperature under a high vacuum to obtain a polymer. A catalyst may be added in the esterification or transesterification stage, and the catalyst is a compound containing a metal element such as sodium, lithium, magnesium, calcium, manganese, titanium, zinc, cobalt, or tin, preferably an acetate containing these metal elements, and most preferably a titanate-based compound.
The invention also relates to a preparation method of the polyester fiber, in the method, polyester and poly N-vinyl lactam are blended on a biaxial extruder with the length-diameter ratio L/D of more than 45, wherein the addition amount of the poly N-vinyl lactam accounts for 3-15 wt% of the weight of the polyester fiber; carrying out melt spinning on the obtained blend to obtain nascent fiber, and further stretching the nascent fiber to obtain polyester fiber; a phosphorus-based heat stabilizer is added in the blending stage or the melt spinning stage in an amount of 50 ppm-500 ppm based on the weight of the polyester fiber.
The invention adopts a biaxial extruder with L/D of more than 45 for mixing, can improve the dispersibility of the poly-N-vinyl lactam in the polyester, and lead the dispersion diameter to reach less than 200nm, thereby improving the spinning property of the blend. If the L/D is less than 45, the dispersion diameter of the poly-N-vinyllactam will be increased, and the subsequent spinning will frequently cause yarn breakage and poor fiber properties.
On the other hand, since most of poly-N-vinyl lactams have a glass transition temperature in the vicinity of 170 ℃, the mixing and spinning temperatures must be set above this temperature to give good flowability to the poly-N-vinyl lactam. Therefore, in the present invention, it is preferable to use a polyester having a melting point of 200-240 ℃, which can be blended with poly-N-vinyllactam at a lower temperature, to control the melting point temperature to be in the range of 10-20 ℃ higher than the melting point temperature of the polyester during kneading, and to control the temperature of the kneading section to be 180-230 ℃. In addition, the poly-N-vinyl lactam easily absorbs water and is sticky in air, so that a water cooling device can be added into a feeding port of the blending extruder, and the temperature of the feeding port is controlled to be below 80 ℃, so that feeding is smoothly carried out.
The polyvinyl pyrrolidone with the K value of 15-90 is preferably used in the invention. The polyvinyl pyrrolidone with the K value within the range is easier to blend with polyester, has strong complexing ability with the polyester, is difficult to dissolve out in the water cooling process after blending extrusion, and can obtain polyester fiber with good hygroscopicity; in addition, the viscosity of the polyester system blended with the polyvinyl pyrrolidone having a K value within this range is stable, and problems such as poor kneading and discharging, difficulty in granulation, and low production efficiency do not occur. More preferably, the K value of the polyvinyl-pyrrole-alkanyl ketone is 20-70.
In the present invention, the phosphorus-based heat stabilizer may be added during blending or during melt spinning, and the amount of the phosphorus-based heat stabilizer added is 50 ppm-500 ppm in terms of P element, based on the weight of the polyester fiber. The phosphorus-based heat stabilizer is preferably added at the blending stage. The heat stabilizer is added in the blending stage, and the heat stabilizer is uniformly dispersed through the shearing action in the blending, so that the heat stabilizing effect on the matrix can be exerted to the maximum extent. Meanwhile, the uniformly dispersed heat stabilizer does not influence the subsequent melt spinning.
In the method of the invention, melt spinning is preferably carried out at a lower temperature, in particular preferably with a spinning temperature of 220-C-270 ℃, more preferably 235-260 ℃. Spinning at lower temperature can reduce the thermal decomposition of the blending components, thereby obtaining the fiber with excellent color.
In the present invention, the moisture-absorbing polyester fiber preferably has a moisture-absorbing parameter AMR of 1.0% or more, a hue b value of 5.0 or less, and a light fastness of 3 or more. The fiber has a strength-elongation product of 15.0 or more, and has mechanical properties for general clothing applications.
In the present invention, the obtained polyester fiber was evaluated by the following method.
(1) Mixing stability
The judgment was made by observing the degree of extrusion swell of the polyester at the outlet of the extruder. The evaluation results were good for no die swell, good for slight die swell, and good for severe die swell, and evaluated as good as X.
(2) Spinnability
The spinning condition within 2 hours of spinning was evaluated by the following method, and the yarn was evaluated as good, with no yarn breakage being recorded as good, with a small amount of yarn breakage (1 to 3 times) being recorded as △, and with a frequent yarn breakage (4 times or more) being recorded as X, among which good and judged as good.
(3) Average dispersion diameter of poly N-vinyl lactam
Fibers are cut perpendicularly to the length direction, monofilament section slices are taken for ruthenium staining, and the blending state is observed and photographed by a transmission electron microscope (euphe Μ) (10 ten thousand times). The fiber has a sea-island structure in which a continuous matrix component (white portion) is a sea component and a component (gray component) dispersed in a nearly circular shape is an island component. The island component is regarded as a circle, and the diameter is converted from the area of the island component. This diameter is defined as the dispersion diameter of the polyvinyl-pyrrolidone constituting the island component, and the average dispersion diameter is defined as the average of 20 island components.
(4) Poly N-vinyl lactam K value poly N-vinyl lactam was prepared as an aqueous solution at a mass concentration of 1%, the relative viscosity was measured, and the K value was calculated using fikentscher,
logZ = C[75K2/ (1+1.5KC) +K]，
wherein Kk is X103C is the concentration of the aqueous solution (W/V%), and Z is the relative viscosity of the aqueous solution having the concentration of C.
(5) Elongation product of fiber
Product of strength and elongation = strength X (elongation)5，
The strength is the stress/titer (cN/dtex) of the maximum breaking point when the fiber is stretched under stress-strain, and the elongation is the strain (%) of the maximum breaking point of the fiber.
(6) Moisture absorption parameter AMR
The oil was removed from the fibers and approximately lg of the sample was placed in a glass weighing bottle with a weight of W and dried in a drier at 110 ℃ for 2 hours. The vial was sealed and placed in a desiccator for cooling for 30 minutes. The weight Wi of the weighing bottle containing the sample is measured. Then, the resultant was placed in an open state in a constant temperature and humidity apparatus set at 20 ℃ and 65% RH, and left to stand for 24 hours. Subsequently, the mixture was placed in a desiccator in a sealed state for 30 minutes. Then, the weight W of the weighing flask was measured again2. Placing the mixture in a constant temperature and humidity machine with 30 deg.C and 90% RH in an open state, standing for 24 hr, placing in a drier in a sealed state for 30 min, and measuring the weight W of the weighing bottle3，
(W2-W!) *100%/ (Wj-W) ，
M2= (Ws-Wj) *100%/ (Wj-W) ，
AM =M2-M1O
(7) Fastness to light
The test was carried out in accordance with JIS L-0842, and the higher the number of the grades, the better the light fastness.
(8) Determination of hygroscopic substances and their content in fibers
The position and intensity of the characteristic peak of the hygroscopic substance are measured according to the hydrogen spectrum of the nuclear magnetic resonance, and the content of the hygroscopic substance is calculated according to the chemical formula.
(9) Metal content in polyester
The 6g polymer is pressed into a sheet, its intensity is measured by a fluorescent X-ray analyzer (X-ray analyzer 3270 manufactured by Chong electric Co., Ltd.), and the measurement is performed by using a detection line prepared in advance for a sample having a known metal content
The present invention will be further described with reference to the following examples. Example 1
Adding dimethyl terephthalate, dimethyl isophthalate-5-sodium Sulfonate (SIPM), ethylene glycol, adipic acid and tetrabutyl titanate serving as a catalyst into an esterification kettle, wherein the addition amount of the SIPM is 2.6mol% of the addition amount of the dimethyl terephthalate, the addition amount of the adipic acid is 5.4mol% of the addition amount of the dimethyl terephthalate, the addition amount of the tetrabutyl titanate is 10.5ppm of the copolyester in terms of titanium element, the molar ratio of a total acid component consisting of the dimethyl terephthalate, the SIPM and the adipic acid to a dihydric alcohol component (ethylene glycol) is 1: 1.8, and manganese acetate which is 200ppm of the copolyester in terms of manganese element is also simultaneously added into the esterification kettle; the reaction is carried out for 4 hours at 230 ℃ and normal pressure, and the small molecular prepolymer is obtained after the distillation fraction of methanol reaches more than 95 percent. The prepolymer was kept at 230 ℃ under normal pressure, phosphoric acid, which is a phosphorus stabilizer and corresponds to 50ppm of the copolyester in terms of phosphorus element, was added, and after 5 minutes, the pressure was reduced and the temperature was raised. The temperature was increased from 250 ℃ to 290V and the pressure was reduced to 80Pa over 90 minutes. After the stirring, nitrogen gas was introduced into the reaction system to return to normal pressure, and the polycondensation reaction was stopped, whereby a polyester having a melting point of 230 ℃ was obtained.
Polyvinyl pyrrolidone (PVP, a product of basf corporation) having a K value of 30, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphate, and a polyester having a melting point of 230 ℃ obtained by the above-described method were co-extruded on a biaxial extruder (Φ 44 iota η iota η, L/D:52), wherein the amount of PVP added was 3wt% of the polyester fiber, the amount of diphosphate was 150ppm in terms of phosphorus element, the temperature of the extruder was set to be 245 ℃ in the melt portion, and the extrusion condition was good in the kneading portion at 200 ℃, the average dispersion diameter of PVP in the obtained blend was 80nm, the obtained blend was melt-spun, the spinning temperature was 255V, the spinning speed was 2500m/min, a virgin fiber was obtained, and the polyester fiber was obtained by 2.2-fold stretch processing of the virgin fiber, and the above-described parameters and properties were evaluated on the polyester fiber, and the results are shown in table 1, examples 2 to 4
The PVP addition amounts to the polyester fibers were changed to 5wt%, 10wt%, and 15wt%, respectively, as in example 1. The evaluation results are shown in Table 1. Comparative examples 1 to 2
The PVP addition amounts to the polyester fibers were changed to lwt% and 20% by weight, respectively, and the same procedure as in example 1 was repeated. The evaluation results are shown in Table 1. TABLE 1
The results in Table 1 show that in examples 1 to 4, the polyester fibers obtained had a moisture absorption parameter A MR of 1.1% or more, a hue b value of 4.8 or less, a tenacity product of 19.8 or less, and a light fastness of 3 or more. In examples 1 to 3, the kneading stability and spinning property were good, and in example 4, the kneading stability and spinning property were practically required. On the other hand, in comparative example 1, the amount of PVP added to the polyester fiber was lwt%, and kneading and spinning were practically satisfactory, but the moisture absorption of the obtained fiber was not good. In comparative example 2, when the amount of PVP added to the polyester fiber was 20wt%, the swelling during kneading became serious and granulation became difficult. Examples 5〜8
The same procedure as in example 1 was repeated except that the amount of PVP added to the polyester fiber was changed to 7% by weight, and the amounts of bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphate added to the polyester fiber in terms of the P element were changed to 50ppm, 250ppm, 350ppm and 450ppm, respectively. The evaluation results are shown in Table 2. Comparative example 3
Fibers were obtained in the same manner as in example 5, except that no phosphorus-based heat stabilizer was added. The evaluation results are shown in Table 2. Comparative example 4
Adding terephthalic acid, ethylene glycol and a catalyst antimony trioxide into an esterification kettle, wherein the molar ratio of the terephthalic acid to the ethylene glycol is 1: 1.8, and carrying out esterification reaction for 4 hours at 230 ℃ under normal pressure to obtain a small-molecular prepolymer. The prepolymer was kept at 230 ℃ under normal pressure, and a stabilizer phosphorus compound phosphoric acid corresponding to 50ppm of the copolyester in terms of phosphorus element was added thereto, and after 5 minutes, the pressure and temperature were reduced. The temperature was increased from 250 ℃ to 290 ℃ and the pressure was reduced to 80Pa over 90 minutes. After the stirring, nitrogen gas was introduced into the reaction system to return to normal pressure, and the polycondensation reaction was stopped, whereby a polyester having a melting point of 252 ℃ was obtained.
The amount of PVP added was 7% by weight based on the polyester fiber, and the amount of bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphate added was 150ppm in terms of the phosphorus element content.
The mixing temperature was 265 ℃ and the spinning temperature was 280 ℃. The evaluation results are shown in Table 2.
TABLE 2
The results in Table 2 show that the polyester fibers obtained in examples 5 to 8 are excellent in the moisture absorption parameter A MR, hue b value, elongation at break and light fastness, and in the kneading stability and spinning property. On the other hand, in comparative examples 3 and 4, the obtained fibers had hue b values of 6.0 and 10.0, respectively, and the fiber light fastness was of grade 3 or less and of grade 1, respectively. Examples 9 to 11
A biaxial extruder having an aspect ratio L/D of 45, 48 or 55 was selected for blending, and the other examples were conducted in the same manner as in example 5. The evaluation results are shown in Table 3. Comparative examples 5 to 6
A biaxial extruder having an aspect ratio L/D of 30 and 35 was selected for blending, and the procedure of example 5 was otherwise repeated. The evaluation results are shown in Table 3. TABLE 3
The results in table 3 show that the average dispersion diameter of polyvinyl pyrrolidone in the polyester fibers obtained in examples 9 to 11 was 180nm or less, and the average dispersion diameter of the polyester fiber of example 11 was as small as 90 nm. In comparative examples 5 and 6, the average dispersion diameter of the polyester fiber was 250nm or more. The use of a biaxial extruder with a specific length-diameter ratio/D is shown to be of great significance in controlling the average dispersion diameter of the polyvinyl-pyrrolidone in the polyester fibers. Example 12
Taking 5.7Kg of terephthalic acid, 5.4Kg of butanediol and 3.75Kg of polyethylene glycol (molecular weight 4000), fully mixing, putting into a reactor with stirring and heating temperature control, adding 8g of tetrabutyl titanate and 15g of IR1010 serving as catalysts, gradually heating to 230 ℃ for dehydration esterification reaction, ending the esterification reaction when the esterification rate reaches 95% or more, gradually heating to 250 ℃, simultaneously reducing the reaction pressure to below 130Pa, removing small molecular reaction, discharging cut materials after the set polymer viscosity is reached, and obtaining the polyester with the melting point of 220 ℃.
PVP (product of BASF Co.) having a K value of 60 and the polyester having a melting point of 220 ℃ were co-extruded on a biaxial extruder (phi 44 iota η iota η, L/D:52) in which the amount of PVP added was 7wt% of the polyester fiber, the temperature of the extruder was set to 235 ℃ in the melting section and 180 ℃ in the kneading section, and the extrusion condition was good, the average dispersion diameter of PVP in the obtained blend was 100nm, the obtained blend was melt-spun, bis (2, 4-t-butylphenyl) pentaerythritol diphosphate was added during the spinning, the amount of bis (2, 4-t-butylphenyl) pentaerythritol diphosphate was added in an amount equivalent to 150ppm in terms of phosphorus element of the polyester fiber, the spinning temperature was 245 ℃ and the spinning speed was 2000m/min to obtain a spun fiber, and the spun fiber was subjected to 2.4-fold elongation processing to obtain a polyester fiber, and the evaluation results of the obtained polyester fiber are shown in Table 4
The same procedure as in example 1 was repeated except that the polyester having a melting point of 230 ℃ obtained in example 1 and the polyester having a melting point of 240 ℃ were used (except that the amount of adipic acid added was 4.0mol% based on the amount of methyl terephthalate added, they were obtained), and the spinning temperatures in the melt spinning were changed to 255 ℃ and 260 ℃ respectively, which was otherwise the same as in example 12. Examples 15 to 17
PVP (product of BASF Corp.) having a K value of 60 and the polyester having a melting point of 230 ℃ obtained in example 1 were subjected to extrusion by blending in a biaxial extruder (phi 44 iota η iota η, L/D:52) in which the amount of PVP added was 7wt% of the polyester fiber and the temperature of the extruder was set to 180 ℃ in the kneading section of the melting section 245, and the extrusion was good, the obtained blend was subjected to melt spinning, and trimethyl phosphate (example 15), methyl methacrylate (example 16), and resorcinol bis (pentaerythritol) phosphate (example 17) were added during the spinning in an amount of 150ppm in terms of phosphorus element, the spinning temperature was 255 ℃ and the spinning speed was 3000m/min to obtain a spun fiber, and the spun fiber was subjected to 1.7-fold elongation processing to obtain a polyester fiber, and the evaluation results of the obtained polyester fiber are shown in Table 4
PVP (products of BASF corporation) having K values of 10 and 120 was selected, and the procedure was otherwise the same as in example 12. In comparative example 7, when the K value of PVP was 10, kneading was stable, but the heat resistance was poor, and many yarn breaks were caused during spinning. When the K value of PVP in comparative example 8 was 120, the kneading system had a high viscosity, causing swelling and deteriorated kneading property.
TABLE 4
The results of examples 12 to 17 in table 4 show that in the process for producing polyester fibers of the present invention, a phosphorus-based heat stabilizer was added in the stage of melt spinning, and polyester fibers having good hygroscopicity parameter a MR, hue b value, elongation, light fastness, kneading stability and spinning property were similarly obtained.
Claims (11)
- Claims book1. The hygroscopic polyester fiber is characterized in that the polyester fiber contains polyester, poly-N-vinyl lactam and phosphorus heat stabilizer, wherein the poly-N-vinyl lactam accounts for 3-15 wt% of the weight of the polyester fiber, and the dispersion diameter is less than 200 nm; the phosphorus-based heat stabilizer is present in an amount of 50-500 ppm in terms of P element based on the weight of the polyester fiber.
- 2. The hygroscopic polyester fiber according to claim 1, wherein said polyester is a polyester having a melting point of 200 to 240 ℃.
- 3. The moisture-absorbing polyester fiber according to claim 1 or 2, wherein the poly-N-vinyl lactam accounts for 5 to 12wt% of the weight of the polyester fiber.
- 4. The moisture-absorbing polyester fiber according to claims 1 to 3, wherein the poly-N-vinyl lactam is polyvinyl pyrrolidone.
- 5. The hygroscopic polyester fiber according to claim 4, wherein said polyvinyl-pyrrolidone has a K value of 15 to 90.
- 6. The moisture-absorbing polyester fiber according to claim 1 to 5, wherein the phosphorus-based heat stabilizerWherein Ri, R2Each independently of the other mayAn aromatic hydrocarbon group having a substituent.
- 7. The hygroscopic polyester fiber as claimed in claim 6, wherein said phosphorus-based heat stabilizer is bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate or bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphate.
- 8. The moisture-absorbent polyester fiber according to claim 1, wherein the polyester fiber has a moisture absorption parameter AMR of 1.0% or more, a hue b value of 5.0 or less, and a light fastness of 3 or more.
- 9. The preparation method of the hygroscopic polyester fiber is characterized in that polyester and poly-N-vinyl lactam are blended on a biaxial extruder with the length-diameter ratio L/D of more than 45, wherein the addition amount of the poly-N-vinyl lactam accounts for 3-15 wt% of the weight of the polyester fiber; carrying out melt spinning on the obtained blend to obtain nascent fiber, and further stretching the nascent fiber to obtain polyester fiber; a phosphorus-based heat stabilizer is added in the blending stage or the melt spinning stage in an amount of 50 ppm-500 ppm based on the weight of the polyester fiber in terms of phosphorus element.
- 10. The method of producing hygroscopic polyester fiber according to claim 9, wherein said phosphorus-based heat stabilizer is added at the blending stage.
- The method for producing a hygroscopic polyester fiber according to claim 9 or 10, wherein the polyester is a polyester having a melting point of 200 to 240 ℃ and the melt-spinning temperature is in the range of 220 to 270 ℃.
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| CN201380045855.XA CN104619897B (en) | 2012-10-09 | 2013-10-09 | Moisture absorption type polyester fiber and preparation method thereof |
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| CN201210379074.1A CN103710781A (en) | 2012-10-09 | 2012-10-09 | Hygroscopic polyester fiber and manufacturing method thereof |
| CN2012103790741 | 2012-10-09 | ||
| PCT/CN2013/084901 WO2014056429A1 (en) | 2012-10-09 | 2013-10-09 | Hygroscopic polyester fiber and manufacturing method thereof |
| CN201380045855.XA CN104619897B (en) | 2012-10-09 | 2013-10-09 | Moisture absorption type polyester fiber and preparation method thereof |
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| CN107502990A (en) * | 2017-08-30 | 2017-12-22 | 广州弘雅服装科技有限公司 | A kind of high water absorption moisture absorption polyester fiber, high water absorption Hygroscopic material and preparation and application |
| CN118127662B (en) * | 2024-05-08 | 2024-07-05 | 广东安之伴实业有限公司 | Antibacterial and moisture-absorbing modified polyester fabric as well as preparation method and application thereof |
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| JP3139315B2 (en) * | 1995-01-25 | 2001-02-26 | 東レ株式会社 | Hygroscopic composite fiber using copolyester excellent in hygroscopic property |
| JPH09132823A (en) * | 1995-11-06 | 1997-05-20 | Nippon Ester Co Ltd | Polyester conjugate fiber |
| JP3804097B2 (en) * | 1996-03-29 | 2006-08-02 | 東レ株式会社 | Support stockings with excellent wearing comfort |
| JP2000178845A (en) * | 1998-12-10 | 2000-06-27 | Du Pont Toray Co Ltd | Covered elastic yarn and its production |
| JP2002155425A (en) * | 2000-11-15 | 2002-05-31 | Nippon Shokubai Co Ltd | Hygroscopic fiber and method for producing thermoplastic polyester-based resin composition |
| JP2003129340A (en) * | 2001-10-19 | 2003-05-08 | Teijin Ltd | Polyester fiber and method for producing the same |
| CN1258010C (en) * | 2002-03-29 | 2006-05-31 | 东华大学 | Anti-electrostatic nano compound polyester fibre and making method thereof |
| JP4375073B2 (en) * | 2004-03-24 | 2009-12-02 | 東レ株式会社 | Hygroscopic polyester fiber and method for producing the same |
| JP5946255B2 (en) * | 2010-09-17 | 2016-07-06 | 株式会社日本触媒 | N-vinyl lactam polymer and process for producing the same |
| JP5655632B2 (en) * | 2011-02-28 | 2015-01-21 | 東レ株式会社 | Sea-island composite cross-section fiber made of alkali-eluting polyester |
| CN102796352B (en) * | 2011-05-23 | 2016-04-13 | 东丽纤维研究所（中国）有限公司 | A kind of damp absorbent polyester, preparation method and the fiber be made up of it |
| CN102838739B (en) * | 2011-06-22 | 2015-08-05 | 东丽纤维研究所（中国）有限公司 | A kind of Moisture-absorption copolyester and preparation method thereof |
| CN103120375B (en) * | 2011-11-18 | 2016-03-30 | 东丽纤维研究所（中国）有限公司 | A kind of hygroscopicity fabric and uses thereof |
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| CN104619897B (en) | 2016-05-04 |
| WO2014056429A1 (en) | 2014-04-17 |
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| JP6296059B2 (en) | 2018-03-20 |
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