CN109401214B - Polyester composition and elastic fiber and method for producing the same - Google Patents

Polyester composition and elastic fiber and method for producing the same Download PDF

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Publication number
CN109401214B
CN109401214B CN201710703617.3A CN201710703617A CN109401214B CN 109401214 B CN109401214 B CN 109401214B CN 201710703617 A CN201710703617 A CN 201710703617A CN 109401214 B CN109401214 B CN 109401214B
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polyester
repeating unit
polyester composition
weight
temperature
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CN109401214A (en
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祝桂香
郑萃
任敏巧
刘立志
张伟
韩翎
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Priority to CN201710703617.3A priority Critical patent/CN109401214B/en
Priority to PCT/CN2017/107106 priority patent/WO2018072746A1/en
Priority to US16/343,711 priority patent/US11466151B2/en
Priority to CA3040988A priority patent/CA3040988A1/en
Priority to EP17862862.4A priority patent/EP3530694A4/en
Priority to JP2019520899A priority patent/JP2020502288A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/12—Shape memory
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The invention relates to the field of high polymer materials, and discloses a polyester composition, elastic fibers and a preparation method thereof. Specifically, the polyester composition comprises the following components by taking the total weight of the components as a reference: (1)30-98 wt.% of polyester A; (2)1-69 wt.% of polyester B; (3)1 to 69% by weight of polyester C. The elastic fiber prepared from the polyester composition has moderate elasticity and strength, and has wide adjustable range of performance and good application prospect. In addition, the elastic fiber is prepared by adopting a method of high-temperature filament forming, low-temperature placement and high-temperature stretching, the method can further improve the breaking strength of the elastic fiber, expand the adjustable range of the performance and reduce the stress relaxation and the permanent strain rate of the elastic fiber.

Description

Polyester composition and elastic fiber and method for producing the same
Technical Field
The invention relates to the field of high polymer materials, in particular to a polyester composition, a preparation method of the polyester composition, an elastic fiber and a preparation method of the elastic fiber.
Background
Elastic fibers are a generic term for a class of fibers having high elasticity, low modulus, and high elastic recovery. With the improvement of the requirement of comfort, elastic fibers are gradually superior in the fiber field, and the application field is also expanded from traditional knitted socks, underwear, sportswear and the like to emerging fields such as casual wear, high-elasticity fashion wear, high-grade ready-made clothes and the like, and is continuously expanded to the automobile decoration field, the medical field and the like.
The original elastic fibers were natural rubber filaments. After DuPont developed polyurethane fiber "Lycra" in 1958, a number of elastic fibers appeared in the market. These elastic fibers are roughly classified into two types, and one type is an elastic fiber obtained by utilizing the elasticity of the material itself, for example, a natural rubber fiber, a polyurethane fiber (spandex), a polyacrylate fiber, a polybutylene terephthalate (PBT) fiber, a polyether ester elastomer (TPEE) fiber, a polytrimethylene terephthalate (PTT) fiber, and a polyolefin (XLA) fiber. The elasticity of such elastic fibers is largely determined by the material itself. Wherein, the elasticity of the polyacrylate fiber, the PBT fiber and the PTT fiber is low, and the elasticity is only slight; the natural rubber fiber has strong elasticity but weak strength and is easy to age; the strength of the polyurethane fiber is weak; the polyether ester elastomer fiber has excellent comprehensive performance and wide performance adjustable range, but the cost is too high; XLA fiber has good elasticity, good heat resistance and good mechanical strength, but the performance is relatively fixed and the adjustability is insufficient. The other is a multifilament composite elastic fiber, typically a T400 fiber, which utilizes the helical elasticity created by the difference in shrinkage of the two materials. The elasticity of such fibers can be controlled by the manufacturing process, but the amount of elasticity caused by the spiral is very low, usually much less than the elasticity imparted by the material itself. At present, the market is still lack of such an elastic fiber, and it has moderate elasticity and intensity simultaneously on the basis of having lower cost to but the performance adjustable range is wide, can adapt to the demand of diversified product.
Disclosure of Invention
The present invention has been made to overcome the above-mentioned drawbacks of the prior art, and an object of the present invention is to provide a polyester composition, a method for preparing the same, and an elastic fiber and a method for preparing the same. The elastic fiber prepared from the polyester composition provided by the invention has moderate elasticity and strength, and the adjustable range of performance is wide.
In order to achieve the above object, in a first aspect, the present invention provides a polyester composition comprising the following components, based on the total weight of the components:
(1)30 to 98% by weight of a polyester A which is a copolymer comprising a repeating unit A represented by the formula (I) and a repeating unit B represented by the formula (II), wherein the content of the repeating unit A is 51 to 80% by mole, preferably 60 to 75% by mole, based on the total number of moles of the repeating unit A and the repeating unit B in the polyester A; the content of the repeating unit B is 20 to 49 mol%, preferably 25 to 40 mol%,
Figure BDA0001380988950000021
wherein m1 is an integer of 2 to 8, n1 is an integer of 2 to 6, and m1 and n1 are the same or different; the weight average molecular weight of the polyester A is 50,000-900,000;
(2)1 to 69% by weight of a polyester B which is a copolymer comprising a repeating unit C represented by the formula (III) and a repeating unit B represented by the formula (II), wherein the content of the repeating unit C is 81 to 99 mol%, preferably 83 to 95 mol%, and the content of the repeating unit B is 1 to 19 mol%, preferably 5 to 17 mol%, based on the total number of moles of the repeating unit C and the repeating unit B in the polyester B,
Figure BDA0001380988950000031
wherein m2 is an integer of 2 to 8, n2 is an integer of 2 to 6, and m2 and n2 are the same or different; the weight average molecular weight of the polyester B is 50,000-900,000;
(3)1 to 69% by weight of a polyester C which is a copolymer comprising a repeating unit D represented by the formula (IV) and a repeating unit B represented by the formula (II), and the content of the repeating unit D is 0 to 49 mol%, preferably 15 to 45 mol%, and the content of the repeating unit B is 51 to 100 mol%, preferably 55 to 85 mol%, based on the total number of moles of the repeating unit D and the repeating unit B in the polyester C,
Figure BDA0001380988950000032
wherein m3 is an integer of 2 to 8, n3 is an integer of 2 to 6, and m3 and n3 are the same or different; the weight average molecular weight of the polyester C was 50,000-900,000.
In a second aspect, the present invention also provides a process for preparing the above polyester composition, which comprises: the polyester A, the polyester B and the polyester C are blended, and the obtained mixture is subjected to extrusion granulation.
In a third aspect, the present invention also provides an elastic fiber comprising the above polyester composition and/or the polyester composition obtained by the above production method.
In a fourth aspect, the present invention also provides a method for preparing an elastic fiber, comprising: the polyester composition is subjected to filamentation, low-temperature placement and stretching in sequence to obtain the elastic fiber.
The invention obtains the polyester composition by blending the specific polyester A, the specific polyester B and the specific polyester C according to the specific mixture ratio (30-98 wt% of polyester A, 1-69 wt% of polyester B and 1-69 wt% of polyester C), the breaking strength of the elastic fiber prepared by using the polyester composition is more than or equal to 1cN/dtex, and the maximum breaking strength is close to 20cN/dtex by adjusting the formula and the molecular structure; in addition, the elongation at break of the elastic fiber provided by the invention is as high as more than 130%, and both the stress relaxation rate and the permanent strain rate can be less than or equal to 12%, which shows that the elastic fiber provided by the invention has moderate elasticity and strength and wide performance adjustability range, so that the elastic fiber has good application prospect.
In addition, the elastic fiber is prepared by adopting the method and the conditions of high-temperature filamentation, low-temperature placement and high-temperature stretching, the method can further improve the breaking strength of the elastic fiber, expand the adjustable range of the performance and reduce the stress relaxation and the permanent strain rate of the elastic fiber.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a polyester composition comprising, based on the total weight of the components:
(1)30 to 98% by weight of a polyester A which is a copolymer comprising a repeating unit A represented by the formula (I) and a repeating unit B represented by the formula (II), wherein the content of the repeating unit A is 51 to 80% by mole, preferably 60 to 75% by mole, based on the total number of moles of the repeating unit A and the repeating unit B in the polyester A; the content of the repeating unit B is 20 to 49 mol%, preferably 25 to 40 mol%,
Figure BDA0001380988950000041
wherein m1 is an integer from 2 to 8, preferably an integer from 2 to 4; n1 is an integer from 2 to 6, preferably an integer from 2 to 4; and m1 and n1 are the same or different; the weight average molecular weight of the polyester A is 50,000-900,000, preferably 100,000-500,000;
(2)1 to 69% by weight of a polyester B which is a copolymer comprising a repeating unit C represented by the formula (III) and a repeating unit B represented by the formula (II), wherein the content of the repeating unit C is 81 to 99 mol%, preferably 83 to 95 mol%, and the content of the repeating unit B is 1 to 19 mol%, preferably 5 to 17 mol%, based on the total number of moles of the repeating unit C and the repeating unit B in the polyester B,
Figure BDA0001380988950000051
wherein m2 is an integer from 2 to 8, preferably an integer from 2 to 4; n2 is an integer from 2 to 6, preferably an integer from 2 to 4; and m2 and n2 are the same or different; the weight average molecular weight of the polyester B is 50,000-900,000, preferably 100,000-500,000;
(3)1 to 69% by weight of a polyester C which is a copolymer comprising a repeating unit D represented by the formula (IV) and a repeating unit B represented by the formula (II), and the content of the repeating unit D is 0 to 49 mol%, preferably 15 to 45 mol%, and the content of the repeating unit B is 51 to 100 mol%, preferably 55 to 85 mol%, based on the total number of moles of the repeating unit D and the repeating unit B in the polyester C,
Figure BDA0001380988950000052
wherein m3 is an integer from 2 to 8, preferably an integer from 2 to 4; n3 is an integer from 2 to 6, preferably an integer from 2 to 4; and m3 and n3 are the same or different; the weight average molecular weight of the polyester C is 50,000-900,000, preferably 100,000-500,000.
In the present invention, m1, m2 and m3 may be the same or different, and n1, n2 and n3 may be the same or different. However, when m1, m2 and m3 are the same and n1, n2 and n3 are the same, the content of the repeating unit B in the polyester A, the polyester B and the polyester C is different from each other.
In the present invention, the weight average molecular weight of the polymer is measured according to Gel Permeation Chromatography (GPC).
Preferably, the polyester composition comprises 60 to 93% by weight of polyester A, 5 to 38% by weight of polyester B and 1 to 20% by weight of polyester C.
In the present invention, each of the polyester a, the polyester B, and the polyester C may be at least one of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer, and is preferably a random copolymer and/or a block copolymer. The sources of the polyester A, the polyester B and the polyester C are not particularly limited in the present invention, and the polyester A, the polyester B and the polyester C can be obtained by a conventional means in the field, can be obtained commercially, or can be prepared according to the method disclosed in example B13-B21 in CN 100429256C. Specifically, the preparation method of the polyester A comprises the following steps:
(1) reacting a monomer A and a monomer B in the presence of a first catalyst in an inert atmosphere;
(2) reacting a monomer C and a monomer D in the presence of a first catalyst in an inert atmosphere;
(3) reacting the reaction product obtained in the step (1) and the reaction product obtained in the step (2) in the presence of a second catalyst;
wherein the monomer A is butanediol; the monomer B is terephthalic acid and/or ester thereof, preferably at least one of terephthalic acid, dimethyl terephthalate and diethyl terephthalate; the monomer C is dihydric alcohol (especially saturated straight-chain dihydric alcohol) of C2-C8; the monomer D is dibasic acid (especially saturated straight chain dibasic acid) of C4-C8; the first catalyst is at least one of tetrabutyl titanate, titanium dioxide, diethoxy titanium and zinc acetate, and tetrabutyl titanate is preferred; the second catalyst is at least one of lanthanum acetylacetonate, lanthanum trichloride, triphenoxy lanthanum and lanthanum propionate, and is preferably lanthanum acetylacetonate.
In the present invention, in step (1), the molar ratio of the monomer B to the first catalyst is 1: 0.0001-0.02: 0.0001-0.02, more preferably 1: 0.001-0.003: 0.001-0.003.
In the present invention, in the step (2), the molar ratio of the monomer D to the first catalyst is 1: 0.0001-0.02: 0.0001-0.02, more preferably 1: 0.001-0.003: 0.001-0.003.
In a preferred case, the molar ratio of the total amount of the first catalyst (sum of the amounts of the first catalyst used in step (1) and step (2)) to the amount of the second catalyst is 1: 0.5-1.5, preferably 1: 0.8-1.2.
In the present invention, the types of the respective reaction monomers can be adjusted correspondingly according to the composition and molecular weight of the target product, and the molecular weight of the product and the content of the respective repeating units in the product can be controlled by adjusting the amount and ratio of the charge.
In the present invention, in step (1), the temperature of the reaction is preferably 160-220 ℃; in the present invention, in step (2), the temperature of the reaction is preferably 160-220 ℃; in the present invention, in the step (3), the temperature of the reaction is preferably 180-240 ℃.
In a preferred embodiment of the present invention, when m1 is 4, the preparation method of polyester A comprises the following steps:
(S1) reacting butanediol and monomer a' in the presence of a first catalyst in an inert atmosphere;
(S2) reacting the reaction product obtained from the step (S1) with a monomer B' in the presence of a second catalyst;
wherein the monomer A' is terephthalic acid and/or ester thereof, preferably at least one of terephthalic acid, dimethyl terephthalate and diethyl terephthalate; the monomer B' is dibasic acid (especially saturated straight chain dibasic acid) of C4-C8; the first catalyst and the second catalyst are as described above and will not be described in detail herein.
In the present invention, in the step (S1), the molar ratio of the monomer a' to the first catalyst is 1: 0.0001-0.02: 0.0001-0.02, more preferably 1: 0.001-0.003: 0.001-0.003.
In a preferred case, the molar ratio of the amount of the first catalyst to the amount of the second catalyst is 1: 0.5-1.5, preferably 1: 0.8-1.2.
In the present invention, the types of the respective reaction monomers can be adjusted correspondingly according to the composition and molecular weight of the target product, and the molecular weight of the product and the content of the respective repeating units in the product can be controlled by adjusting the amount and ratio of the charge.
In the present invention, in the step (S1), the temperature of the reaction is preferably 160-220 ℃; in the present invention, in the step (S2), the temperature of the reaction is preferably 180-240 ℃.
According to the present invention, the polyester B and the polyester C can also be prepared according to the preparation method of the polyester A, wherein the types of the reaction monomers can be adjusted correspondingly according to the composition and the molecular weight of the target product, and the molecular weight of the product and the content of each repeating unit in the product can be controlled by adjusting the feeding amount and the feeding ratio to obtain the polyester B and the polyester C.
According to the invention, the polyester composition may also contain auxiliary fillers; preferably, the content of the auxiliary filler is 1 to 20% by weight, more preferably 2 to 10% by weight, based on the total weight of the polyester composition.
In the present invention, the auxiliary filler may have the effects of accelerating the melt solidification of the composition, adjusting the mechanical strength of the composition, improving the flame retardancy and oxidation resistance of the composition, adjusting the color and gloss of the composition, and may be a conventional choice in the art, for example, the auxiliary filler is selected from one or more of calcium carbonate, carbon black, talc, erucamide, titanium dioxide, low density polyethylene, polyphosphate, phosphite, hindered phenol, hindered amine, dibenzyl sorbitol and its derivatives, hyperbranched polyamide, and ethylene-methacrylic acid ionomer; preferably one or more of calcium carbonate, carbon black, erucamide, titanium dioxide, tris (2, 3-dibromopropyl) phosphate (TDBPP) and low density polyethylene.
In a second aspect, the present invention also provides a process for preparing the above polyester composition, which comprises: polyester A, polyester B and polyester C were blended, and the resulting mixture was subjected to extrusion granulation.
In the preparation method of the polyester composition of the present invention, the composition of the polyester a, the composition of the polyester B, the composition of the polyester C, and the amounts of the respective components are as described above, and are not described herein again.
According to the invention, the blending is preferably carried out in the presence of an auxiliary filler; preferably, the content of the auxiliary filler is 1 to 20% by weight, preferably 2 to 10% by weight, based on the total weight of the polyester composition.
In the process for preparing the polyester composition of the present invention, the kind of the auxiliary filler is as described above and will not be described herein again.
In the present invention, the inventors have unexpectedly found during the research that: the polyester A, the polyester B and the polyester C have good compatibility, so that no compatilizer can be added in the blending process. The compatibilizer is a substance conventionally used in the art to improve compatibility of blending raw materials, and may be, for example, at least one of PE-g-ST, PP-g-ST, ABS-g-MAH, PE-g-MAH, and PP-g-MAH.
According to the invention, the blending process can be carried out under stirring. In the present invention, the stirring conditions are not particularly limited as long as the raw materials can be uniformly mixed, and in a preferred case, the stirring speed is 10 to 150r/min, and the stirring time is 5 to 15 min.
According to the present invention, the extrusion granulation process may be performed according to a conventional extrusion granulation method, for example, the extrusion granulation may be performed in a screw extruder. In a preferred case, the temperature of the extrusion granulation is 110-270 ℃, preferably 130-230 ℃.
In a third aspect, the present invention also provides an elastic fiber, wherein the elastic fiber contains the polyester composition and/or the polyester composition obtained by the preparation method, that is, the elastic fiber is prepared from the polyester composition and/or the polyester composition obtained by the preparation method.
According to the invention, the titer of the elastic fibers can be 5 to 500 dtex. The breaking strength is more than or equal to 1cN/dtex, and is preferably 3-19 cN/dtex; the elongation at break is more than or equal to 100 percent, and preferably 130-620 percent; the stress relaxation rate is less than or equal to 12 percent, and preferably 1 to 12 percent; the permanent strain rate is less than or equal to 12 percent, and the preferential rate is 1 to 11 percent. In the present invention, the fineness can be detected using a conventional fineness meter.
In a fourth aspect, the present invention also provides a method for preparing an elastic fiber, comprising: sequentially carrying out filamentation, low-temperature placement and stretching on the polyester composition to obtain elastic fibers; wherein the polyester composition is the polyester composition and/or the polyester composition obtained by the preparation method.
According to the present invention, the manner of said filamentation may be a matter of conventional choice in the art, preferably melt spinning. Preferably, the temperature of the filamentation is 120-270 ℃, preferably 150-220 ℃.
According to the invention, the conditions of the cryogenic storage include: the temperature is 20-55 ℃, preferably 25-45 ℃; the time is 2-120min, preferably 15-60 min.
According to the invention, the conditions of said stretching comprise: the temperature is 56-110 ℃, preferably 60-90 ℃; the stretching magnification is 1.2 to 10 times, preferably 2 to 5 times.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the weight average molecular weight of the polymer was measured using Gel Permeation Chromatography (GPC) with Tetrahydrofuran (THF) as the solvent on a Waters-208 (with Waters 2410RI detector, 1.5mL/min flow rate, 30 ℃ C.) instrument, calibrated with styrene standards;
the composition of the polyester composition is determined by the raw material charge;
the polyester used in the present invention is prepared by itself, without specific mention, according to the method disclosed in example B13-B21 of CN100429256C, wherein the types of the reaction raw materials can be adjusted correspondingly according to the composition and molecular weight of the target product, and the molecular weight of the product and the content of each repeating unit in the product are controlled by adjusting the amount and ratio of the charged materials.
Example 1
This example illustrates the elastic fibers and the method of making the same provided by the present invention.
(1) Preparation of polyester composition
Under the condition of stirring (the stirring speed is 10r/min, the stirring time is 10min), 150g of terephthalic acid butanediol-butanediol succinate copolyester A (the weight-average molecular weight is 130,000, wherein the content of the terephthalic acid butanediol repeating unit is 30 mol% based on the total molar number of the terephthalic acid butanediol repeating unit and the butanediol succinate repeating unit), 30g of terephthalic acid butanediol-butanediol succinate copolyester B (the weight-average molecular weight is 100,000, wherein the content of the terephthalic acid butanediol repeating unit is 10 mol% based on the total molar number of the terephthalic acid butanediol repeating unit and the butanediol succinate repeating unit), 20g of terephthalic acid butanediol-butanediol adipate copolyester C (the weight-average molecular weight is 100,000, wherein the total molar number of the terephthalic acid butanediol repeating unit and the butanediol adipate repeating unit is used as the reference, wherein the content of the repeating unit of butylene terephthalate is 60 mol%) and 10g of titanium dioxide, and stirring at a speed of 10r/min for 10min, then adding into a twin-screw extruder, melt-extruding at a temperature of 220 ℃ and granulating to obtain a polyester composition A1.
(2) Preparation of elastic fibers
The above polyester polymer A1 was spun into a fiber having a fineness of 72dtex by a melt spinning method at 170 ℃. The fibers were left at 40 ℃ for 60min, then warmed to 70 ℃ and stretched to 4 times the original length. After cooling, the elastic fiber B1 is obtained.
Example 2
This example illustrates the elastic fibers and the method of making the same provided by the present invention.
(1) Preparation of polyester composition
Under the condition of stirring (the stirring speed is 10r/min, the stirring time is 10min), 186g of terephthalic acid butanediol-butanediol succinate copolyester A (the weight-average molecular weight is 130,000, wherein the content of the terephthalic acid butanediol repeating unit is 30 mol% based on the total molar number of the terephthalic acid butanediol repeating unit and the butanediol succinate repeating unit), 12g of terephthalic acid butanediol-butanediol succinate copolyester B (the weight-average molecular weight is 100,000, wherein the content of the terephthalic acid butanediol repeating unit is 10 mol% based on the total molar number of the terephthalic acid butanediol repeating unit and the butanediol succinate repeating unit), 4g of terephthalic acid butanediol-butanediol adipate copolyester C (the weight-average molecular weight is 100,000, wherein the total molar number of the terephthalic acid butanediol repeating unit and the butanediol adipate repeating unit is used as the reference, wherein the content of the repeating unit of butylene terephthalate is 60 mol%) and 10g of titanium dioxide, and stirring at a speed of 10r/min for 10min, then adding into a twin-screw extruder, melt-extruding at a temperature of 220 ℃ and granulating to obtain a polyester composition A2.
(2) Preparation of elastic fibers
The above polyester polymer A2 was spun into a fiber having a fineness of 72dtex by a melt spinning method at 170 ℃. The fibers were left at 40 ℃ for 60min, then warmed to 70 ℃ and stretched to 4 times the original length. After cooling, the elastic fiber B2 is obtained.
Example 3
This example illustrates the elastic fibers and the method of making the same provided by the present invention.
(1) Preparation of polyester composition
Under the condition of stirring (the stirring speed is 10r/min, the stirring time is 10min), 120g of terephthalic acid butanediol-butanediol succinate copolyester A (the weight-average molecular weight is 130,000, wherein the content of the terephthalic acid butanediol repeating unit is 40 mol% based on the total molar number of the terephthalic acid butanediol repeating unit and the butanediol succinate repeating unit), 40g of terephthalic acid butanediol-butanediol succinate copolyester B (the weight-average molecular weight is 100,000, wherein the content of the terephthalic acid butanediol repeating unit is 17 mol% based on the total molar number of the terephthalic acid butanediol repeating unit and the butanediol succinate repeating unit), 40g of terephthalic acid butanediol-butanediol adipate copolyester C (the weight-average molecular weight is 100,000, wherein the total molar number of the terephthalic acid butanediol repeating unit and the butanediol adipate repeating unit is used as the reference, wherein the content of the butylene terephthalate repeating unit was 85 mol%), 10g of titanium dioxide, and stirred at a speed of 10r/min for 10min, and then added to a twin-screw extruder, melt-extruded at a temperature of 220 ℃ and pelletized, to obtain a polyester composition A3.
(2) Preparation of elastic fibers
The above polyester polymer A3 was spun into a fiber having a fineness of 72dtex by a melt spinning method at 170 ℃. The fibers were left at 40 ℃ for 60min, then warmed to 70 ℃ and stretched to 4 times the original length. After cooling, the elastic fiber B3 is obtained.
Example 4
This example illustrates the elastic fibers and the method of making the same provided by the present invention.
(1) Preparation of polyester composition
Under the condition of stirring (the stirring speed is 10r/min, the stirring time is 10min), 120g of terephthalic acid butanediol-butanediol succinate copolyester A (the weight-average molecular weight is 130,000, wherein the content of the terephthalic acid butanediol repeating unit is 25 mol% based on the total molar number of the terephthalic acid butanediol repeating unit and the butanediol succinate repeating unit), 70g of terephthalic acid butanediol-butanediol succinate copolyester B (the weight-average molecular weight is 100,000, wherein the content of the terephthalic acid butanediol repeating unit is 5 mol% based on the total molar number of the terephthalic acid butanediol repeating unit and the butanediol succinate repeating unit), 10g of terephthalic acid butanediol-butanediol adipate copolyester C (the weight-average molecular weight is 100,000, wherein the total molar number of the terephthalic acid butanediol repeating unit and the butanediol adipate repeating unit is used as a reference, wherein the content of the repeating unit of butylene terephthalate is 55 mol%) and 10g of titanium dioxide, and stirring at a speed of 10r/min for 10min, then adding into a twin-screw extruder, melt-extruding at a temperature of 220 ℃ and granulating to obtain a polyester composition A4.
(2) Preparation of elastic fibers
The above polyester polymer A4 was spun into a fiber having a fineness of 72dtex by a melt spinning method at 170 ℃. The fibers were left at 40 ℃ for 60min, then warmed to 70 ℃ and stretched to 4 times the original length. After cooling, the elastic fiber B4 is obtained.
Example 5
This example illustrates the elastic fibers and the method of making the same provided by the present invention.
(1) Preparation of polyester composition
60g of butylene terephthalate-butylene succinate copolyester A (with a weight-average molecular weight of 130,000, wherein the content of butylene terephthalate repeat units is 49 mol% based on the total number of moles of butylene terephthalate repeat units and butylene succinate repeat units), 138g of butylene terephthalate-butylene succinate copolyester B (with a weight-average molecular weight of 100,000, wherein the content of butylene terephthalate repeat units is 19 mol% based on the total number of moles of butylene terephthalate repeat units and butylene succinate repeat units), 2g of polybutylene terephthalate (available from DuPont under the trademark Crastin SC164 NC010) particles, 10g of titanium dioxide were mixed under stirring (stirring rate of 10r/min for 10min), then, the mixture was fed into a twin-screw extruder, melt-extruded at a temperature of 220 ℃ and pelletized to obtain a polyester composition A5.
(2) Preparation of elastic fibers
The above polyester polymer A5 was spun into a fiber having a fineness of 72dtex by a melt spinning method at 170 ℃. The fibers were left at 40 ℃ for 60min, then warmed to 70 ℃ and stretched to 4 times the original length. After cooling, the elastic fiber B5 is obtained.
Example 6
This example illustrates the elastic fibers and methods of making the same provided by the present invention.
(1) Preparation of polyester composition
Under the condition of stirring (the stirring speed is 10r/min, the stirring time is 10min), 60g of particles of terephthalic acid butanediol-butanediol succinate copolyester A (the weight-average molecular weight is 130,000, wherein the content of the terephthalic acid butanediol repeating units is 20 mol% based on the total moles of the terephthalic acid butanediol repeating units and the butanediol succinate repeating units), 2g of particles of terephthalic acid butanediol-butanediol succinate copolyester B (the weight-average molecular weight is 100,000, wherein the content of the terephthalic acid butanediol repeating units is 1 mol% based on the total moles of the terephthalic acid butanediol repeating units and the butanediol succinate repeating units), 138g of terephthalic acid butanediol-butanediol adipate copolyester C (the weight-average molecular weight is 100,000, wherein the total moles of the terephthalic acid butanediol repeating units and the butanediol adipate repeating units are taken as the reference, wherein the content of the repeating unit of butylene terephthalate is 51 mol%) and 10g of titanium dioxide are mixed and stirred at a speed of 10r/min for 10min, and then added into a twin-screw extruder, melt-extruded at a temperature of 220 ℃ and pelletized to obtain a polyester composition A6.
(2) Preparation of elastic fibers
The above polyester polymer A6 was spun into a fiber having a fineness of 72dtex by a melt spinning method at 170 ℃. The fibers were left at 40 ℃ for 60min, then warmed to 70 ℃ and stretched to 4 times the original length. After cooling, the elastic fiber B6 is obtained.
Example 7
This example illustrates the elastic fibers and the method of making the same provided by the present invention.
(1) Preparation of polyester composition
Under the condition of stirring (the stirring speed is 10r/min, the stirring time is 10min), 196g of terephthalic acid butanediol-butanediol succinate copolyester A (the weight-average molecular weight is 130,000, wherein the content of the terephthalic acid butanediol repeating unit is 30 mol% based on the total molar number of the terephthalic acid butanediol repeating unit and the butanediol succinate repeating unit), 2g of terephthalic acid butanediol-butanediol succinate copolyester B (the weight-average molecular weight is 100,000, wherein the content of the terephthalic acid butanediol repeating unit is 10 mol% based on the total molar number of the terephthalic acid butanediol repeating unit and the butanediol succinate repeating unit), 2g of terephthalic acid butanediol-butanediol adipate copolyester C (the weight-average molecular weight is 100,000, wherein the total molar number of the terephthalic acid butanediol repeating unit and the butanediol adipate repeating unit is used as a reference, wherein the content of the repeating unit of butylene terephthalate is 60 mol%) and 10g of titanium dioxide, and stirring at a speed of 10r/min for 10min, then adding into a twin-screw extruder, melt-extruding at a temperature of 220 ℃ and granulating to obtain a polyester composition A7.
(2) Preparation of elastic fibers
The above polyester polymer A7 was spun into a fiber having a fineness of 72dtex by a melt spinning method at 170 ℃. The fibers were left at 40 ℃ for 60min, then warmed to 70 ℃ and stretched to 4 times their original length. After cooling, the elastic fiber B7 is obtained.
Example 8
This example illustrates the elastic fibers and the method of making the same provided by the present invention.
The procedure is as in example 1, except that polyester A is a butylene terephthalate-butylene adipate copolyester (weight average molecular weight 130,000, wherein the content of butylene terephthalate repeat units is 30 mole%, based on the total moles of butylene terephthalate repeat units and butylene adipate repeat units); the polyester B is butylene terephthalate-ethylene succinate (the weight-average molecular weight is 100,000, wherein the content of the butylene terephthalate repeating unit is 10 mol percent based on the total mole number of the butylene terephthalate repeating unit and the ethylene succinate repeating unit); the polyester C was butylene terephthalate-ethylene succinate (weight average molecular weight 100,000, wherein the content of butylene terephthalate repeat units was 60 mol%, based on the total number of moles of butylene terephthalate repeat units and ethylene succinate repeat units). Polyester composition A8 and elastic fiber B8 were obtained.
Example 9
This example illustrates the elastic fibers and the method of making the same provided by the present invention.
The procedure was followed as in example 1, except that polyester A was butylene terephthalate-ethylene succinate copolyester (weight average molecular weight 130,000, in which the content of butylene terephthalate repeat units was 30 mol% based on the total number of moles of butylene terephthalate repeat units and ethylene succinate repeat units); polyester B is butylene terephthalate-adipate (weight average molecular weight 100,000, wherein the content of butylene terephthalate repeat units is 10 mole% based on the total number of moles of butylene terephthalate repeat units and butylene adipate repeat units); polyester C was butylene terephthalate-adipate (weight average molecular weight 100,000, wherein the content of butylene terephthalate repeat units was 60 mol% based on the total number of moles of butylene terephthalate repeat units and butylene adipate repeat units). Polyester composition A9 and elastic fiber B9 were obtained.
Example 10
This example illustrates the elastic fibers and the method of making the same provided by the present invention.
The procedure of example 1 was followed except that the same weight of calcium carbonate was used in place of the titanium dioxide in example 1. Polyester composition A10 and elastic fiber B10 were obtained.
Example 11
This example illustrates the elastic fibers and the method of making the same provided by the present invention.
The procedure is as in example 1, except that 10g of titanium dioxide are not added. Polyester composition A11 and elastic fiber B11 were obtained.
Example 12
This example illustrates the elastic fibers and the method of making the same provided by the present invention.
(1) Preparation of polyester composition
The procedure of example 1 was repeated to obtain polyester composition A1.
(2) Preparation of elastic fibers
The above polyester polymer A1 was spun into a fiber having a fineness of 72dtex by a melt spinning method at 170 ℃. The fibers were left at 55 ℃ for 120min, then warmed to 110 ℃ and stretched to 10 times the original length. After cooling, the elastic fiber B12 is obtained.
Example 13
This example illustrates the elastic fibers and the method of making the same provided by the present invention.
(1) Preparation of polyester composition
The procedure of example 1 was repeated to obtain polyester composition A1.
(2) Preparation of elastic fibers
The above polyester polymer A1 was spun into a fiber having a fineness of 72dtex by a melt spinning method at 170 ℃. The fibers were left at 20 ℃ for 2min, then warmed to 56 ℃ and stretched to 1.2 times the original length. After cooling, the elastic fiber B13 is obtained.
Example 14
This example illustrates the elastic fibers and the method of making the same provided by the present invention.
(1) Preparation of polyester composition
The procedure of example 1 was repeated to obtain polyester composition A1.
(2) Preparation of elastic fibers
The above polyester polymer A1 was spun into a fiber having a fineness of 72dtex by a melt spinning method at 170 ℃. Then directly cooled to 70 ℃ and stretched 4 times the original length, excluding the procedure of example 1, which was left at 40 ℃. After cooling, the elastic fiber B14 is obtained.
Comparative example 1
The procedure is as in example 1, except that in step (1), 150g of the polyester A used in example 1, 50g of the polyester B used in example 1 and 10g of titanium dioxide are mixed without adding the polyester C used in example 1. Polyester composition DA1 and elastane DB1 were obtained.
Comparative example 2
The procedure of example 1 was followed except that, in step (1), 150g of the polyester A used in example 1, 50g of the polyester C used in example 1 and 10g of titanium dioxide were mixed without adding the polyester B used in example 1. Polyester composition DA2 and elastane DB2 were obtained.
Comparative example 3
The procedure is as in example 1, except that in step (1), 120g of the polyester B used in example 1, 80g of the polyester C used in example 1 and 10g of titanium dioxide are mixed without adding the polyester A used in example 1. Polyester composition DA3 and elastane DB3 were obtained.
Comparative example 4
The procedure is as in example 1, except that, in step (1), 20g of the polyester A used in example 1, 160g of the polyester B used in example 1, 20g of the polyester C used in example 1 and 10g of titanium dioxide are mixed. Polyester composition DA4 and elastane DB4 were obtained.
Comparative example 5
The procedure is as in example 1, except that, in step (1), instead of the polyester A used in example 1, the same weight of polybutylene succinate (available from BASF corporation under the designation 1111HTA4) is used. Polyester composition DA5 and elastane DB5 were obtained.
Comparative example 6
The procedure is as in example 1, except that, in step (1), instead of the polyester B used in example 1, the same weight of polybutylene succinate (available from BASF corporation under the designation 1111HTA4) is used. Polyester composition DA6 and elastane DB6 were obtained.
Comparative example 7
The procedure is as in example 1, except that, in step (1), instead of the polyester C used in example 1, the same weight of polybutylene adipate is used, the preparation of which comprises the following steps: in the nitrogen atmosphere, adipic acid and butanediol are stirred at 240 ℃ in the presence of tetrabutyl titanate and lanthanum acetylacetonate for reaction; the ratio of adipic acid, butanediol, tetrabutyl titanate and lanthanum acetylacetonate is 1800: 2000: 1: 1. after 2 hours of reaction, the system was evacuated until the pressure stabilized at 100Pa for half an hour. The residual substance in the system is the product. Polyester composition DA7 and elastane DB7 were obtained.
Comparative example 8
The procedure is as in example 1, except that, in step (1), 200g of the polyester A used in example 1 and 10g of titanium dioxide are mixed. Polyester composition DA8 and elastane DB8 were obtained.
Comparative example 9
The procedure is as in example 1, except that, in step (1), 200g of the polyester B used in example 1 and 10g of titanium dioxide are mixed. Polyester composition DA9 and elastane DB9 were obtained.
Comparative example 10
The procedure is as in example 1, except that, in step (1), 200g of the polyester C used in example 1 and 10g of titanium dioxide are mixed. Polyester composition DA10 and spandex DB10 were obtained.
Test examples 1 to 24
The elastic fibers obtained in examples 1 to 14 and comparative examples 1 to 10 were evaluated for breaking strength, elongation at break, stress relaxation and permanent set, respectively, according to the following methods. The results are shown in Table 1.
Specifically, a sample having a length of 2cm (L1) was stretched to 2 times the original length (strain: 100%) on an Instron 5965 stretcher at a speed of 50mm/min, and the stress at this time was designated as E1. After the length was maintained for 20 seconds, the stress at this time was recorded as E2. The strain was then reduced until the stress was 0, at which time the length of the specimen was L2. Then, the specimen was pulled at a speed of 50mm/min until it was broken, the specimen length at the time of breaking was L3, and the stress value was E3. The calculation formula of each parameter is as follows:
breaking strength E3
Elongation at break of 100% × (L3-L1)/L1
Stress relaxation rate%
Permanent strain rate of 100% × (L2-L1)/L1
TABLE 1
Figure BDA0001380988950000211
Note: "a" means that no intact fiber can be produced;
"b" indicates that the produced fiber has many broken filaments and poor uniformity;
"-" indicates no measurement.
As can be seen from the results of the above Table 1, the invention obtains the polyester composition by blending the specific polyester A, the specific polyester B and the specific polyester C according to the specific mixture ratio (30-98 wt% of the polyester A, 1-69 wt% of the polyester B, 1-69 wt% of the polyester C), the elastic fiber made of the polyester composition has good elastic performance, the breaking strength is more than or equal to 1cN/dtex, and the maximum breaking strength is close to 20cN/dtex by adjusting the formula and the molecular structure; in addition, the elongation at break of the elastic fiber provided by the invention is as high as more than 130%, and both the stress relaxation rate and the permanent strain rate can be less than or equal to 12%, which shows that the elastic fiber provided by the invention has moderate elasticity and strength and wide performance adjustability range, so that the elastic fiber has good application prospect.
In addition, as can be seen from the comparison of the results of example 1 with examples 12 to 14, the present invention particularly adopts the method and conditions of high temperature filamentation, low temperature standing and high temperature stretching to prepare the elastic fiber, which can further improve the breaking strength of the elastic fiber, expand the adjustable range of the performance, and reduce the stress relaxation and the permanent strain rate of the elastic fiber.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (30)

1. A polyester composition, characterized in that the polyester composition comprises the following components, based on the total weight of the components:
(1)30 to 98% by weight of a polyester A which is a copolymer comprising a repeating unit A represented by the formula (I) and a repeating unit B represented by the formula (II), wherein the content of the repeating unit A is 60 to 75% by mole and the content of the repeating unit B is 25 to 40% by mole, based on the total number of moles of the repeating unit A and the repeating unit B in the polyester A,
Figure FDF0000016511690000011
wherein m1 is an integer of 2 to 8, n1 is an integer of 2 to 4, and m1 and n1 are the same or different; the weight average molecular weight of the polyester A is 50,000-900,000;
(2)1 to 69% by weight of a polyester B which is a copolymer comprising a repeating unit C represented by the formula (III) and a repeating unit B represented by the formula (II), wherein the content of the repeating unit C is 83 to 95% by mole and the content of the repeating unit B is 5 to 17% by mole, based on the total number of moles of the repeating unit C and the repeating unit B in the polyester B,
Figure FDF0000016511690000012
wherein m2 is an integer of 2 to 8, n2 is an integer of 2 to 4, and m2 and n2 are the same or different; the weight average molecular weight of the polyester B is 50,000-900,000;
(3)1 to 69% by weight of a polyester C which is a copolymer comprising a repeating unit D represented by the formula (IV) and a repeating unit B represented by the formula (II), and the content of the repeating unit D is 15 to 45 mol% and the content of the repeating unit B is 55 to 85 mol% based on the total number of moles of the repeating unit D and the repeating unit B in the polyester C,
Figure FDF0000016511690000021
wherein m3 is an integer of 2 to 8, n3 is an integer of 2 to 4, and m3 and n3 are the same or different; the weight average molecular weight of the polyester C was 50,000-900,000.
2. The polyester composition of claim 1, wherein the polyester composition comprises 60 to 93 weight percent polyester a, 5 to 38 weight percent polyester B, and 1 to 20 weight percent polyester C.
3. The polyester composition according to claim 1, wherein the weight average molecular weight of the polyester A is 100,000-500,000.
4. The polyester composition according to claim 1, wherein in formula (I), m1 is an integer from 2 to 4.
5. The polyester composition according to claim 1, wherein the weight average molecular weight of the polyester B is 100,000-500,000.
6. The polyester composition according to claim 1, wherein in formula (III), m1 is an integer from 2 to 4.
7. The polyester composition according to claim 1, wherein the weight average molecular weight of the polyester C is 100,000-500,000.
8. The polyester composition according to claim 1, wherein in formula (IV), m3 is an integer from 2 to 4.
9. The polyester composition of claim 1, wherein the polyester composition further comprises an auxiliary filler.
10. The polyester composition of claim 9, wherein the auxiliary filler is present in an amount of 1 to 20 wt.%, based on the total weight of the polyester composition.
11. The polyester composition of claim 10, wherein the auxiliary filler is present in an amount of 2 to 10 wt.%, based on the total weight of the polyester composition.
12. The polyester composition of claim 9, wherein the auxiliary filler is selected from one or more of calcium carbonate, carbon black, talc, erucamide, titanium dioxide, low density polyethylene, polyphosphate, phosphite, hindered phenol, hindered amine, dibenzyl sorbitol and its derivatives, hyperbranched polyamide, and ethylene-methacrylic acid ionomer.
13. The polyester composition of claim 12, wherein the auxiliary filler is selected from one or more of calcium carbonate, carbon black, erucamide, titanium dioxide, tris (2, 3-dibromopropyl) phosphate, and low density polyethylene.
14. A process for the preparation of a polyester composition according to any of claims 1 to 13, characterized in that it comprises: polyester A, polyester B and polyester C were blended, and the resulting mixture was subjected to extrusion granulation.
15. The production method according to claim 14, wherein the blending is performed in the presence of an auxiliary filler.
16. The method of claim 14, wherein the auxiliary filler is used in an amount of 1 to 20 wt% based on the total weight of the polyester composition.
17. The method of claim 16, wherein the auxiliary filler is used in an amount of 2 to 10 wt% based on the total weight of the polyester composition.
18. The method of claim 14, wherein the blending is performed without the addition of a compatibilizer.
19. The method as claimed in claim 14, wherein the temperature of the extrusion granulation is 110-270 ℃.
20. The method as claimed in claim 19, wherein the temperature of the extrusion granulation is 130-230 ℃.
21. An elastic fiber comprising the polyester composition according to any one of claims 1 to 13 and/or the polyester composition obtained by the production method according to any one of claims 14 to 20.
22. The elastic fiber according to claim 21, wherein the elastic fiber has a fineness of 5 to 500 dtex; the breaking strength is 3-19 cN/dtex; the breaking elongation is 130-620 percent; the stress relaxation rate is 1-12%; the permanent strain rate is 1-11%.
23. A method of making an elastic fiber, comprising: sequentially carrying out filamentation, low-temperature placement and stretching on the polyester composition to obtain elastic fibers;
wherein the polyester composition is the polyester composition of any one of claims 1 to 13 and/or the polyester composition obtained by the preparation method of any one of claims 14 to 20.
24. The method of claim 23, wherein the filamentation is melt spinning.
25. The method as claimed in claim 24, wherein the filamentation temperature is 120-270 ℃.
26. The method as claimed in claim 25, wherein the filamentation temperature is 150-220 ℃.
27. The production method according to claim 24, wherein the condition of the low-temperature standing includes: the temperature is 20-55 deg.C, and the time is 2-120 min.
28. The production method according to claim 27, wherein the condition of the low-temperature standing includes: the temperature is 25-45 deg.C, and the time is 15-60 min.
29. The production method according to claim 24, wherein the conditions for the stretching include: the temperature is 56-110 ℃, and the stretching magnification is 1.2-10 times.
30. The production method according to claim 29, wherein the conditions for the stretching include: the temperature is 60-90 ℃, and the stretching magnification is 2-5 times.
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