CN112760740B

CN112760740B - Bio-based 2, 5-furandicarboxylic acid based copolyester fiber and preparation method and application thereof

Info

Publication number: CN112760740B
Application number: CN202110060463.7A
Authority: CN
Inventors: 陈鹏; 王鹏
Original assignee: Ningbo Institute of Material Technology and Engineering of CAS
Current assignee: Ningbo Institute of Material Technology and Engineering of CAS
Priority date: 2021-01-18
Filing date: 2021-01-18
Publication date: 2022-12-23
Anticipated expiration: 2041-01-18
Also published as: CN112760740A

Abstract

The invention discloses a bio-based 2, 5-furandicarboxylic acid based copolyester fiber and a preparation method and application thereof. The 2, 5-furandicarboxylic acid-based copolyester fiber is mainly prepared by reacting 2, 5-furandicarboxylic acid, terephthalic acid, ethylene glycol and C ₁₂ ‑C ₂₀ The glycol ether composition is polymerized to form 2, 5-furan diformyl copolyester, and then the polyester is prepared by melt spinning and hot drawing treatment. Compared with the prior PET fiber with the same molecular weight and molecular weight distribution, the 2, 5-furandicarboxylic acid based copolyester fiber prepared by the invention has higher tensile strength and elongation at break, breaks through the performance bottleneck of low tensile strength of the conventional copolyester fiber, expands the application range of the furan based copolyester fiber, has higher dye uptake and excellent normal pressure dyeability of the disperse dye under the condition of dyeing by the disperse dye, overcomes the problem of damage of high-temperature dyeing to the fiber quality, and obviously reduces the energy consumption during dyeing.

Description

Bio-based 2, 5-furandicarboxylic acid based copolyester fiber and preparation method and application thereof

Technical Field

The invention belongs to the technical field of fibers, and relates to a bio-based 2, 5-furandicarboxylic acid based copolyester fiber, and a preparation method and application thereof.

Background

In the past decades, synthetic fibers have been widely used in a variety of fields such as textiles, biomedicine, and agriculture. Polyesters such as polyethylene terephthalate (PET) are one of the polymers commonly used in these fields, but are petroleum based. With the global emphasis on environmental protection and sustainable development in recent years, the development of bio-based or partially bio-based polyesters is underway, and representative varieties include polylactic acid (PLA), polyhydroxyalkanoate (PHA), polybutylene succinate (PBS), and the like. However, all of the bio-based polyesters are aliphatic, and have a chain structure lacking rigid rings, and thus have insufficient properties in terms of strength, heat resistance, toughness, and the like.

The rigidity of polyesters is derived from terephthalic acid (PTA), and is currently not amenable to large scale production via biological routes. Fortunately, bio-based diacid-2, 5-furandicarboxylic acid (FDCA) is structurally similar to PTA and thus can be a suitable substitute for PTA. Polyethylene 2, 5-furandicarboxylate (PEF) obtained by polymerizing FDCA and bio-based Ethylene Glycol (EG) is a full bio-based polyester, and the mechanical and thermal properties of the polyester are similar to those of PET and are superior to those of the bio-based aliphatic polyester.

Although FDCA can be produced in small scale by biological routes, its price is still higher than PTA. A more practical strategy at present is to partially replace PTA with FDCA, i.e. to prepare 2, 5-furandicarboxylic acid based polyesters. Generally, introducing other diacid or diol into the PET molecular chain will destroy the regularity of the original molecular chain, thus hindering the orientation and crystallization of the molecular chain, and finally resulting in that the tensile strength of the copolyester fiber is reduced and lower than that of the PET fiber with the same molecular weight and molecular weight distribution while the elongation at break is increased. For example, PTA, EG, adipic acid and polyethylene glycol were copolymerized to obtain a copolyester and spun into a fiber (Textile Research Journal,2015, 16, 1691-1703), and when the copolymerized content of adipic acid reached 0.117mol relative to PTA, the elongation at break reached 186.7%, which was improved as compared with PET fiber, but the tensile strength was only 1.19gf/den (1.05 cN/dtex), which was reduced by 44.9% as compared with PET fiber. Currently, there are few published reports of fibers made using 2,5-furandicarboxylic acid based polyesters. Importantly, no reports have been made on 2, 5-furandicarboxylic acid based polyester fibers having both tensile strength and elongation at break higher than those of PET fibers of the same molecular weight, molecular weight distribution.

On the other hand, due to the lack of hydrophilic groups, the high stereoregular chain structure and the high crystallinity of the PET fibers, the dyeing rate of the PET fibers is low in normal-pressure dyeing, and the PET fibers can only be dyed under the conditions of high temperature and high pressure at present. Copolymerization is one of the main means for improving the dyeing performance of PET fibers, however, the prior art generally sacrifices the mechanical property of the PET fibers to improve the dye uptake. For example, PTA, EG, neopentyl glycol and sodium bis-hydroxyethyl isophthalate-5-sulfonate were copolymerized to obtain copolyester and spun into fiber (The Journal of The Textile Institute,2017, 11, 1949-1956), when The neopentyl glycol content in The copolyester was 9mol%, the dye uptake of The copolyester fiber was 95.91%, which was improved by 79.3% compared to PET fiber, but The tensile strength was only 2.03cN/dtex, which was reduced by 36.7% compared to PET fiber.

In conclusion, the development of the 2, 5-furandicarboxylic acid based polyester fiber with the dye uptake, the tensile strength and the elongation at break all higher than those of the PET fiber with the same molecular weight and molecular weight distribution has practical significance.

Disclosure of Invention

The invention mainly aims to provide a bio-based 2, 5-furandicarboxylic acid based copolyester fiber, a preparation method and an application thereof, so as to overcome the defects of the prior art.

In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:

the embodiment of the invention provides a bio-based 2, 5-furandicarboxylic acid based copolyester fiber, wherein the 2, 5-furandicarboxylic acid based copolyester fiber is prepared by mixing 2, 5-furandicarboxylic acid, terephthalic acid, ethylene glycol and C ₁₂ -C ₂₀ The glycol ether composition is polymerized to form 2, 5-furandicarboxylic acid copolyester, and then the copolyester is prepared by melt spinning and hot drawing.

Further, said C ₁₂ -C ₂₀ The glycol ether composition comprises any one or the combination of more than two of hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol and decaethylene glycol, the 2, 5-furandicarboxylic acid-based copolyester is random copolyester, the intrinsic viscosity of the 2, 5-furandicarboxylic acid-based copolyester is 0.65-1.00dL/g, and the entanglement molecular weight (M) of the 2, 5-furandicarboxylic acid-based copolyester _e ) Is 1000-1400g/mol. Further, the filament number of the 2, 5-furandicarboxylic acid-based copolyester fiber is 0.5-10dtex, the orientation degree of the 2, 5-furandicarboxylic acid-based copolyester fiber is 0.30-0.95, and the crystallinity degree of the 2, 5-furandicarboxylic acid-based copolyester fiber is 5-70%.

The embodiment of the invention also provides a preparation method of the bio-based 2, 5-furandicarboxylic acid-based copolyester fiber, which comprises the following steps:

under a protective atmosphere, 2, 5-furan dicarboxylic acid, terephthalic acid, ethylene glycol and C are added ₁₂ -C ₂₀ The glycol ether composition, the esterification catalyst, the polycondensation catalyst, the stabilizer and the antioxidant are reacted to prepare the catalyst2, 5-furandicarboxylic acid-based copolyester;

drying the obtained 2, 5-furandicarboxylic acid-based copolyester to ensure that the water content of the 2, 5-furandicarboxylic acid-based copolyester is at least below 70ppm;

and spinning the dried 2, 5-furandicarboxylic acid-based copolyester to obtain 2, 5-furandicarboxylic acid-based copolyester nascent fiber, and then performing hot drawing treatment to obtain the 2, 5-furandicarboxylic acid-based copolyester fiber.

The embodiment of the invention also provides the application of the bio-based 2, 5-furandicarboxylic acid-based copolyester fiber in the fields of home textile, clothing or agriculture.

Compared with the prior art, the invention has the beneficial effects that:

(1) The invention provides a preparation method of bio-based 2, 5-furandicarboxylic acid based copolyester fiber, which selects C containing-C-O-ether oxygen bond ₁₂ -C ₂₀ Glycol ether composition as comonomer, and regulation C ₁₂ -C ₂₀ Molar ratio of glycol ether composition to FDCA increases compliance of 2, 5-furandicarboxylic acid-based copolyester, entanglement molecular weight (M) of prepared 2, 5-furandicarboxylic acid-based copolyester _e ) PET of less than the same molecular weight, molecular weight distribution;

(2) Compared with PET fibers with the same molecular weight and molecular weight distribution, the bio-based 2, 5-furandicarboxylic acid based copolyester fibers prepared by the invention have higher tensile strength and elongation at break, break through the performance bottleneck of low tensile strength of conventional copolyester fibers, and expand the application range of the furan based copolyester fibers;

(3) Compared with PET fibers with the same molecular weight and molecular weight distribution, the bio-based 2, 5-furandicarboxylic acid based copolyester fibers prepared by the method have higher dye uptake rate under the condition of dyeing by adopting disperse dyes;

(4) Compared with PET fibers with the same molecular weight and molecular weight distribution, the bio-based 2, 5-furandicarboxylic acid based copolyester fibers prepared by the method have excellent dyeability of disperse dyes under normal pressure, can be dyed at 100 ℃, have high dye uptake, overcome the problem of damage of high-temperature dyeing to fiber quality, and remarkably reduce energy consumption during dyeing.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and it is also possible for those skilled in the art to obtain other drawings based on the drawings without creative efforts.

FIG. 1 is a drawing graph showing the drawing curves of 2, 5-furandicarboxylic acid-based copolyester fibers, PET fibers, prepared in example 7, example 8 and comparative example 2 according to the present invention;

FIG. 2 is a differential scanning calorimetry trace of 2, 5-furandicarboxylic acid-based copolyester fibers and PET fibers prepared in example 2 and comparative example 1 of the present invention;

FIG. 3 is a wide-angle X-ray diffraction curve of 2, 5-furandicarboxylic acid-based copolyester fibers, PET fibers prepared in example 1, example 2 and comparative example 1 of the present invention.

Detailed Description

In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to propose the technical solution of the present invention, which will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

An aspect of an embodiment of the present invention provides a bio-based 2, 5-furandicarboxylic acid-based copolyester fiber, the 2, 5-furandicarboxylic acid-based copolyester fiber being prepared by reacting 2, 5-furandicarboxylic acid (FDCA), terephthalic acid (PTA), ethylene Glycol (EG), and C ₁₂ -C ₂₀ Polymerization of glycol ether compositions to form 2,5-The furan dicarboxylic acid based copolyester is prepared by melt spinning and hot drawing treatment.

In some more specific embodiments, the 2, 5-furandicarboxylic acid-based copolyester is a random copolyester.

Further, the intrinsic viscosity of the 2, 5-furandicarboxylic acid-based copolyester is 0.65 to 1.00dL/g, preferably 0.70 to 0.95dL/g.

Further, the entanglement molecular weight (M) of the 2, 5-furandicarboxylic acid-based copolyester _e ) Is 1000 to 1400g/mol, preferably 1100 to 1300g/mol, where M _e Is calculated from the plateau modulus, M _e The calculation formula of (c) is as follows:

in the formula

The plateau modulus, T the scanning temperature, ρ the melt density at temperature T, and R the gas constant.

Further, the filament number of the 2, 5-furandicarboxylic acid-based copolyester fiber is 0.5 to 10dtex, preferably 1 to 5dtex.

Further, the orientation degree of the 2, 5-furandicarboxylic acid-based copolyester fiber is 0.30 to 0.95, preferably 0.60 to 0.90.

Further, the crystallinity of the 2, 5-furandicarboxylic acid-based copolyester fiber is 5 to 70%, preferably 25 to 65%.

Furthermore, when the 2, 5-furandicarboxylic acid-based copolyester fiber is dyed at 100-130 ℃, the dye-uptake of the 2, 5-furandicarboxylic acid-based copolyester fiber is more than 87%.

Further, said C ₁₂ -C ₂₀ The glycol ether composition includes any one or a combination of two or more of hexa glycol, hepta glycol, octa glycol, nona glycol, and deca glycol, and is not limited thereto.

Another aspect of the embodiments of the present invention also provides a method for preparing the aforementioned bio-based 2, 5-furandicarboxylic acid-based copolyester fiber, which includes:

under a protective atmosphere, 2, 5-furan dicarboxylic acid, terephthalic acid, ethylene glycol and C are added ₁₂ -C ₂₀ The mixed reaction system of the glycol ether composition, the esterification catalyst, the polycondensation catalyst, the stabilizer and the antioxidant reacts to prepare 2, 5-furandicarboxylic acid-based copolyester;

In some more specific embodiments, the method of making comprises: reacting the 2, 5-furandicarboxylic acid, terephthalic acid, ethylene glycol, C under a protective atmosphere ₁₂ -C ₂₀ Mixing the glycol ether composition with an esterification catalyst, reacting at 150-200 ℃ for 1-4h, adding a polycondensation catalyst, a stabilizer and an antioxidant, prepolymerizing at 180-240 ℃ and under the vacuum degree of 0.01-0.05MPa for 1-2h, reducing the vacuum degree to below 300Pa, and reacting at 250-270 ℃ for 3-6h to obtain the 2, 5-furandicarboxylic acid based copolyester.

Further, the molar ratio of the 2, 5-furandicarboxylic acid to the sum of the 2, 5-furandicarboxylic acid and terephthalic acid is from 0.01 to 0.99.

Further, said C ₁₂ -C ₂₀ The molar ratio of the glycol ether composition to the 2, 5-furandicarboxylic acid is from 0.01 to 0.05, preferably from 0.02 to 0.04.

Further, the molar ratio of the ethylene glycol to the sum of 2, 5-furandicarboxylic acid and terephthalic acid is 1.2 to 1.8.

Further, the molar ratio of the esterification catalyst to the sum of 2, 5-furandicarboxylic acid and terephthalic acid is 0.001 to 0.003.

Further, the molar ratio of the polycondensation catalyst to the sum of 2, 5-furandicarboxylic acid and terephthalic acid is 0.001 to 0.0035.

Further, the molar ratio of the stabilizer to the sum of 2, 5-furandicarboxylic acid and terephthalic acid is 0.0010 to 0.0025.

Further, the molar ratio of the antioxidant to the sum of 2, 5-furandicarboxylic acid and terephthalic acid is from 0.001 to 0.002.

Further, the esterification catalyst includes any one or a combination of two or more of anhydrous zinc acetate, anhydrous manganese acetate, anhydrous cobalt acetate, n-butyl titanate, stannous octoate, and is not limited thereto.

Further, the polycondensation catalyst includes any one or a combination of two or more of antimony trioxide, tetrabutyl titanate, isobutyl titanate, and dibutyltin oxide, and is not limited thereto.

Further, the stabilizer includes any one or a combination of two or more of phosphoric acid, phosphorous acid, triphenyl phosphate, triphenyl phosphite, trimethyl phosphate, trimethyl phosphite, triisooctyl phosphite, and tri-p-tolyl phosphite, and is not limited thereto.

Further, the antioxidant includes any one or a combination of two or more of antioxidant-176, antioxidant-168, and antioxidant-1010, and is not limited thereto.

In some more specific embodiments, the method of making comprises: and (3) blowing the 2, 5-furandicarboxylic acid-based copolyester by using hot air with the temperature of 100-170 ℃ for 7-15h, so that the water content of the 2, 5-furandicarboxylic acid-based copolyester is below 70 ppm.

Further, the 2, 5-furandicarboxylic acid-based copolyester is subjected to a purging treatment for 9-13h by using hot air with the temperature of 130-160 ℃, so that the water content of the 2, 5-furandicarboxylic acid-based copolyester is below 40ppm.

In some comparativelyIn a particular embodiment, the method of preparation comprises: melting the dried 2, 5-furandicarboxylic acid-based copolyester into a spinning manifold through a screw, spraying the melted copolyester into a spinneret plate of a spinning assembly through a metering pump to form a strand silk, and cooling and winding the strand silk in an air cooling zone to obtain the 2, 5-furandicarboxylic acid-based copolyester as-spun fiber, wherein the temperature of the screw is 200-300 ℃, the temperature of the spinning assembly is 230-300 ℃, and the apparent shear rate at the hole wall of the spinneret plate is 1000-3500s ^-1 The metering pump speed is 1.0-4.0ml/rev, the spinneret aperture is 0.2-0.8mm, the number of holes is 1-200 holes, the length-diameter ratio (L/D) is 1-10, the temperature of an air cooling zone is 10-120 ℃, the winding speed is 100-5000m/min, wherein the apparent shear rate at the hole wall of the spinneret

Is determined using the following equation:

wherein Q is the melt flow (mm) ³ And/s), r is the radius (mm) of the spinneret hole.

Further, the temperature of the screw is 220-290 ℃, and the temperature of the spinning assembly is 240-290 ℃.

Further, the apparent shear rate at the hole wall of the spinneret plate is 1200-3200s ^-1 The speed of the metering pump is 1.2-3.6ml/rev, the aperture of the spinneret plate is 0.28-0.60mm, the number of holes is 4-100 holes, and the length-diameter ratio (L/D) is 3-8.

Further, the air cooling area comprises a slow cooling area with the temperature of 80-120 ℃ and a cooling area with the temperature of 25-40 ℃; preferably, the slow cooling area is arranged at a position 40-140mm below the spinneret plate.

In some more specific embodiments, the method of making comprises: the obtained 2, 5-furandicarboxylic acid based copolyester nascent fiber is subjected to hot drawing treatment under the conditions that the temperature is 85-130 ℃ and the drawing ratio is 1.0-6.0, so as to obtain the 2, 5-furandicarboxylic acid based copolyester fiber.

Further, when the hot drawing treatment is a one-step drawing method, the draw ratio is 2.0 to 4.0 and the drawing temperature is 95 to 120 ℃.

Further, when the hot drawing treatment is a two-step drawing method, the draw ratio is 1.4 to 4.0, and the drawing temperature is 90 to 110 ℃.

In some more specific embodiments, the method for preparing the bio-based 2, 5-furandicarboxylic acid-based copolyester fiber comprises:

(1) FDCA, PTA, EG and C ₁₂ -C ₂₀ Polymerizing the glycol ether composition to obtain random copolyester;

(2) Continuously blowing the 2, 5-furandicarboxylic acid-based copolyester for 7-15h by using hot air with the temperature of 100-170 ℃ to ensure that the water content of the copolyester is lower than 70ppm;

preferably, the hot air temperature is 130-160 ℃, the purging time is 9-13h, and the water content is lower than 40ppm, wherein the water content is measured by a differential pressure type micro-moisture meter at 220 ℃.

(3) Melting the dried 2, 5-furandicarboxylic acid-based copolyester by a screw, feeding the melt into a spinning manifold, spraying the melt from a spinneret plate of a spinning component by a metering pump to form filaments, cooling the filaments by an air cooling zone, and winding to obtain the 2, 5-furandicarboxylic acid-based copolyester as-spun fiber, wherein the temperature of the screw is 200-300 ℃, the temperature of the spinning component is 230-300 ℃, and the apparent shear rate at the hole wall of the spinneret plate is 1000-3500s ^-1 The metering pump speed is 1.0-4.0ml/rev, the spinneret plate aperture is 0.2-0.8mm, the number of holes is 1-200, the length-diameter ratio (L/D) is 1-10, the air cooling zone temperature is 10-120 ℃, and the winding speed is 100-5000m/min.

Preferably, the screw temperature is 220-290 ℃ and the spin pack temperature is 240-290 ℃.

Preferably, the apparent shear rate at the wall of the spinneret hole is 1200-3200s ^-1 The metering pump speed is 1.2-3.6ml/rev, the spinneret aperture is 0.28-0.60mm, the number of holes is 4-100 holes, the length-diameter ratio (L/D) is 3-8, wherein the apparent shear rate at the hole wall of the spinneret plate

Is determined using the following equation:

wherein Q is melt flow (mm) ³ And/s), r is the radius (mm) of the spinneret hole.

Preferably, the air cooling zone comprises a slow cooling zone which is 40-140mm away from the lower part of the spinneret and has the hot air temperature of 80-120 ℃, and a cooling zone which is closely adjacent to the slow cooling zone and enables the filament to be rapidly cooled in air of 25-40 ℃.

(4) The 2, 5-furan diformyl copolyester nascent fiber is subjected to hot drawing at the temperature of 85-130 ℃ and the drawing ratio of 1.0-6.0 to prepare the 2, 5-furan diformyl copolyester fiber.

Preferably, when a single drawing mode is selected, the drawing temperature is 95 to 120 ℃ and the drawing ratio is 2.0 to 4.0.

Preferably, when the two-stage drawing mode is selected, the drawing temperature is 90 to 110 ℃ and the drawing ratio is 1.4 to 4.0.

The method of the invention comprises the following steps of ₁₂ -C ₂₀ The glycol ether composition is copolymerized with FDCA, PTA and EG to improve the flexibility of the molecular chain of 2, 5-furan diformyl copolyester, and further ensure the entanglement molecular weight (M) of the molecular chain of the copolyester _e ) Less than PET, M of the same molecular weight and molecular weight distribution _e The decrease of (2) increases the number of entanglement points of the molecular chain, prolongs the disentanglement time of the molecular chain, and finally results in that the extensional viscosity of the 2, 5-furandicarboxylic acid-based copolyester is higher than that of PET with the same molecular weight and molecular weight distribution. Published reports indicate that the tension on the melt spinning stroke is composed of friction, inertial force, and rheological force, where rheological force is positively correlated with extensional viscosity. Thus, C ₁₂ -C ₂₀ The introduction of the glycol ether composition makes the tension of the copolyester on the spinning process higher than that of PET with the same molecular weight and molecular weight distribution. The high tensile forces on the spinning process produce a high degree of orientation, which does not induce a high degree of crystallinity in the copolyester fibers, but rather exhibits a lower degree of crystallinity than PET fibers of the same molecular weight, molecular weight distribution, primarily due to the disruption of the molecular chain regularity of the copolyester.

Due to high orientation degree, low crystallinity and increased molecular chain flexibility, the tensile strength and elongation at break of the 2, 5-furandicarboxylic acid based copolyester fiber are higher than those of PET fiber with the same molecular weight and molecular weight distribution; on the other hand, the increase of the flexibility of the copolyester molecular chain means that the motion capability of the chain segment is enhanced, thereby facilitating the disperse dye molecules to enter the copolyester fiber; the loss of molecular chain regularity increases the amorphous region of the copolyester fiber and increases the space for holding the disperse dye molecules. More importantly, FDCA and C ₁₂ -C ₂₀ Ether oxygen bond (-C-O-) on the molecular chain of the glycol ether and amino (-NH) on the molecule of the disperse dye ₂ ) Functional groups such as hydroxyl (-OH) and the like have stronger intermolecular interaction force, and are favorable for adsorption of disperse dye molecules. The factors together result in higher dye uptake of the 2, 5-furandicarboxylic acid-based copolyester fiber and excellent atmospheric dyeability of the disperse dye compared with PET fiber with the same molecular weight and molecular weight distribution.

Another aspect of an embodiment of the present invention also provides the use of the aforementioned bio-based 2, 5-furandicarboxylic acid-based copolyester fiber in the field of home textile, clothing or agriculture.

The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments. In the present invention, the intrinsic viscosity [ eta ] of the copolyester]Measuring by adopting a Ubbelohde viscometer; weight average molecular weight (M) of the copolyester _w ) And molecular weight Distribution (DI) by Gel Permeation Chromatography (GPC); plateau modulus of copolyester

Measured in parallel plate mode using a rotational rheometer and the entanglement molecular weight (M) calculated _e ) (ii) a The orientation degree of the copolyester fiber is measured by a sound velocity orientation method; the crystallinity of the copolyester fiber is jointly determined by Differential Scanning Calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) methods; stretching of copolyester fibersThe strength and the elongation at break are measured by a universal material testing machine; the dye uptake of the disperse dye of the copolyester fiber is determined by a residual liquid colorimetric method.

The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.

Example 1

Firstly, 2, 5-furandicarboxylic acid (FDCA), terephthalic acid (PTA), ethylene Glycol (EG), hexaethylene glycol and nonaethylene glycol composition (the molar ratio of the two is 1; then antimony trioxide accounting for 0.12 percent of the total molar weight of FDCA and PTA, triphenyl phosphate accounting for 0.20 percent of the total molar weight of FDCA and PTA and antioxidant-176 accounting for 0.15 percent of the total molar weight of FDCA and PTA are added into a reaction kettle, the reaction kettle is slowly vacuumized to 0.03MPa, and prepolymerization is carried out for 1 hour at the temperature of 198 ℃; finally, gradually heating to 260 ℃, continuously vacuumizing to below 200Pa and reacting for 4 hours to obtain the 2, 5-furandicarboxylic acid copolyester. The intrinsic viscosity of the copolyester is detected to be 0.70dL/g; weight average molecular weight (M) _w ) And a molecular weight Distribution (DI) of 23700g/mol, 1.63, respectively; entanglement molecular weight (M) _e ) Was 1273g/mol.

The copolyester was continuously purged with hot air at 130 ℃ for 10 hours to bring the water content to 40ppm. Injecting the dried copolyester into a screw extruder for melting, spraying the copolyester from a spinneret plate of a spinning component through a spinning box body and a metering pump, cooling the copolyester through an air cooling zone and then winding the copolyester to prepare 2, 5-furandicarboxylic acid group copolyester as-spun fiber, and finally performing hot drawing treatment to prepare the 2, 5-furandicarboxylic acid group copolyester fiber, wherein the temperature of the spinning component is 275 ℃, the spinning speed is 2500m/min, and the apparent shear rate at the hole wall of the spinneret plate is 2000s ^-1 The temperatures of the slow cooling zone and the cooling zone of the air cooling zone were 100 ℃ and 40 ℃ respectively, the hot drawing temperature was 110 ℃ and the draw ratio was 2.0, and the filament fineness of the 2, 5-furandicarboxylic acid based copolyester fiber was 5dtex. The copolyester fiber is dyed by using conventional disperse dyes at the temperatures of 90, 100, 110, 120 and 130 ℃.

Through detection, the orientation degree of the 2, 5-furandicarboxylic acid-based copolyester fiber is 0.67; the crystallinity of the copolyester fiber was measured to be 36% and 48% by Differential Scanning Calorimetry (DSC) curve (fig. 2) and wide-angle X-ray diffraction (WAXD) curve (fig. 3), respectively; the tensile strength and elongation at break of the copolyester fiber are 3.2cN/dtex and 70 percent respectively; the dye uptake of the copolyester fiber at 90, 100, 110, 120 and 130 ℃ is respectively 56.8%, 87.8%, 88.3%, 90.2% and 92.3%.

Example 2

Firstly, 2, 5-furandicarboxylic acid (FDCA), terephthalic acid (PTA), ethylene Glycol (EG), decaethylene glycol, anhydrous zinc acetate are added to a reaction kettle according to a molar ratio of 0.10; then tetrabutyl titanate accounting for 0.12 percent of the total molar weight of FDCA and PTA, triphenyl phosphate accounting for 0.20 percent of the total molar weight of FDCA and PTA and antioxidant-1010 accounting for 0.15 percent of the total molar weight of FDCA and PTA are added into a reaction kettle, the reaction kettle is slowly vacuumized to 0.03MPa, and prepolymerization is carried out for 1h at the temperature of 190 ℃; finally, gradually heating to 260 ℃, continuously vacuumizing to below 200Pa and reacting for 4 hours to obtain the 2, 5-furandicarboxylic acid copolyester. The intrinsic viscosity of the copolyester is detected to be 0.75dL/g; weight average molecular weight (M) _w ) And molecular weight Distribution (DI) of 27910g/mol, 1.55; entanglement molecular weight (M) _e ) Was 1180g/mol.

Continuously blowing the copolyester for 10 hours by using hot air at 130 ℃ to ensure that the water content is 35ppm, injecting the dried copolyester into a screw extruder for melting, spraying the copolyester from a spinneret plate of a spinning assembly through a spinning box body and a metering pump, cooling the copolyester through an air cooling zone, then winding the cooled copolyester to prepare 2, 5-furandicarboxylic acid group copolyester as-spun fiber, and finally carrying out hot drafting treatment to prepare the 2, 5-furandicarboxylic acid group copolyester fiber, wherein the temperature of the spinning assembly is 272 ℃, the spinning speed is 2500m/min, and the apparent shear rate at the hole wall of the spinneret plate is 1920s ^-1 The temperatures of the slow cooling zone and the cooling zone of the air cooling zone were 100 ℃ and 35 ℃, respectively, the hot drawing temperature was 110 ℃, and the draw ratio was 2.0, 5-furandicarboxylic acid based copolyester fiber having a single fiber fineness of 5dtex. The copolyester fibers are dyed with conventional disperse dyes at temperatures of 90, 100, 110, 120, 130 ℃ respectively.

The detection proves that the orientation degree of the 2, 5-furan diformyl copolyester fiber is 0.77; the crystallinity of the copolyester fiber was measured by DSC (fig. 2) and WAXD (fig. 3) to be 35% and 46%, respectively; the tensile strength and the elongation at break of the copolyester fiber are respectively 4.1cN/dtex and 45%; the dye uptake of the copolyester fiber at 90 ℃, 100 ℃, 110 ℃, 120 ℃ and 130 ℃ is 67.2%, 92.1%, 93.2%, 93.9% and 94.1% respectively.

Example 3

Firstly, 2, 5-furandicarboxylic acid (FDCA), terephthalic acid (PTA), ethylene Glycol (EG), octaglycol and nonaethylene glycol composition (the molar ratio of the two is 1; then adding dibutyltin oxide accounting for 0.11 percent of the total molar weight of FDCA and PTA, trimethyl phosphate accounting for 0.23 percent of the total molar weight of FDCA and PTA and antioxidant-1010 accounting for 0.15 percent of the total molar weight of FDCA and PTA into a reaction kettle, slowly vacuumizing to 0.04MPa, and prepolymerizing for 1 hour at 187 ℃; finally, gradually heating to 257 ℃, continuously vacuumizing to below 200Pa, and reacting for 4 hours to obtain 2, 5-furandicarboxylic acid copolyester; the intrinsic viscosity of the copolyester is detected to be 0.71dL/g; weight average molecular weight (M) _w ) And molecular weight Distribution (DI) of 24740g/mol, 1.37, respectively; entanglement molecular weight (M) _e ) Is 1245g/mol.

Continuously blowing the copolyester for 10 hours by using hot air at 130 ℃ to ensure that the water content of the copolyester is 32ppm, injecting the dried copolyester into a screw extruder to be melted, spraying the copolyester from a spinneret plate of a spinning assembly through a spinning box and a metering pump, cooling the copolyester through an air cooling zone, winding the cooled copolyester to prepare 2, 5-furandicarboxylic acid based copolyester nascent fiber, and finally carrying out hot drafting treatment to prepare the 2, 5-furandicarboxylic acid based copolyester fiber, wherein the temperature of the spinning assembly is 272 ℃, the spinning speed is 2500m/min, and the apparent shear rate at the hole wall of the spinneret plate is 2120s ^-1 The temperatures of the slow cooling zone and the cooling zone of the air cooling zone were 100 ℃ and 32 ℃ respectively, the hot drawing temperature was 110 ℃ and the draw ratio was 2.0, and the filament fineness of the 2, 5-furandicarboxylic acid based copolyester fiber was 5dtex. The copolyester fibers are dyed with conventional disperse dyes at temperatures of 90, 100, 110, 120, 130 ℃ respectively.

Through detection, the orientation degree of the 2, 5-furandicarboxylic acid-based copolyester fiber is 0.69; the crystallinity of the copolyester fiber was 25% and 38% as determined by DSC and WAXD, respectively; the tensile strength and the elongation at break of the copolyester fiber are respectively 3.3cN/dtex and 65%; the dye uptake of the copolyester fiber at 90, 100, 110, 120 and 130 ℃ is respectively 68.4%, 93.2%, 93.8%, 94.2% and 94.7%.

Example 4

Firstly, 2, 5-furandicarboxylic acid (FDCA), terephthalic acid (PTA), ethylene Glycol (EG), nonaethylene glycol and anhydrous zinc acetate are added into a reaction kettle according to a molar ratio of 0.30; then adding dibutyltin oxide accounting for 0.12 percent of the total molar weight of FDCA and PTA, 0.17 percent of triphenyl phosphite and 0.15 percent of antioxidant-168 into a reaction kettle, slowly vacuumizing to 0.04MPa, and prepolymerizing for 1 hour at 185 ℃; finally, gradually heating to 255 ℃, continuously vacuumizing to below 200Pa and reacting for 4h to obtain the 2, 5-furandicarboxylic acid copolyester. The intrinsic viscosity of the copolyester is detected to be 0.73dL/g; weight average molecular weight (M) _w ) And a molecular weight Distribution (DI) of 26430g/mol, 1.52; entanglement molecular weight (M) _e ) Is 1240g/mol.

Continuously blowing the copolyester for 10 hours by using hot air at 130 ℃ to ensure that the water content of the copolyester is 37ppm, injecting the dried copolyester into a screw extruder to be melted, spraying the copolyester from a spinneret plate of a spinning assembly through a spinning box and a metering pump, cooling the copolyester through an air cooling zone, winding the cooled copolyester to prepare 2, 5-furandicarboxylic acid based copolyester nascent fiber, and finally carrying out hot drafting treatment to prepare the 2, 5-furandicarboxylic acid based copolyester fiber, wherein the temperature of the spinning assembly is 270 ℃, the spinning speed is 2500m/min, and the apparent shear rate at the hole wall of the spinneret plate is 2120s ^-1 The temperatures of the air-cooling zones a and b were 100 ℃ and 30 ℃ respectively, the hot-drawing temperature was 110 ℃ and the draw ratio was 2.0, and the filament fineness of the 2, 5-furandicarboxylic acid-based copolyester fiber was 5dtex. The copolyester fiber is dyed by using conventional disperse dyes at the temperatures of 90, 100, 110, 120 and 130 ℃.

The orientation degree of the copolyester fiber is detected to be 0.71; the crystallinity of the copolyester fiber measured by DSC and WAXD was 29% and 40%, respectively; the tensile strength and elongation at break of the copolyester fiber are respectively 3.5cN/dtex and 60%; the dye uptake of the copolyester fiber at 90, 100, 110, 120 and 130 ℃ is respectively 70.2%, 95.0%, 95.4%, 96.1% and 96.8%.

Example 5

Firstly, adding 2, 5-furandicarboxylic acid (FDCA), terephthalic acid (PTA), ethylene Glycol (EG), hexaethylene glycol and anhydrous zinc acetate into a reaction kettle according to a molar ratio of 0.80. The intrinsic viscosity of the copolyester is detected to be 0.72dL/g; weight average molecular weight (M) _w ) And a molecular weight Distribution (DI) of 25690g/mol, 1.38, respectively; entanglement molecular weight (M) _e ) The concentration was 1300g/mol.

Continuously blowing the copolyester for 10 hours by using hot air at 130 ℃ to ensure that the water content of the copolyester is 37ppm, injecting the dried copolyester into a screw extruder to be melted, spraying the copolyester out of a spinneret plate of a spinning assembly through a spinning box and a metering pump, cooling the copolyester through an air cooling zone and then winding the copolyester to prepare 2, 5-furandicarboxylic acid based copolyester nascent fiber, and finally carrying out hot drafting treatment to prepare the 2, 5-furandicarboxylic acid based copolyester fiber, wherein the temperature of the spinning assembly is 270 ℃, the spinning speed is 2500m/min, and the apparent shear rate at the hole wall of the spinneret plate is 2085s ^-1 The temperatures of the air-cooling zones a and b were 100 ℃ and 25 ℃, respectively, the hot-drawing temperature was 110 ℃, and the single-filament fineness of the 2.0,2, 5-furandicarboxylic acid-based copolyester fiber was 5dtex. The copolyester fibers are dyed with conventional disperse dyes at temperatures of 90, 100, 110, 120, 130 ℃ respectively.

The orientation degree of the copolyester fiber is detected to be 0.66; the crystallinity of the copolyester fiber measured by DSC and WAXD was 31% and 43%, respectively; the tensile strength and elongation at break of the copolyester fiber are 3.1cN/dtex and 75% respectively; the dye uptake of the copolyester fiber at 90, 100, 110, 120 and 130 ℃ is respectively 70.8%, 95.1%, 95.8%, 96.4% and 97.2%.

Example 6

Firstly, adding 2, 5-furandicarboxylic acid (FDCA), terephthalic acid (PTA), ethylene Glycol (EG), a composition of nonaethylene glycol and decaethylene glycol (the molar ratio of the two is 1. The intrinsic viscosity of the copolyester is detected to be 0.75dL/g; weight average molecular weight (M) _w ) And molecular weight Distribution (DI) of 27910g/mol, 1.55; entanglement molecular weight (M) _e ) Was 1229g/mol.

Continuously blowing the copolyester for 10 hours by using hot air at 130 ℃ to ensure that the water content of the copolyester is 32ppm, injecting the dried copolyester into a screw extruder to be melted, spraying the copolyester out of a spinneret plate of a spinning assembly through a spinning box and a metering pump, cooling the copolyester through an air cooling zone, winding the cooled copolyester to prepare 2, 5-furandicarboxylic acid based copolyester nascent fiber, and finally carrying out hot drafting treatment to prepare the 2, 5-furandicarboxylic acid based copolyester fiber, wherein the temperature of the spinning assembly is 270 ℃, the spinning speed is 2500m/min, and the apparent shear rate at the hole wall of the spinneret plate is 2145s ^-1 The temperatures of the air-cooling zones a and b were 100 ℃ and 25 ℃, respectively, the hot-drawing temperature was 110 ℃, and the draw ratio was 2.0, and the filament fineness of the 2, 5-furandicarboxylic acid-based copolyester fiber was 5dtex. The copolyester fiber is dyed by using conventional disperse dyes at the temperatures of 90, 100, 110, 120 and 130 ℃.

The orientation degree of the copolyester fiber is detected to be 0.73; the crystallinity of the copolyester fiber was 33% and 45% as measured by DSC and WAXD, respectively; the tensile strength and elongation at break of the copolyester fiber are 3.7cN/dtex and 50% respectively; the dye uptake of the copolyester fiber at 90, 100, 110, 120 and 130 ℃ is 72.3%, 96.4%, 97.2%, 97.7% and 98.3% respectively.

Example 7

Firstly, adding 2, 5-furandicarboxylic acid (FDCA), terephthalic acid (PTA), ethylene Glycol (EG), decaethylene glycol and anhydrous cobalt acetate into a reaction kettle according to a molar ratio of 0.10. The intrinsic viscosity of the copolyester is detected to be 0.90dL/g; weight average molecular weight (M) _w ) And molecular weight Distribution (DI) of 33750g/mol, 1.47, respectively; entanglement molecular weight (M) _e ) Was 1180g/mol.

Continuously blowing the copolyester for 10 hours by using hot air at 130 ℃ to ensure that the water content of the copolyester is 40ppm, injecting the dried copolyester into a screw extruder to be melted, spraying the copolyester out of a spinneret plate of a spinning assembly through a spinning box and a metering pump, cooling the copolyester through an air cooling zone, winding the cooled copolyester to prepare 2, 5-furandicarboxylic acid based copolyester nascent fiber, and finally carrying out hot drafting treatment to prepare the 2, 5-furandicarboxylic acid based copolyester fiber, wherein the temperature of the spinning assembly is 276 ℃, the spinning speed is 2500m/min, and the apparent shear rate at the hole wall of the spinneret plate is 2000s ^-1 The temperatures of the air-cooling zones a and b were 100 ℃ and 40 ℃ respectively, the hot-drawing temperature was 115 ℃ and the draw ratio was 3.0, and the filament fineness of the 2, 5-furandicarboxylic acid-based copolyester fiber was 1 dtex. The copolyester fiber is dyed by using conventional disperse dyes at the temperatures of 90, 100, 110, 120 and 130 ℃.

The detection proves that the orientation degree of the copolyester fiber is 0.89; the crystallinity of the copolyester fiber was 40% and 49% by DSC and WAXD, respectively; the tensile strength and elongation at break (FIG. 1) of the copolyester fibers were 7.2cN/dtex and 19.6%, respectively; the dye uptake of the copolyester fiber at 90, 100, 110, 120 and 130 ℃ is respectively 62.6%, 90.2%, 91.1%, 91.7% and 92.3%.

Example 8

Firstly, 2, 5-furandicarboxylic acid (FDCA), terephthalic acid (PTA), ethylene Glycol (EG), heptaglycol and nonaglycol composition (the molar ratio of the two is 1). The intrinsic viscosity of the copolyester is detected to be 0.87dL/g; weight average molecular weight (M) _w ) And a molecular weight Distribution (DI) of 31800g/mol and 1.53, respectively; entanglement molecular weight (M) _e ) It was 1270g/mol.

Continuously blowing the copolyester for 10 hours by using hot air at 130 ℃ to ensure that the water content of the copolyester is 30ppm, injecting the dried copolyester into a screw extruder for melting, spraying the copolyester from a spinneret plate of a spinning assembly through a spinning box and a metering pump, cooling the copolyester through an air cooling zone, winding the cooled copolyester to prepare 2, 5-furandicarboxylic acid group copolyester as-spun fiber, and finally carrying out hot drafting treatment to prepare the 2, 5-furandicarboxylic acid group copolyester fiber, wherein the temperature of the spinning assembly is 275 ℃, the spinning speed is 2500m/min, and the apparent shear rate at the hole wall of the spinneret plate is 2204s ^-1 The temperatures of the air-cooling zones a and b were 100 ℃ and 32 ℃ respectively, the hot-drawing temperature was 115 ℃ and the draw ratio was 3.0, and the filament fineness of the 2, 5-furandicarboxylic acid-based copolyester fiber was 1 dtex. The copolyester fiber is dyed by using conventional disperse dyes at the temperatures of 90, 100, 110, 120 and 130 ℃.

The detection shows that the orientation degree of the copolyester fiber is 0.85; the crystallinity of the copolyester fiber was 38% and 46% as determined by DSC and WAXD, respectively; the tensile strength and elongation at break (FIG. 1) of the copolyester fibers were 6.3cN/dtex and 20.5%, respectively; the dye uptake of the copolyester fiber at 90, 100, 110, 120 and 130 ℃ is respectively 68.1%, 94.2%, 94.7%, 95.1% and 96.2%.

Example 9

Firstly, 2, 5-furan is addedAdding furandicarboxylic acid (FDCA), terephthalic acid (PTA), ethylene Glycol (EG), nonaethylene glycol and anhydrous manganese acetate into a reaction kettle according to a molar ratio of 0.70. The intrinsic viscosity of the copolyester is detected to be 0.75dL/g; weight average molecular weight (M) _w ) And molecular weight Distribution (DI) of 27910g/mol, 1.82; entanglement molecular weight (M) _e ) The content was 1350g/mol.

Continuously blowing the copolyester for 13 hours by using hot air at 130 ℃ to ensure that the water content is 30ppm, injecting the dried copolyester into a screw extruder for melting, spraying the copolyester from a spinneret plate of a spinning assembly through a spinning box body and a metering pump, cooling the copolyester through an air cooling zone, then winding the copolyester to prepare 2, 5-furandicarboxylic acid group copolyester as-spun fiber, and finally carrying out hot drafting treatment to prepare the 2, 5-furandicarboxylic acid group copolyester fiber, wherein the temperature of the spinning assembly is 240 ℃, the spinning speed is 2500m/min, and the apparent shear rate at the hole wall of the spinneret plate is 1200s ^-1 The temperatures of the air-cooling zones a and b were 120 ℃ and 25 ℃ respectively, the hot-drawing temperature was 95 ℃ and the draw ratio was 2.0, and the filament fineness of the 2, 5-furandicarboxylic acid based copolyester fiber was 5dtex. The copolyester fibers are dyed with conventional disperse dyes at temperatures of 90, 100, 110, 120, 130 ℃ respectively.

The orientation degree of the copolyester fiber is detected to be 0.68; the crystallinity of the copolyester fiber was measured by DSC and WAXD to be 27% and 37%, respectively; the tensile strength and elongation at break of the copolyester fiber are respectively 2.8cN/dtex and 75%; the dye uptake of the copolyester fiber at 90 ℃, 100 ℃, 110 ℃, 120 and 130 ℃ is respectively 68.7%, 93.8%, 94.2%, 95.6% and 96.0%.

Example 10

Firstly, 2, 5-furandicarboxylic acid (FDCA), terephthalic acid (PTA), ethylene Glycol (EG), nonaethylene glycol and decaethylene glycol are combined (two mol)The ratio is 1). The intrinsic viscosity of the copolyester is detected to be 0.72dL/g; weight average molecular weight (M) _w ) And a molecular weight Distribution (DI) of 25690g/mol, 1.38, respectively; entanglement molecular weight (M) _e ) It was 1120g/mol.

Continuously blowing the copolyester for 9 hours by using hot air at 160 ℃ to ensure that the water content of the copolyester is 37ppm, injecting the dried copolyester into a screw extruder to be melted, spraying the copolyester out of a spinneret plate of a spinning assembly through a spinning box and a metering pump, cooling the copolyester through an air cooling zone, winding the cooled copolyester to prepare 2, 5-furandicarboxylic acid based copolyester nascent fiber, and finally carrying out hot drafting treatment to prepare the 2, 5-furandicarboxylic acid based copolyester fiber, wherein the temperature of the spinning assembly is 290 ℃, the spinning speed is 2500m/min, and the apparent shear rate at the hole wall of the spinneret plate is 3200s ^-1 The temperatures of the air-cooling zones a and b were 80 ℃ and 40 ℃ respectively, the hot-drawing temperature was 120 ℃ and the draw ratio was 4.0, and the filament fineness of the 2, 5-furandicarboxylic acid-based copolyester fiber was 5dtex. The copolyester fiber is dyed by using conventional disperse dyes at the temperatures of 90, 100, 110, 120 and 130 ℃.

The orientation degree of the copolyester fiber is detected to be 0.77; the crystallinity of the copolyester fiber was 38% and 47% as determined by DSC and WAXD, respectively; the tensile strength and elongation at break of the copolyester fiber are respectively 4.2cN/dtex and 38%; the dye uptake of the copolyester fiber at 90, 100, 110, 120 and 130 ℃ is 74.2%, 97.5%, 98.2%, 98.9% and 99.3% respectively.

Example 11

First, 2, 5-furandicarboxylic acid (FDCA), terephthalic acid (PTA), ethylene Glycol (EG), nonaethylene glycol, anhydrous manganese acetate were added to a reaction kettle in a molar ratio of 0.70Gradually heating to 150 ℃ under the protection of nitrogen, stirring and reacting for 4h, then adding antimony trioxide accounting for 0.12 percent of the total molar weight of FDCA and PTA, triphenyl phosphate accounting for 0.14 percent of the total molar weight of FDCA and PTA, antioxidant-168 accounting for 0.12 percent of the total molar weight of FDCA and PTA, slowly vacuumizing to 0.01MPa, prepolymerizing for 2h at the temperature of 180 ℃, finally gradually heating to 250 ℃, continuously vacuumizing to below 300Pa and reacting for 6h to obtain the 2, 5-furandicarboxylic acid based copolyester. The intrinsic viscosity of the copolyester is detected to be 0.68dL/g; weight average molecular weight (M) _w ) And a molecular weight Distribution (DI) of 24630g/mol, 1.90; entanglement molecular weight (M) _e ) It was 1350g/mol.

Continuously blowing the copolyester by using hot air at 100 ℃ for 15 hours to ensure that the water content of the copolyester is 40ppm, injecting the dried copolyester into a screw extruder to be melted, spraying the copolyester from a spinneret plate of a spinning assembly through a spinning box and a metering pump, cooling the copolyester through an air cooling zone, winding the cooled copolyester to prepare 2, 5-furandicarboxylic acid based copolyester nascent fiber, and finally carrying out hot drafting treatment to prepare the 2, 5-furandicarboxylic acid based copolyester fiber, wherein the temperature of the spinning assembly is 230 ℃, the spinning speed is 2500m/min, and the apparent shear rate at the hole wall of the spinneret plate is 1000s ^-1 The temperatures of the air-cooling zones a and b were 120 ℃ and 25 ℃, respectively, the hot-drawing temperature was 85 ℃ and the draw ratio was 6.0, and the filament fineness of the 2 dtex, 2, 5-furandicarboxylic acid based copolyester fiber, was used. The copolyester fiber is dyed by using conventional disperse dyes at the temperatures of 90, 100, 110, 120 and 130 ℃.

The orientation degree of the copolyester fiber is detected to be 0.66; the crystallinity of the copolyester fiber was 25% and 34% as determined by DSC and WAXD, respectively; the tensile strength and elongation at break of the copolyester fiber are respectively 3.1cN/dtex and 80%; the dye uptake of the copolyester fiber at 90, 100, 110, 120 and 130 ℃ is 69.2%, 94.1%, 94.8%, 95.9% and 96.1% respectively.

Example 12

Firstly, 2, 5-furandicarboxylic acid (FDCA), terephthalic acid (PTA), ethylene Glycol (EG), nonaethylene glycol and decaethylene glycol composition (the molar ratio of the two is 1And 1h, adding antimony trioxide accounting for 0.12 percent of the total molar weight of FDCA and PTA, triphenyl phosphate accounting for 0.17 percent of the total molar weight of FDCA and PTA and antioxidant-168 accounting for 0.15 percent of the total molar weight of FDCA and PTA into a reaction kettle, slowly vacuumizing to 0.05MPa, prepolymerizing for 1h at the temperature of 240 ℃, gradually heating to 270 ℃, and continuously vacuumizing to below 200Pa to react for 3h to obtain the 2, 5-furandicarboxylic acid based copolyester. The intrinsic viscosity of the copolyester is detected to be 0.65dL/g; weight average molecular weight (M) _w ) And a molecular weight Distribution (DI) of 23540g/mol, 1.87, respectively; entanglement molecular weight (M) _e ) It was 1120g/mol.

Continuously blowing the copolyester for 9 hours by using hot air at 170 ℃ to ensure that the water content of the copolyester is 37ppm, injecting the dried copolyester into a screw extruder to be melted, spraying the copolyester out of a spinneret plate of a spinning assembly through a spinning box and a metering pump, cooling the copolyester through an air cooling zone, winding the cooled copolyester to prepare 2, 5-furandicarboxylic acid based copolyester nascent fiber, and finally carrying out hot drafting treatment to prepare the 2, 5-furandicarboxylic acid based copolyester fiber, wherein the temperature of the spinning assembly is 300 ℃, the spinning speed is 2500m/min, and the apparent shear rate at the hole wall of the spinneret plate is 3500s ^-1 The temperatures of the air-cooling zones a and b were 80 ℃ and 40 ℃ respectively, the hot-drawing temperature was 130 ℃ and the draw ratio was 1.0, and the filament fineness of the 2, 5-furandicarboxylic acid-based copolyester fiber was 8 dtex. The copolyester fibers are dyed with conventional disperse dyes at temperatures of 90, 100, 110, 120, 130 ℃ respectively.

The detection proves that the orientation degree of the copolyester fiber is 0.65; the crystallinity of the copolyester fiber was 30% and 43% as determined by DSC and WAXD, respectively; the tensile strength and elongation at break of the copolyester fiber are respectively 2.8cN/dtex and 60%; the dye uptake of the copolyester fiber at 90 ℃, 100 ℃, 110, 120 and 130 ℃ is 76.4%, 98.2%, 98.7%, 99.2% and 99.7% respectively.

Comparative example 1

Firstly, terephthalic acid (PTA), ethylene Glycol (EG) and anhydrous zinc acetate are added into a reaction kettle according to the molar ratio of 1.6Prepolymerization is carried out for 1h at the temperature of 200 ℃, finally, the temperature is gradually increased to 265 ℃, and the reaction is carried out for 4h after the vacuum pumping is carried out until the pressure is lower than 200Pa, so as to obtain the polyethylene terephthalate (PET). The intrinsic viscosity of the PET is detected to be 0.75dL/g; weight average molecular weight (M) _w ) And molecular weight Distribution (DI) of 27910g/mol, 1.55; entanglement molecular weight (M) _e ) It was 1450g/mol.

Continuously blowing PET for 10 hours by using hot air at 130 ℃ to ensure that the water content is 40ppm, injecting the dried PET into a screw extruder to be melted, spraying the PET from a spinneret plate of a spinning assembly through a spinning box and a metering pump, cooling the PET through an air cooling zone, winding to prepare PET nascent fiber, and finally carrying out hot drawing treatment to prepare the PET fiber. Wherein the temperature of the spinning assembly is 288 ℃, the spinning speed is 2500m/min, and the apparent shear rate at the hole wall of the spinneret plate is 2000s ^-1 The temperatures of the air-cooling zones a and b were 110 ℃ and 40 ℃, respectively, the hot-drawing temperature was 110 ℃, the draw ratio was 2.0, and the filament fineness of the PET fiber was 5dtex. The PET fibers were dyed with conventional disperse dyes at temperatures of 90, 100, 110, 120, 130 c, respectively.

The orientation degree of the PET fibers is detected to be 0.63; the crystallinity of the PET fiber measured by DSC (fig. 2) and WAXD (fig. 3) was 40% and 53%, respectively; the tensile strength and the elongation at break of the PET drawn fibers are respectively 2.3cN/dtex and 33%; the dye uptake of the PET drawn fiber at 90, 100, 110, 120 and 130 ℃ is respectively 27.4%, 46.3%, 78.4%, 83.2% and 90.1%.

Comparative example 2

Firstly, adding terephthalic acid (PTA), ethylene Glycol (EG) and anhydrous cobalt acetate into a reaction kettle according to a molar ratio of 1.6. The intrinsic viscosity of the PET is detected to be 0.90dL/g; weight average molecular weight (M) _w ) And a molecular weight Distribution (DI) of 33750g/mol, 1.47; entanglement molecular weight (M) _e ) It was 1450g/mol.

The PET was continuously purged with 130 ℃ hot air for 10 hours to bring the water content to 39ppm. Injecting the dried PET into a screw extruder for melting, spraying the PET from a spinneret plate of a spinning assembly through a spinning box body and a metering pump, cooling the PET through an air cooling zone, and finally preparing the PET fiber through a one-step hot drawing mode. Wherein the spinning temperature is 293 ℃, the spinning speed is 2500m/min, and the apparent shear rate at the hole wall of the spinneret plate is 2100s ^-1 The temperatures of the air-cooling zones a and b were 110 ℃ and 40 ℃, respectively, the hot-drawing temperature was 115 ℃, the draw ratio was 3.0, and the filament fineness of the PET fiber was 1 dtex. The PET fibers were dyed with conventional disperse dyes at temperatures of 90, 100, 110, 120, 130 ℃ respectively.

The orientation degree of the PET fiber is detected to be 0.75; the crystallinity of the PET fibers measured by DSC and WAXD was 53% and 61%, respectively; the tensile strength and elongation at break of the PET fibers (FIG. 1) were 4.7cN/dtex and 7.1% respectively; the dye uptake of the PET fiber at 90, 100, 110, 120 and 130 ℃ is respectively 13.4%, 37.6%, 71.8%, 75.6% and 83.2%.

Comparative example 3

Firstly, adding 2, 5-furandicarboxylic acid (FDCA), terephthalic acid (PTA), ethylene Glycol (EG) and anhydrous cobalt acetate into a reaction kettle according to a molar ratio of 0.80. The intrinsic viscosity of the copolyester is detected to be 0.87dL/g; weight average molecular weight (M) _w ) And a molecular weight Distribution (DI) of 31800g/mol, 1.53, respectively; entanglement molecular weight (M) _e ) 3300g/mol.

Continuously blowing the copolyester for 10h by using hot air at 130 ℃ to ensure that the water content of the copolyester is 30ppm, injecting the dried copolyester into a screw extruder for melting, and spinning by using a spinning manifold and a metering pumpSpraying from a spinneret plate of the component, cooling in an air cooling zone and winding to prepare 2, 5-furandicarboxylic acid based copolyester nascent fiber, and finally carrying out hot drafting to prepare the 2, 5-furandicarboxylic acid based copolyester fiber, wherein the temperature of the spinning component is 282 ℃, the spinning speed is 2500m/min, and the apparent shear rate at the hole wall of the spinneret plate is 2324s ^-1 The temperatures of the air-cooling zones a and b were 100 ℃ and 32 ℃, respectively, the hot-drawing temperature was 118 ℃, and the single-filament fineness of the 3.0,2, 5-furandicarboxylic acid-based copolyester fiber was 1 dtex. The copolyester fibers are dyed with conventional disperse dyes at temperatures of 90, 100, 110, 120, 130 ℃ respectively.

The orientation degree of the copolyester fiber is detected to be 0.71; the crystallinity of the copolyester fiber measured by DSC and WAXD was 30% and 41%, respectively; the tensile strength and elongation at break of the copolyester fiber are 3.5cN/dtex and 40.3% respectively; the dye uptake of the copolyester fiber at 90, 100, 110, 120 and 130 ℃ is respectively 56.8%, 80.3%, 81.7%, 82.6% and 84.1%.

Comparative example 4

Firstly, adding 2, 5-furandicarboxylic acid (FDCA), ethylene Glycol (EG) and anhydrous cobalt acetate into a reaction kettle according to a molar ratio of 1.6. The intrinsic viscosity of the PEF is detected to be 0.75dL/g; weight average molecular weight (M) _w ) And molecular weight Distribution (DI) of 27910g/mol, 1.32; entanglement molecular weight (M) _e ) Is 3500g/mol.

Continuously blowing PEF for 13h by using hot air at 130 ℃ to ensure that the water content is 30ppm, injecting the dried PEF into a screw extruder for melting, spraying the PEF from a spinneret plate of a spinning assembly through a spinning box and a metering pump, cooling the PEF in an air cooling zone, winding to prepare PEF nascent fiber, and finally carrying out hot drawing treatment to prepare PEF fiber, wherein the temperature of the spinning assembly is 265 ℃, and the temperature of the spinning assembly is 265 ℃The filament speed was 2500m/min and the apparent shear rate at the wall of the spinneret hole was 2440s ^-1 The temperatures of the air-cooling zones a and b were 90 ℃ and 28 ℃, respectively, the hot-drawing temperature was 115 ℃ and the draw ratio was 2.0, and the filament fineness of the PEF fiber was 5dtex. PEF fibers were dyed with conventional disperse dyes at temperatures of 90, 100, 110, 120, 130 ℃ respectively.

The orientation degree of the PEF fiber is detected to be 0.57; the crystallinity of the PEF fibers measured by DSC and WAXD was 33% and 45%, respectively; the tensile strength and elongation at break of the PEF fiber are respectively 1.9cN/dtex and 30%; the dye uptake of the PEF fiber at 90, 100, 110, 120 and 130 ℃ is 65.6%, 84.3%, 86.7%, 87.2% and 91.7% respectively.

As can be seen from the above examples and comparative examples, C is compared with PET fiber of the same molecular weight and molecular weight distribution ₁₂ -C ₂₀ Incorporation of glycol ether composition to impart entanglement molecular weight (M) to 2, 5-furandicarboxylic acid-based copolyester fibers _e ) The tensile strength, the elongation at break and the dye uptake are obviously increased, and the excellent normal pressure dyeability of the disperse dye is also endowed.

In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.

The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.

The use of headings and sections in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.

Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.

It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.

Although the present invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.

Claims

1. A bio-based 2, 5-furandicarboxylic acid based copolyester fiber is characterized in that: the 2, 5-furan diformyl copolyester fiber is prepared by reacting 2, 5-furan diformic acid, terephthalic acid, ethylene glycol and C ₁₂ -C ₂₀ The glycol ether composition is polymerized to form 2, 5-furandicarboxylic acid copolyester, and then the copolyester is prepared by melt spinning and hot drawing treatment; said C is ₁₂ -C ₂₀ The glycol ether composition is selected from any two or more of hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol and decaethylene glycol; the 2, 5-furandicarboxylic acid-based copolyester is a random copolyester; the intrinsic viscosity of the 2, 5-furandicarboxylic acid-based copolyester is 0.65-1.00dL/g; the entanglement molecular weight of the 2, 5-furandicarboxylic acid-based copolyester is 1000-1400g/mol;

wherein the orientation degree of the 2, 5-furandicarboxylic acid-based copolyester fiber is 0.30-0.95; the crystallinity of the 2, 5-furandicarboxylic acid-based copolyester fiber is 5-70%; when the 2, 5-furandicarboxylic acid-based copolyester fiber is dyed at 100-130 ℃, the dye-uptake of the 2, 5-furandicarboxylic acid-based copolyester fiber is more than 87%.

2. The bio-based 2, 5-furandicarboxylic acid-based copolyester fiber according to claim 1, wherein: the intrinsic viscosity of the 2, 5-furandicarboxylic acid-based copolyester is 0.70-0.95dL/g.

3. The bio-based 2, 5-furandicarboxylic acid-based copolyester fiber according to claim 1, wherein: the entanglement molecular weight of the 2, 5-furandicarboxylic acid-based copolyester is 1100-1300g/mol.

4. The bio-based 2, 5-furandicarboxylic acid-based copolyester fiber according to claim 1, wherein: the filament number of the 2, 5-furandicarboxylic acid-based copolyester fiber is 1-5dtex.

5. The bio-based 2, 5-furandicarboxylic acid-based copolyester fiber according to claim 1, wherein: the orientation degree of the 2, 5-furan diformyl copolyester fiber is 0.60-0.90.

6. The bio-based 2, 5-furandicarboxylic acid-based copolyester fiber according to claim 1, wherein: the crystallinity of the 2, 5-furandicarboxylic acid-based copolyester fiber is 25-65%.

7. The method for preparing bio-based 2, 5-furandicarboxylic acid-based copolyester fiber according to any one of claims 1 to 6, comprising:

under a protective atmosphere, 2, 5-furan dicarboxylic acid, terephthalic acid, ethylene glycol and C are added ₁₂ -C ₂₀ The mixed reaction system of the glycol ether composition, the esterification catalyst, the polycondensation catalyst, the stabilizer and the antioxidant is reacted to prepare the 2, 5-furandicarboxylic acidA copolyester;

drying the obtained 2, 5-furandicarboxylic acid-based copolyester to at least make the water content of the 2, 5-furandicarboxylic acid-based copolyester below 70ppm;

8. The production method according to claim 7, characterized by comprising: reacting the 2, 5-furandicarboxylic acid, terephthalic acid, ethylene glycol, C under a protective atmosphere ₁₂ -C ₂₀ Mixing the glycol ether composition and an esterification catalyst, reacting for 1-4h at 150-200 ℃, then adding a polycondensation catalyst, a stabilizer and an antioxidant, prepolymerizing for 1-2h under the conditions that the vacuum degree is 0.01-0.05MPa and the temperature is 180-240 ℃, then reducing the vacuum degree to below 300Pa, and reacting for 3-6h at 250-270 ℃ to prepare the 2, 5-furandicarboxylic acid based copolyester.

9. The method of claim 8, wherein: the molar ratio of the 2, 5-furandicarboxylic acid to the sum of the 2, 5-furandicarboxylic acid and terephthalic acid is 0.01-0.99: 1;

said C is ₁₂ -C ₂₀ The molar ratio of the glycol ether composition to the 2, 5-furandicarboxylic acid is 0.01-0.05: 1;

the molar ratio of the ethylene glycol to the sum of the 2, 5-furandicarboxylic acid and the terephthalic acid is 1.2-1.8: 1;

the molar ratio of the esterification catalyst to the sum of the 2, 5-furandicarboxylic acid and the terephthalic acid is 0.001-0.003: 1;

the molar ratio of the polycondensation catalyst to the sum of the 2, 5-furandicarboxylic acid and the terephthalic acid is 0.0010-0.0035: 1;

the mol ratio of the stabilizer to the sum of the 2, 5-furan dicarboxylic acid and the terephthalic acid is 0.0010-0.0025: 1;

the molar ratio of the antioxidant to the sum of the 2, 5-furandicarboxylic acid and the terephthalic acid is 0.001-0.002:1.

10. The method of claim 9, wherein: said C is ₁₂ -C ₂₀ The molar ratio of the glycol ether composition to the 2, 5-furandicarboxylic acid is 0.02-0.04:1.

11. The method of claim 8, wherein: the esterification catalyst is selected from one or the combination of more than two of anhydrous zinc acetate, anhydrous manganese acetate, anhydrous cobalt acetate, n-butyl titanate and stannous octoate;

the polycondensation catalyst is selected from any one or the combination of more than two of antimony trioxide, tetrabutyl titanate, isobutyl titanate and dibutyltin oxide;

the stabilizer is selected from any one or the combination of more than two of phosphoric acid, phosphorous acid, triphenyl phosphate, triphenyl phosphite, trimethyl phosphate, trimethyl phosphite, triisooctyl phosphite and tri-p-tolyl phosphite;

the antioxidant is selected from one or more of antioxidant-176, antioxidant-168 and antioxidant-1010.

12. The method according to claim 7, characterized by comprising: blowing the 2, 5-furandicarboxylic acid-based copolyester by using hot air with the temperature of 100-170 ℃ for 7-15h, so that the water content of the 2, 5-furandicarboxylic acid-based copolyester is below 70ppm;

wherein the 2, 5-furandicarboxylic acid-based copolyester is subjected to purging treatment for 9-13h by using hot air with the temperature of 130-160 ℃, so that the water content of the 2, 5-furandicarboxylic acid-based copolyester is below 40ppm.

13. The production method according to claim 7, characterized by comprising: melting the dried 2, 5-furandicarboxylic acid-based copolyester by a screw rod, feeding the melted copolyester into a spinning manifold, and then passing the molten copolyester through a metering pumpSpraying the raw materials from a spinneret plate of a spinning assembly to form filaments, cooling the filaments in an air cooling zone, and winding the filaments to obtain the 2, 5-furandicarboxylic acid copolyester nascent fiber, wherein the temperature of a screw is 200-300 ℃, the temperature of the spinning assembly is 230-300 ℃, and the apparent shear rate at the hole wall of the spinneret plate is 1000-3500s ^-1 The metering pump speed is 1.0-4.0ml/rev, the spinneret plate aperture is 0.2-0.8mm, the number of holes is 1-200, the length-diameter ratio (L/D) is 1-10, the air cooling zone temperature is 10-120 ℃, and the winding speed is 100-5000m/min.

14. The method of manufacturing according to claim 13, wherein: the temperature of the screw is 220-290 ℃, and the temperature of the spinning assembly is 240-290 ℃;

the apparent shear rate of the hole wall of the spinneret plate is 1200-3200s ^-1 The speed of a metering pump is 1.2-3.6ml/rev, the aperture of a spinneret plate is 0.28-0.60mm, the number of holes is 4-100 holes, and the length-diameter ratio is 3-8;

the air cooling area comprises a slow cooling area with the temperature of 80-120 ℃ and a cooling area with the temperature of 25-40 ℃; the slow cooling area is arranged at a position 40-140mm below the spinneret plate.

15. The production method according to claim 7, characterized by comprising: carrying out hot drawing treatment on the obtained 2, 5-furandicarboxylic acid-based copolyester nascent fiber under the conditions that the temperature is 85-130 ℃ and the drawing ratio is 1.0-6.0 to prepare the 2, 5-furandicarboxylic acid-based copolyester fiber;

wherein, when the hot drawing treatment is a one-step drawing mode, the drawing ratio is 2.0-4.0, and the drawing temperature is 95-120 ℃; when the hot drawing treatment is a two-step drawing mode, the drawing ratio is 1.4-4.0, and the drawing temperature is 90-110 ℃.

16. Use of the biobased 2, 5-furandicarboxylic acid-based copolyester fiber according to any one of claims 1 to 6 in home textile, clothing or agricultural fields.