A bio-based fiber and a method of making the same

Abstract

The application discloses a kind of bio-based fibers and preparation method thereof, it is related to textile fiber technical field.The application is prepared when bio-based fiber, 1, 4-di (2', 3'-epoxy propyl) perfluorobutane is reacted with diethyl phosphinic acid to obtain flame-retardant dihydric alcohol;Terephthalic acid is dehydrated and condensed with bio-based 1, 3-propanediol, flame-retardant dihydric alcohol, and then reacted with hydroxyl-terminated dimethyl methyl vinyl (silicone and polysiloxane) to obtain modified bio-based polyester;Biomass graphene is reacted with 3-(methacryloyloxy) propyl trimethoxysilane to obtain modified biomass graphene;Modified bio-based polyester and modified biomass graphene are melt-mixed, extruded and granulated to obtain modified bio-based polyester / modified biomass graphene blend chip, and then melt-spun with dicumyl peroxide, false twist texturing to obtain bio-based fiber.The bio-based fiber prepared by the application has good warmth retention, flame retardant, hydrophobic and mechanical properties.

Description

Technical Field

[0001] This invention relates to the field of textile fiber technology, specifically to a bio-based fiber and its preparation method. Background Technology

[0002] Polyester fiber is an important component of synthetic fibers, and large-scale polyester fiber production requires sufficient raw material support. However, the continuous depletion of oil reserves limits the sustainable development of the chemical fiber industry. Therefore, the development of bio-based materials that can replace polyester fiber has become a research hotspot. To address this issue, bio-based polyester fiber has been proposed. This involves using bio-based diols of similar purity while keeping the raw material petroleum-based terephthalic acid unchanged. The resulting bio-based polyester fiber has properties essentially similar to petroleum-based polyester fiber, thus replacing a portion of petroleum-based polyester fiber.

[0003] Polyester fibers possess excellent mechanical properties, dimensional stability, heat resistance, and low cost due to large-scale production, making them widely used in apparel, home textiles, decoration, and industrial applications. They are the synthetic fiber with the largest production capacity, fastest development, and widest application range. However, the chemical structure and combustion characteristics of polyester fibers result in a low limiting oxygen index (LOI), only 20%–22%, and their ignition temperature is extremely close to their decomposition temperature, classifying them as flammable materials. Furthermore, the heat generated during combustion of PET fibers far exceeds their own melting heat, causing the matrix to soften easily, forming molten droplets and triggering secondary combustion, leading to personal injury and severe economic losses. Therefore, improving the flame-retardant properties of polyester fibers is a key focus for researchers.

[0004] Furthermore, with the improvement of living standards, people no longer favor heavy and bulky thermal clothing. Whether it's everyday outerwear, autumn and winter underwear, bed sheets, or other thermal textiles, or thermal and cold-weather clothing for special work environments, comfort, lightweight, and fashion are becoming the new development trends. Therefore, this invention prepares a bio-based fiber with excellent warmth retention and flame retardant properties. Summary of the Invention

[0005] The purpose of this invention is to provide a bio-based fiber and its preparation method to solve the problems existing in the prior art.

[0006] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0007] A bio-based fiber, wherein the bio-based fiber is obtained by melt mixing and extrusion granulation of modified bio-based polyester and modified biomass graphene to obtain modified bio-based polyester / modified biomass graphene blend chips, which are then melt-spun with dicumyl peroxide and false-twist deformed.

[0008] As an optimization, the modified bio-based polyester is prepared by dehydration condensation of terephthalic acid with bio-based 1,3-propanediol and flame-retardant diol, followed by reaction with hydroxyl-terminated dimethylmethyl vinyl (siloxane and polysiloxane).

[0009] As an optimization, the flame-retardant diol is prepared by reacting 1,4-bis(2',3'-epoxypropyl)perfluorobutane with diethylphosphonic acid.

[0010] As an optimization, the modified biomass graphene is prepared by reacting biomass graphene with 3-(methacryloyloxy)propyltrimethoxysilane.

[0011] A method for preparing bio-based fibers includes the following preparation steps:

[0012] (1) Mix 1,4-bis(2',3'-epoxypropyl)perfluorobutane, diethylphosphonic acid, tetrabutylammonium bromide and N,N-dimethylformamide evenly, stir and react at 90~100℃ for 8~10h, distill under reduced pressure, wash and dry to obtain flame-retardant diol;

[0013] (2) Terephthalic acid, bio-based 1,3-propanediol, flame-retardant diol and antimony trioxide are mixed evenly and reacted at 220~250℃ and 0.3~0.4MPa until the water output is 90% of the theoretical value. Then, 0.08~0.1 times the mass of terephthalic acid is added to hydroxyl-terminated dimethyl methyl vinyl (siloxane and polysiloxane). The temperature is raised to 260~280℃ and the vacuum degree is 60~70Pa. When the stirring power reaches 50W / 40Hz, the stirring is stopped, the vacuum is broken and the material is discharged to obtain modified bio-based polyester.

[0014] (3) Mix biomass graphene dispersion and 3-(methacryloyloxy)propyltrimethoxysilane dispersion evenly, stir and react at 50~60℃ for 6~8h, centrifuge, wash, dry, and obtain modified biomass graphene.

[0015] (4) The modified bio-based polyester and modified biomass graphene are mixed evenly at a mass ratio of 1: (0.1~0.2), added to a twin-screw extruder for melt blending, extruded and granulated to obtain modified bio-based polyester / modified biomass graphene blend chips; the modified bio-based polyester / modified biomass graphene blend chips and dicumyl peroxide are mixed evenly at a mass ratio of 1: (0.002~0.004), added to a single-screw spinning machine for melt spinning, and wound to obtain modified bio-based polyester / modified biomass graphene composite hollow fiber pre-oriented yarn; the modified bio-based polyester / modified biomass graphene composite hollow fiber pre-oriented yarn is placed in a false twist texturer for false twist texture to obtain bio-based fiber.

[0016] As an optimization, the preparation steps of the flame-retardant diol in step (1) are as follows: 1,4-bis(2',3'-epoxypropyl)perfluorobutane, diethylphosphonic acid, tetrabutylammonium bromide, and N,N-dimethylformamide are mixed evenly in a mass ratio of 1:(0.8~0.85):(0.03~0.05):(5~10), stirred and reacted at 90~100℃ for 8~10h, N,N-dimethylformamide is removed by vacuum distillation, washed 3~5 times with anhydrous ethanol, and dried under vacuum at 40~50℃ for 10~12h to obtain the flame-retardant diol.

[0017] As an optimization, the mass ratio of terephthalic acid, bio-based 1,3-propanediol, flame-retardant diol, and antimony trioxide in step (2) is 1:(0.6~0.7):(0.03~0.04):(0.002~0.004).

[0018] As an optimization, the preparation steps of the modified biomass graphene in step (3) are as follows: biomass graphene and 90wt% ethanol aqueous solution are mixed evenly at a mass ratio of 1: (400~500), and ultrasonically dispersed to obtain a biomass graphene dispersion; 3-(methacryloyloxy)propyltrimethoxysilane and 90wt% ethanol aqueous solution are mixed evenly at a mass ratio of 1: (40~50), the pH is adjusted to 4 with 2mol / L hydrochloric acid aqueous solution, and stirred for 2~3h to obtain a 3-(methacryloyloxy)propyltrimethoxysilane dispersion; the biomass graphene dispersion and the 3-(methacryloyloxy)propyltrimethoxysilane dispersion are mixed evenly at a mass ratio of 1: (0.1~0.12), stirred at 50~60℃ for 6~8h, centrifuged, washed 3~5 times with anhydrous ethanol, and vacuum dried at 40~50℃ for 10~12h to obtain modified biomass graphene.

[0019] As an optimization, the process parameters for melt blending and extrusion granulation in step (4) are: zone 1 temperature 245℃, zone 2 temperature 260℃, zone 3 temperature 265℃, zone 4 temperature 270℃, zone 5 temperature 275℃, zone 6 temperature 275℃, zone 7 temperature 260℃, zone 8 temperature 255℃, die head temperature 250℃, and screw speed 200rpm.

[0020] As an optimization, the process parameters for melt spinning in step (4) are as follows: zone 1 temperature 240℃, zone 2 temperature 255℃, zone 3 temperature 265℃, zone 4 temperature 270℃, tube bending temperature 275℃, metering pump temperature 275℃, spinning assembly temperature 275℃, spinning speed 3000m / min, side blowing speed 0.45m / s, air temperature 22℃, oil content 0.8%, the spinneret is a 2C-shaped hollow spinneret, the spinneret holes are two concentric rings that are equally spaced, the ring spacing is equal, the inner diameter of the concentric ring is 0.60mm, the outer diameter is 0.72mm, and the ring spacing is 0.06mm.

[0021] As an optimization, the process parameters for false twisting deformation in step (4) are: first hot box temperature 185℃, processing speed 550m / min, D / Y ratio 1.63, and draw ratio 1.68.

[0022] As an optimization, the biomass graphene was purchased from Jinan Shengquan Group.

[0023] As an optimization, the hydroxyl-terminated dimethylmethyl vinyl (siloxane and polysiloxane) was purchased from Shanghai Mairui Biochemical Technology Co., Ltd.

[0024] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0025] In preparing bio-based fibers, this invention involves reacting 1,4-di(2',3'-epoxypropyl)perfluorobutane with diethylphosphonic acid to obtain a flame-retardant diol; dehydrating and condensing terephthalic acid with bio-based 1,3-propanediol and the flame-retardant diol, and then reacting it with hydroxyl-terminated dimethylmethyl vinyl (siloxane and polysiloxane) to obtain a modified bio-based polyester; reacting biomass graphene with 3-(methacryloyloxy)propyltrimethoxysilane to obtain modified biomass graphene; melt-blending the modified bio-based polyester and modified biomass graphene, extruding and granulating to obtain modified bio-based polyester / modified biomass graphene blend chips, and then melt-spinning them with dicumyl peroxide and false-twist deformation to obtain bio-based fibers.

[0026] First, a flame-retardant diol is prepared by reacting 1,4-bis(2',3'-epoxypropyl)perfluorobutane with diethylphosphonic acid. The epoxy groups on 1,4-bis(2',3'-epoxypropyl)perfluorobutane undergo a ring-opening reaction with the phosphonic acid groups on diethylphosphonic acid to generate a diol containing fluorine and phosphorus. The introduction of fluorine and phosphorus elements can improve the flame-retardant properties of bio-based fibers. Simultaneously, fluorine has low surface energy, causing fluorocarbon segments to migrate to the polyester surface, forming a rough structure and thus improving the hydrophobic properties of the bio-based fibers. Then, terephthalic acid is reacted with bio-based 1,3-propanediol and a flame-retardant diol... Modified bio-based polyester is prepared by dehydrating and condensing diols and then reacting them with hydroxyl-terminated dimethylmethyl vinyl groups (siloxanes and polysiloxanes). The hydroxyl-terminated dimethylmethyl vinyl groups (siloxanes and polysiloxanes) have low surface energy and are arranged in an orderly manner on the polyester surface, further promoting the migration of fluorocarbon segments to the surface and forming more ordered nanoscale protrusions on the surface, thereby enhancing the hydrophobic properties of the bio-based fiber. At the same time, double bonds are introduced into the polyester and react with the double bonds on the modified biomass graphene to form a cross-linked network structure, thereby improving the mechanical properties of the bio-based fiber.

[0027] Secondly, modified biomass graphene is prepared by reacting biomass graphene with 3-(methacryloyloxy)propyltrimethoxysilane. Biomass graphene has low-temperature far-infrared properties, which can automatically generate heat and raise the temperature. Through related media, it can dilate human capillaries, thereby accelerating blood circulation, strengthening the metabolism between tissues, and helping to solve the problem of low skin temperature and frequent coldness. When added to polyester fibers, it can improve the warmth retention of the fibers. At the same time, adding biomass graphene to the fibers can also improve flame retardancy and mechanical properties. The reaction with 3-(methacryloyloxy)propyltrimethoxysilane improves the dispersibility of biomass graphene in polyester and introduces double bonds on the biomass graphene. The double bonds on the modified biomass graphene react with the double bonds on the modified bio-based polyester to form a cross-linked network structure, thereby further improving the mechanical properties of bio-based fibers.

[0028] Finally, modified bio-based polyester and modified biomass graphene were melt-blended and extruded to obtain modified bio-based polyester / modified biomass graphene blend chips. These chips were then melt-spun with dicumyl peroxide and false-twist deformed to obtain bio-based fibers. The double bonds on the modified bio-based polyester and the double bonds on the modified biomass graphene reacted under the action of an initiator to form a cross-linked network structure, which improved the mechanical properties. The spinning process used a 2C-shaped hollow spinneret, which gave the obtained bio-based fibers a hollow structure, thereby further improving the thermal insulation performance of the bio-based fibers. Detailed Implementation

[0029] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0030] Example 1:

[0031] A method for preparing bio-based fibers includes the following preparation steps:

[0032] (1) 1,4-bis(2',3'-epoxypropyl)perfluorobutane, diethylphosphonic acid, tetrabutylammonium bromide and N,N-dimethylformamide were mixed evenly in a mass ratio of 1:0.8:0.03:5. The mixture was stirred and reacted at 90°C for 8 h. N,N-dimethylformamide was removed by vacuum distillation. The mixture was washed three times with anhydrous ethanol and dried under vacuum at 40°C for 10 h to obtain a flame-retardant diol.

[0033] (2) Terephthalic acid, bio-based 1,3-propanediol, flame-retardant diol, and antimony trioxide are mixed evenly in a mass ratio of 1:0.6:0.03:0.002. The mixture is reacted at 220°C and 0.3 MPa until the water output is 90% of the theoretical value. Hydroxyl-terminated dimethyl methyl vinyl (siloxane and polysiloxane) with a mass of 0.08 times that of terephthalic acid is added. The mixture is heated to 260°C, the vacuum degree is 60 Pa, and the stirring power reaches 50 W / 40 Hz. The stirring is then stopped, the vacuum is broken, and the material is discharged to obtain the modified bio-based polyester.

[0034] (3) Biomass graphene and 90wt% ethanol aqueous solution were mixed evenly at a mass ratio of 1:400 and ultrasonically dispersed to obtain biomass graphene dispersion; 3-(methacryloyloxy)propyltrimethoxysilane and 90wt% ethanol aqueous solution were mixed evenly at a mass ratio of 1:40, pH was adjusted to 4 with 2mol / L hydrochloric acid aqueous solution, and stirred for 2h to obtain 3-(methacryloyloxy)propyltrimethoxysilane dispersion; biomass graphene dispersion and 3-(methacryloyloxy)propyltrimethoxysilane dispersion were mixed evenly at a mass ratio of 1:0.1, stirred at 50℃ for 6h, centrifuged, washed 3 times with anhydrous ethanol, and vacuum dried at 40℃ for 10h to obtain modified biomass graphene;

[0035] (4) The modified bio-based polyester and modified biomass graphene were mixed evenly at a mass ratio of 1:0.1 and added to a twin-screw extruder for melt blending. The temperatures in zones 1, 2, 3, 4, 5, 6, 7, 8 were 260°C, 250°C, 270°C, 275°C, 260°C, 255°C, and 250°C were maintained. The screw speed was 200 rpm. The mixture was then extruded and granulated to obtain the modified bio-based polyester. Modified biomass graphene blend chips; Modified bio-based polyester / modified biomass graphene blend chips and dicumyl peroxide are mixed evenly at a mass ratio of 1:0.002, and then added to a single-screw spinning machine. The temperatures are as follows: Zone 1: 240℃; Zone 2: 255℃; Zone 3: 265℃; Zone 4: 270℃; Bending tube temperature: 275℃; Metering pump temperature: 275℃; Spinning assembly temperature: 275℃; Spinning speed: 3000 m / min; Side-blowing speed: 0.45. The modified bio-based polyester / modified biomass graphene composite hollow fiber pre-oriented yarn was prepared by winding a 2C-shaped hollow spinneret with two equally spaced concentric rings of equal spacing. The inner diameter of the concentric rings was 0.60 mm, the outer diameter was 0.72 mm, and the ring spacing was 0.06 mm. The pre-oriented yarn was then added to a false-twist texturing machine for false-twist texturing. The first hot box temperature was 185℃, the processing speed was 550 m / min, the D / Y ratio was 1.63, and the draw ratio was 1.68 to obtain bio-based fiber.

[0036] Example 2:

[0037] A method for preparing bio-based fibers includes the following preparation steps:

[0038] (1) 1,4-bis(2',3'-epoxypropyl)perfluorobutane, diethylphosphonic acid, tetrabutylammonium bromide and N,N-dimethylformamide were mixed evenly in a mass ratio of 1:0.82:0.04:8. The mixture was stirred and reacted at 95°C for 9 h. The N,N-dimethylformamide was removed by vacuum distillation. The mixture was washed four times with anhydrous ethanol and dried under vacuum at 45°C for 11 h to obtain a flame-retardant diol.

[0039] (2) Terephthalic acid, bio-based 1,3-propanediol, flame-retardant diol, and antimony trioxide are mixed evenly in a mass ratio of 1:0.65:0.035:0.003. The mixture is reacted at 235°C and 0.35 MPa until the water output is 90% of the theoretical value. Hydroxyl-terminated dimethyl methyl vinyl (siloxane and polysiloxane) with a mass of 0.09 times that of terephthalic acid is added. The mixture is heated to 270°C, the vacuum degree is 65 Pa, and the stirring power reaches 50 W / 40 Hz. The stirring is then stopped, the vacuum is broken, and the material is discharged to obtain the modified bio-based polyester.

[0040] (3) Biomass graphene and 90wt% ethanol aqueous solution were mixed evenly at a mass ratio of 1:450 and ultrasonically dispersed to obtain biomass graphene dispersion; 3-(methacryloyloxy)propyltrimethoxysilane and 90wt% ethanol aqueous solution were mixed evenly at a mass ratio of 1:45, pH was adjusted to 4 with 2mol / L hydrochloric acid aqueous solution, and stirred for 2.5h to obtain 3-(methacryloyloxy)propyltrimethoxysilane dispersion; Biomass graphene dispersion and 3-(methacryloyloxy)propyltrimethoxysilane dispersion were mixed evenly at a mass ratio of 1:0.11, stirred at 55℃ for 7h, centrifuged, washed 4 times with anhydrous ethanol, and vacuum dried at 45℃ for 11h to obtain modified biomass graphene;

[0041] (4) The modified bio-based polyester and modified biomass graphene were mixed evenly at a mass ratio of 1:0.15 and added to a twin-screw extruder for melt blending. The temperatures in zones 1, 2, 3, 4, 5, 6, 7, 8 were 260°C, 250°C, 270°C, 275°C, 260°C, 255°C, and 250°C were maintained. The screw speed was 200 rpm. The mixture was then extruded and granulated to obtain the modified bio-based polyester. Modified biomass graphene blend chips; Modified bio-based polyester / modified biomass graphene blend chips and dicumyl peroxide are mixed evenly at a mass ratio of 1:0.003, and added to a single-screw spinning machine. The temperatures are as follows: Zone 1: 240℃; Zone 2: 255℃; Zone 3: 265℃; Zone 4: 270℃; Bending tube temperature: 275℃; Metering pump temperature: 275℃; Spinning assembly temperature: 275℃; Spinning speed: 3000 m / min; Side-blowing speed: 0.45. The modified bio-based polyester / modified biomass graphene composite hollow fiber pre-oriented yarn was prepared by winding a 2C-shaped hollow spinneret with two equally spaced concentric rings of equal spacing. The inner diameter of the concentric rings was 0.60 mm, the outer diameter was 0.72 mm, and the ring spacing was 0.06 mm. The pre-oriented yarn was then added to a false-twist texturing machine for false-twist texturing. The first hot box temperature was 185℃, the processing speed was 550 m / min, the D / Y ratio was 1.63, and the draw ratio was 1.68 to obtain bio-based fiber.

[0042] Example 3:

[0043] A method for preparing bio-based fibers includes the following preparation steps:

[0044] (1) 1,4-bis(2',3'-epoxypropyl)perfluorobutane, diethylphosphonic acid, tetrabutylammonium bromide and N,N-dimethylformamide were mixed evenly in a mass ratio of 1:0.85:0.05:10. The mixture was stirred and reacted at 100°C for 10 h. N,N-dimethylformamide was removed by vacuum distillation. The mixture was washed 5 times with anhydrous ethanol and dried under vacuum at 50°C for 12 h to obtain a flame-retardant diol.

[0045] (2) Terephthalic acid, bio-based 1,3-propanediol, flame-retardant diol, and antimony trioxide are mixed evenly in a mass ratio of 1:0.7:0.04:0.004. The mixture is reacted at 250°C and 0.4 MPa until the water output is 90% of the theoretical value. Hydroxyl-terminated dimethyl methyl vinyl (siloxane and polysiloxane) with a mass of 0.1 times that of terephthalic acid is added. The mixture is heated to 280°C, the vacuum degree is 70 Pa, and the stirring power reaches 50 W / 40 Hz. The stirring is then stopped, the vacuum is broken, and the material is discharged to obtain the modified bio-based polyester.

[0046] (3) Biomass graphene and 90wt% ethanol aqueous solution were mixed evenly at a mass ratio of 1:500 and ultrasonically dispersed to obtain biomass graphene dispersion; 3-(methacryloyloxy)propyltrimethoxysilane and 90wt% ethanol aqueous solution were mixed evenly at a mass ratio of 1:50, pH was adjusted to 4 with 2mol / L hydrochloric acid aqueous solution, and stirred for 3h to obtain 3-(methacryloyloxy)propyltrimethoxysilane dispersion; Biomass graphene dispersion and 3-(methacryloyloxy)propyltrimethoxysilane dispersion were mixed evenly at a mass ratio of 1:0.12, stirred at 60℃ for 8h, centrifuged, washed 5 times with anhydrous ethanol, and vacuum dried at 50℃ for 12h to obtain modified biomass graphene;

[0047] (4) The modified bio-based polyester and modified biomass graphene were mixed evenly at a mass ratio of 1:0.2 and added to a twin-screw extruder for melt blending. The temperatures in zones 1, 2, 3, 4, 5, 6, 7, 8 were 260°C, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 1 ... Modified biomass graphene blend chips; Modified bio-based polyester / modified biomass graphene blend chips and dicumyl peroxide are mixed evenly at a mass ratio of 1:0.004, and then added to a single-screw spinning machine. The temperatures are as follows: Zone 1: 240℃; Zone 2: 255℃; Zone 3: 265℃; Zone 4: 270℃; Bending tube temperature: 275℃; Metering pump temperature: 275℃; Spinning assembly temperature: 275℃; Spinning speed: 3000 m / min; Side-blowing speed: 0.45. The modified bio-based polyester / modified biomass graphene composite hollow fiber pre-oriented yarn was prepared by winding a 2C-shaped hollow spinneret with two equally spaced concentric rings of equal spacing. The inner diameter of the concentric rings was 0.60 mm, the outer diameter was 0.72 mm, and the ring spacing was 0.06 mm. The pre-oriented yarn was then added to a false-twist texturing machine for false-twist texturing. The first hot box temperature was 185℃, the processing speed was 550 m / min, the D / Y ratio was 1.63, and the draw ratio was 1.68 to obtain bio-based fiber.

[0048] Comparative Example 1:

[0049] The difference between the preparation method of the bio-based fiber in Comparative Example 1 and Example 2 lies in step (1). Step (1) is modified as follows: Ethylene glycol diglycidyl ether, diethylphosphonic acid, tetrabutylammonium bromide, and N,N-dimethylformamide are mixed evenly in a mass ratio of 1:1.45:0.04:8, stirred and reacted at 95°C for 9 hours, N,N-dimethylformamide is removed by vacuum distillation, washed four times with anhydrous ethanol, and dried under vacuum at 45°C for 11 hours to obtain the flame-retardant diol. The remaining steps are the same as in Example 2.

[0050] Comparative Example 2:

[0051] The difference between the preparation method of the bio-based fiber in Comparative Example 2 and Example 2 is that step (1) is omitted, and step (2) is modified as follows: terephthalic acid, bio-based 1,3-propanediol, and antimony trioxide are mixed evenly at a mass ratio of 1:0.65:0.003, and reacted at 235°C and 0.35 MPa until the water output reaches 90% of the theoretical value. Then, 0.09 times the mass of terephthalic acid is added to hydroxyl-terminated dimethyl methyl vinyl (siloxane and polysiloxane), the temperature is raised to 270°C, the vacuum degree is 65 Pa, and the stirring power reaches 50 W / 40 Hz. Stirring is then stopped, the vacuum is broken, and the material is discharged to obtain the modified bio-based polyester. The remaining steps are the same as in Example 2.

[0052] Comparative Example 3:

[0053] The difference between the preparation method of the bio-based fiber in Comparative Example 3 and Example 2 lies in step (2). Step (2) is modified as follows: terephthalic acid, bio-based 1,3-propanediol, flame-retardant diol, and antimony trioxide are mixed evenly in a mass ratio of 1:0.65:0.035:0.003. The mixture is reacted at 235°C and 0.35 MPa until the water output reaches 90% of the theoretical value. Then, 0.09 times the mass of terephthalic acid is added to hydroxyl-terminated polydimethylsiloxane. The temperature is raised to 270°C, the vacuum degree is 65 Pa, and the stirring power reaches 50 W / 40 Hz. Stirring is then stopped, the vacuum is broken, and the material is discharged to obtain the modified bio-based polyester. The remaining steps are the same as in Example 2.

[0054] Comparative Example 4:

[0055] The difference between the preparation method of the bio-based fiber in Comparative Example 4 and Example 2 lies in step (2). Step (2) is modified as follows: terephthalic acid, bio-based 1,3-propanediol, flame-retardant diol, and antimony trioxide are mixed evenly in a mass ratio of 1:0.65:0.035:0.003. The mixture is reacted at 235°C and 0.35 MPa until the water output reaches 90% of the theoretical value. The temperature is then raised to 270°C, the vacuum degree is 65 Pa, and the stirring power reaches 50 W / 40 Hz. Stirring is then stopped, the vacuum is broken, and the material is discharged to obtain the modified bio-based polyester. The remaining steps are the same as in Example 2.

[0056] Comparative Example 5:

[0057] The difference between the preparation method of bio-based fiber in Comparative Example 5 and Example 2 is that step (3) is omitted, and step (4) is modified as follows: the modified bio-based polyester and biomass graphene are mixed evenly at a mass ratio of 1:0.15, and then added to a twin-screw extruder for melt blending. The temperatures in zones 1, 2, 260, 3, 4, 5, 6, 7, 8 are 255°C, the die head temperature is 250°C, and the screw rotation is... Modified bio-based polyester / biomass graphene blend chips were obtained by extrusion granulation at a speed of 200 rpm. The modified bio-based polyester / biomass graphene blend chips and dicumyl peroxide were mixed uniformly at a mass ratio of 1:0.003 and added to a single-screw spinning mill. The temperatures in zones 1, 2, 3, and 4 were 240℃, 255℃, 265℃, and 270℃, respectively. The temperature of the bending tube, metering pump, and spinning assembly were all 275℃. The spinning speed was 3000 m / min, and the side-blowing speed was 0.45 m / min. The modified bio-based polyester / biomass graphene composite hollow fiber pre-oriented yarn was prepared by winding a 2C-shaped hollow spinneret with two equally spaced concentric rings of equal spacing. The inner diameter of the concentric rings was 0.60 mm, the outer diameter was 0.72 mm, and the ring spacing was 0.06 mm. The pre-oriented yarn was then added to a false-twist texturing machine for false-twist texturing. The first heating chamber temperature was 185 °C, the processing speed was 550 m / min, the D / Y ratio was 1.63, and the draw ratio was 1.68. The remaining steps were the same as in Example 2.

[0058] Comparative Example 6:

[0059] The preparation method of the bio-based fiber in Comparative Example 6 differs from that in Example 2 in that step (3) is omitted, and step (4) is modified as follows: the modified bio-based polyester is added to a twin-screw extruder for melt mixing, with the following temperatures: Zone 1 temperature 245°C, Zone 2 temperature 260°C, Zone 3 temperature 265°C, Zone 4 temperature 270°C, Zone 5 temperature 275°C, Zone 6 temperature 275°C, Zone 7 temperature 260°C, Zone 8 temperature 255°C, die head temperature 250°C, and screw speed 2. Modified bio-based polyester chips were obtained by extrusion granulation at 00 rpm. The modified bio-based polyester chips and dicumyl peroxide were mixed uniformly at a mass ratio of 1:0.003 and added to a single-screw spinning mill. The temperatures in zones 1, 2, 3, and 4 were 240℃, 255℃, 265℃, and 270℃, respectively. The temperature of the bending tube, metering pump, and spinning assembly were all 275℃. The spinning speed was 3000 m / min, and the side-blowing speed was 0.45 m / min. The modified bio-based polyester hollow fiber pre-oriented yarn was prepared by winding a 2C-shaped hollow spinneret with two equally spaced concentric rings of equal spacing. The inner diameter of the concentric rings was 0.60 mm, the outer diameter was 0.72 mm, and the ring spacing was 0.06 mm. The pre-oriented yarn was then added to a false-twist texturing machine for false-twist texturing. The first heating chamber temperature was 185 °C, the processing speed was 550 m / min, the D / Y ratio was 1.63, and the draw ratio was 1.68. The remaining steps were the same as in Example 2.

[0060] Test Example 1:

[0061] Thermal insulation performance test:

[0062] The bio-based fibers obtained from the various embodiments and comparative examples were woven into plain weave fabrics with a warp density of 45 threads / cm and a weft density of 33 threads / cm. The far-infrared emissivity and far-infrared radiation temperature rise were tested in accordance with GB / T30127-2013 "Detection and Evaluation of Far-Infrared Properties of Textiles".

[0063] The results are shown in Table 1.

[0064] Table 1

[0065]

[0066] A comparison of the experimental data from Examples 1-3 and Comparative Examples 1-6 in Table 1 reveals that the bio-based fibers prepared by this invention have excellent heat retention properties.

[0067] By comparison, the far-infrared emissivity and far-infrared radiation temperature rise of Examples 1-3 are greater than those of Comparative Example 6, indicating that biomass graphene has low-temperature far-infrared function, can automatically generate heat and raise the temperature, and dilate human capillaries through related media, thereby accelerating blood circulation, strengthening the metabolism between tissues, and helping to solve the problem of low human skin temperature and frequent coldness. After modification, it can be melt-spun with modified bio-based polyester to improve the warmth retention performance of bio-based fibers.

[0068] Test Example 2:

[0069] Flame retardant performance test:

[0070] The bio-based fibers obtained in each embodiment and comparative example were woven into plain weave fabrics with a warp density of 45 threads / cm and a weft density of 33 threads / cm. The limiting oxygen index was tested in accordance with GB / T5454-1997 "Test of Burning Performance of Textiles - Oxygen Index Method".

[0071] The results are shown in Table 2.

[0072] Table 2

[0073]

[0074] A comparison of the experimental data from Examples 1-3 and Comparative Examples 1-6 in Table 2 reveals that the bio-based fibers prepared by this invention have good flame-retardant properties.

[0075] By comparison, the limiting oxygen index of Examples 1-3 is greater than that of Comparative Examples 1-2, indicating that the epoxy group on 1,4-bis(2',3'-epoxypropyl)perfluorobutane undergoes a ring-opening reaction with the phosphonic acid group on bis(ethylphosphonic acid) to generate a diol containing fluorine and phosphorus. The introduction of fluorine and phosphorus elements can improve the flame retardant properties of bio-based fibers.

[0076] By comparison, the limiting oxygen index of Examples 1-3 is greater than that of Comparative Example 6, indicating that biomass graphene can promote the formation of char layer during combustion. After modification, it is mixed with modified bio-based polyester and melt-spun, which improves the flame retardant properties of bio-based fibers.

[0077] Test Example 3:

[0078] Hydrophobicity test:

[0079] The bio-based fibers obtained in the various embodiments and comparative examples were woven into plain weave fabrics with a warp density of 45 threads / cm and a weft density of 33 threads / cm. The static water contact angle of the fabric was tested using a contact angle meter, with the droplet volume used to measure the water contact angle being 8 μL. Five tests were performed at different locations on the fabric, and the average value was calculated.

[0080] The results are shown in Table 3.

[0081] Table 3

[0082]

[0083] A comparison of the experimental data from Examples 1-3 and Comparative Examples 1-6 in Table 3 reveals that the bio-based fibers prepared by this invention have good hydrophobic properties.

[0084] By comparison, the contact angles of Examples 1-3 are greater than those of Comparative Examples 1-2, indicating that the epoxy groups on 1,4-bis(2',3'-epoxypropyl)perfluorobutane undergo a ring-opening reaction with the phosphonic acid groups on diethylphosphonic acid to generate a diol containing fluorine and phosphorus. Fluorine has low surface energy, and the fluorocarbon segments migrate to the polyester surface, forming a rough structure on the polyester surface, thereby improving the hydrophobic properties of bio-based fibers.

[0085] By comparison, the contact angles of Examples 1-3 are greater than those of Comparative Example 4, indicating that the hydroxyl-terminated dimethylmethyl vinyl (siloxane and polysiloxane) has low surface energy, is orderly arranged on the polyester surface, and further promotes the migration of fluorocarbon segments to the surface, forming more orderly arranged nanoscale protrusions on the surface, thereby enhancing the hydrophobic properties of the bio-based fiber.

[0086] Test Example 4:

[0087] Mechanical property testing: The bio-based fibers prepared in each example and comparative example were tested for breaking strength according to GB / T14344-2008 "Test Method for Tensile Properties of Chemical Fiber Filaments". The settings were: clamping distance of 500 mm, tensile speed of 500 mm / min, pre-tension of 0.05 cN / dtex, test temperature of 20℃, and relative humidity of 65%. Each sample was tested 15 times, and the average value of the test results was taken.

[0088] The results are shown in Table 4.

[0089] Table 4

[0090]

[0091] A comparison of the experimental data from Examples 1-3 and Comparative Examples 1-6 in Table 4 reveals that the bio-based fibers prepared by this invention possess excellent mechanical properties.

[0092] By comparison, the breaking strength of Examples 1-3 is greater than that of Comparative Examples 3-6, indicating that adding biomass graphene to the fiber can improve the mechanical properties of the fiber; the double bonds on the modified biomass graphene react with the double bonds on the modified bio-based polyester under the action of the initiator to form a cross-linked network structure, thereby further improving the mechanical properties of the bio-based fiber.

[0093] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A bio-based fiber, characterized in that, The bio-based fiber is obtained by melt mixing and extruding modified bio-based polyester and modified biomass graphene to obtain modified bio-based polyester / modified biomass graphene blend chips, which are then melt-spun with dicumyl peroxide and false-twist deformed. The modified bio-based polyester is prepared by dehydration condensation of terephthalic acid with bio-based 1,3-propanediol and flame-retardant diol, followed by reaction with hydroxyl-terminated dimethylmethyl vinyl (siloxane and polysiloxane). The flame-retardant diol is prepared by reacting 1,4-bis(2',3'-epoxypropyl)perfluorobutane with diethylphosphonic acid; The modified biomass graphene is prepared by reacting biomass graphene with 3-(methacryloyloxy)propyltrimethoxysilane.

2. A method for preparing bio-based fibers, characterized in that, The preparation steps include the following: (1) Mix 1,4-bis(2',3'-epoxypropyl)perfluorobutane, diethylphosphonic acid, tetrabutylammonium bromide and N,N-dimethylformamide evenly, stir and react at 90~100℃ for 8~10h, distill under reduced pressure, wash and dry to obtain flame-retardant diol; (2) Terephthalic acid, bio-based 1,3-propanediol, flame-retardant diol and antimony trioxide are mixed evenly and reacted at 220~250℃ and 0.3~0.4MPa until the water output is 90% of the theoretical value. Then, 0.08~0.1 times the mass of terephthalic acid is added to hydroxyl-terminated dimethyl methyl vinyl (siloxane and polysiloxane). The temperature is raised to 260~280℃ and the vacuum degree is 60~70Pa. When the stirring power reaches 50W / 40Hz, the stirring is stopped, the vacuum is broken and the material is discharged to obtain modified bio-based polyester. (3) Mix biomass graphene dispersion and 3-(methacryloyloxy)propyltrimethoxysilane dispersion evenly, stir and react at 50~60℃ for 6~8h, centrifuge, wash, dry, and obtain modified biomass graphene. (4) The modified bio-based polyester and modified biomass graphene are mixed evenly at a mass ratio of 1: (0.1~0.2), added to a twin-screw extruder for melt blending, extruded and granulated to obtain modified bio-based polyester / modified biomass graphene blend chips; the modified bio-based polyester / modified biomass graphene blend chips and dicumyl peroxide are mixed evenly at a mass ratio of 1: (0.002~0.004), added to a single-screw spinning machine for melt spinning, and wound to obtain modified bio-based polyester / modified biomass graphene composite hollow fiber pre-oriented yarn; the modified bio-based polyester / modified biomass graphene composite hollow fiber pre-oriented yarn is placed in a false twist texturer for false twist texture to obtain bio-based fiber.

3. The method for preparing a bio-based fiber according to claim 2, characterized in that, The preparation steps of the flame-retardant diol in step (1) are as follows: 1,4-bis(2',3'-epoxypropyl)perfluorobutane, diethylphosphonic acid, tetrabutylammonium bromide and N,N-dimethylformamide are mixed evenly in a mass ratio of 1:(0.8~0.85):(0.03~0.05):(5~10), stirred and reacted at 90~100℃ for 8~10h, N,N-dimethylformamide is removed by vacuum distillation, washed 3~5 times with anhydrous ethanol, and dried under vacuum at 40~50℃ for 10~12h to obtain the flame-retardant diol.

4. The method for preparing a bio-based fiber according to claim 2, characterized in that, The mass ratio of terephthalic acid, bio-based 1,3-propanediol, flame-retardant diol, and antimony trioxide in step (2) is 1:(0.6~0.7):(0.03~0.04):(0.002~0.004).

5. The method for preparing a bio-based fiber according to claim 2, characterized in that, The preparation steps of the modified biomass graphene in step (3) are as follows: Biomass graphene and 90wt% ethanol aqueous solution are mixed evenly at a mass ratio of 1: (400~500), and ultrasonically dispersed to obtain a biomass graphene dispersion; 3-(methacryloyloxy)propyltrimethoxysilane and 90wt% ethanol aqueous solution are mixed evenly at a mass ratio of 1: (40~50), the pH is adjusted to 4 with 2mol / L hydrochloric acid aqueous solution, and stirred for 2~3h to obtain a 3-(methacryloyloxy)propyltrimethoxysilane dispersion; Biomass graphene dispersion and 3-(methacryloyloxy)propyltrimethoxysilane dispersion are mixed evenly at a mass ratio of 1: (0.1~0.12), stirred at 50~60℃ for 6~8h, centrifuged, washed 3~5 times with anhydrous ethanol, and vacuum dried at 40~50℃ for 10~12h to obtain modified biomass graphene.

6. The method for preparing a bio-based fiber according to claim 2, characterized in that, The process parameters for melt blending and extrusion granulation in step (4) are as follows: zone 1 temperature 245℃, zone 2 temperature 260℃, zone 3 temperature 265℃, zone 4 temperature 270℃, zone 5 temperature 275℃, zone 6 temperature 275℃, zone 7 temperature 260℃, zone 8 temperature 255℃, die head temperature 250℃, and screw speed 200rpm.

7. The method for preparing a bio-based fiber according to claim 2, characterized in that, The process parameters for melt spinning in step (4) are as follows: zone 1 temperature 240℃, zone 2 temperature 255℃, zone 3 temperature 265℃, zone 4 temperature 270℃, tube bending temperature 275℃, metering pump temperature 275℃, spinning assembly temperature 275℃, spinning speed 3000m / min, side blowing speed 0.45m / s, air temperature 22℃, oil content 0.8%, the spinneret is a 2C-shaped hollow spinneret, the spinneret holes are two concentric rings that are equally spaced, the ring spacing is equal, the inner diameter of the concentric ring is 0.60mm, the outer diameter is 0.72mm, and the ring spacing is 0.06mm.

8. The method for preparing a bio-based fiber according to claim 2, characterized in that, The process parameters for false twisting deformation in step (4) are: first hot box temperature 185℃, processing speed 550m / min, D / Y ratio 1.63, and draw ratio 1.68.

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