Bio-based fiber for fabric and preparation method thereof

Abstract

The invention discloses a bio-based fiber for fabric and a preparation method thereof, and relates to the field of fiber technology. The bio-based fiber for fabric in the present invention is prepared by introducing a hygroscopic agent on the surface of polyamide ester fiber; the hygroscopic agent is furan alcohol acid, the polyamide ester fiber is prepared by spinning polyamide ester slices and coating dopamine-modified silicone oil, the dopamine-modified silicone oil is prepared by reacting 3-isocyanate propyl trimethoxy silane with dopamine and then co-hydrolyzing with dimethyl dimethoxy silane to enhance the mechanical properties of the polyamide ester fiber; furan alcohol acid is prepared by reacting polyhydroxy polytetrahydrofuran with pyromellitic dianhydride, and polyhydroxy polytetrahydrofuran is prepared by ring-opening polymerization of polytetrahydrofuran and 3-hydroxymethyl-3-methyloxetane, so that the bio-based fiber has not only excellent hydrophilicity, but also strong washability.

Description

Technical Field

[0001] The invention relates to the field of fiber technology, in particular to a bio-based fiber for fabric and a preparation method thereof. Background Art

[0002] Traditional chemical fibers are mainly made of petroleum-based polymers. Since petroleum is a non-renewable resource and is becoming increasingly depleted, it poses a huge crisis to the sustainable development of chemical fibers. Introducing bio-based materials into fiber materials allows bio-based fibers to replace chemical fibers. Not only can it be sustainable, but the raw materials of bio-based materials are also renewable, most of them are biodegradable, and the manufacturing process is green and environmentally friendly, with less carbon dioxide emissions, which can effectively alleviate the greenhouse effect.

[0003] However, during the synthesis process of bio-based materials, due to the poor structural stability of bio-based monomers, it is difficult to control the molecular weight of the polymer, and it is impossible to meet the spinning grade requirements. It is urgent to improve its comprehensive performance through synthesis technology to meet the requirements. Therefore, the present invention studies and prepares a bio-based fiber for fabric that can replace chemical fibers, which not only has excellent mechanical properties, but also has excellent hydrophilicity and washability. Summary of the invention

[0004] The object of the present invention is to provide a bio-based fiber for fabric and a preparation method thereof, so as to solve the problems raised in the above background technology.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions: a bio-based fiber for fabric, wherein the bio-based fiber for fabric is prepared by introducing a moisture absorbent on the surface of polyamide ester fiber; the moisture absorbent is furan alcohol acid.

[0006] Preferably, the polyamide polyester fiber is prepared by spinning polyamide polyester slices and then coating them with dopamine-modified silicone oil.

[0007] Preferably, the dopamine-modified silicone oil is prepared by reacting 3-isocyanatepropyltrimethoxysilane with dopamine and then co-hydrolyzing with dimethyldimethoxysilane.

[0008] Preferably, the furan alcohol acid is prepared by the reaction of polyhydroxy polytetrahydrofuran and pyromellitic dianhydride; the polyhydroxy polytetrahydrofuran is prepared by the ring-opening polymerization of polytetrahydrofuran and 3-hydroxymethyl-3-methyloxetane.

[0009] Preferably, a method for preparing bio-based fibers for fabrics comprises the following specific steps:

[0010] (1) melt spinning polyamide polyester slices to obtain polyamide polyester yarns;

[0011] (2) Under a nitrogen atmosphere, dimethyldimethoxysilane, dopamine alkoxysilane, triethylamine and deionized water were mixed in a mass ratio of 1-3:2-4:1:8-10, heated to 80-90°C, reacted for 4-6 hours, cooled to 55-65°C, distilled under reduced pressure, then heated to 110-120°C, balanced for 8-10 hours, and distilled under reduced pressure at 55-65°C again to obtain dopamine-modified silicone oil;

[0012] (3) immersing the polyamide polyester yarn in dopamine-modified silicone oil, stirring the reaction at 100-200 rpm and room temperature for 1-3 hours, taking it out and washing it with deionized water for 3-5 times, and then drying it in a vacuum drying oven at 60-70°C, and then bundling, stretching, heat setting, curling, shaping, cutting, and packaging to obtain polyamide polyester fiber;

[0013] (4) Under a nitrogen atmosphere, polyhydroxy polytetrahydrofuran and pyromellitic anhydride are mixed in a mass ratio of 1:9-11, the oil bath is heated to 95-105°C, and the mixture is stirred at 100-200 rpm for 4-6 hours to obtain furan alcohol acid;

[0014] (5) Immerse the polyamide ester fiber in furan alcohol acid, raise the temperature to 50-70°C, react at 50-100 rpm for 6-8 hours, remove the fiber, wash it with deionized water for 3-5 times, and dry it to obtain a bio-based fiber for fabric.

[0015] Preferably, in the above step (1): the preparation method of polyamide ester slices is: terephthalic acid, ethylene glycol, antimony trioxide, triphenyl phosphite and water are mixed and slurried in a mass ratio of 1:1.2~1.4:0.003~0.05:0.02~0.04:3~5, the temperature is raised to 220~240°C, the pressure is adjusted to 150~360kPa, the reaction is carried out for 2~3h, and then the pressure is evacuated to 30~50Pa, the reaction is continued for 50~70min, the pressure is adjusted to atmospheric pressure by nitrogen, 0.22~0.24 times the mass of terephthalic acid of bio-based polyamide 56 oligomer is added, the temperature is again raised to 20~30Pa, the reaction is carried out for 30~50min, the temperature is raised to 260~275°C, the reaction is carried out for 2~3h, and the polyamide ester slices are obtained.

[0016] Preferably, in the above step (1): during melt spinning, the spinning metering pump supply is controlled to be 700-800 g / min, the spinning temperature is 280-300° C., the spinning speed is 800-1000 m / min, and the draft ratio is 2.0-3.0 times.

[0017] Preferably, in the above step (2): the preparation method of dopamine alkoxysilane is: heating a saturated solution of dopamine hydrochloride in N,N-dimethylformamide to 40-45°C, adding 3-isocyanatepropyltrimethoxysilane in an amount of 0.003-0.006 times the volume of the saturated solution of dopamine hydrochloride in N,N-dimethylformamide at a rate of 3-5 ml / min under a nitrogen atmosphere, reacting for 4-6 hours and then rotary evaporating to obtain dopamine alkoxysilane.

[0018] Preferably, in the above step (4), the preparation method of polyhydroxy polytetrahydrofuran is as follows: polytetrahydrofuran, dichloromethane and boron trifluoride·ether complex are mixed in a mass ratio of 1~5:15~20:0.08 and stirred evenly, then cooled to 0~2°C, 3-hydroxymethyl-3-methyloxetane in an amount of 1.8~2.2 times the mass of polytetrahydrofuran is added dropwise at a rate of 1~3 ml / min, and the reaction is continued for 18~24 hours, and then the reaction is terminated with a sodium carbonate solution with a mass fraction of 2~4%, and the solution is allowed to stand for separation and washed with water for 3~5 times, and then distilled under reduced pressure to obtain polyhydroxy polytetrahydrofuran.

[0019] Preferably, the preparation method of the polytetrahydrofuran is as follows: in a nitrogen atmosphere, tetrahydrofuran and acetic anhydride are mixed in a mass ratio of 2.4-2.8:0.3-0.5, placed in an ice bath and stirred evenly, and then perchloric acid with a mass of 0.06-0.08 times that of tetrahydrofuran is added, stirred evenly and reacted for 2-3 hours, deionized water is added to terminate the reaction, stirred at 400-800 rpm for 20-40 minutes, and then transferred to -10--20°C and frozen until no solidified product is generated, and removed After the solidified product is precipitated into liquid, it is dissolved in dichloromethane, washed with deionized water, allowed to stand, and separated. After rotary evaporation of the lower layer of liquid, methanol 2 to 2.3 times the mass of tetrahydrofuran and sodium hydroxide 0.01 to 0.02 times the mass of tetrahydrofuran are added, the temperature is raised to 70 to 80°C, refluxed for 4 to 5 hours, rotary evaporated, dissolved again with dichloromethane, and the pH is adjusted to 6.8 to 7.2 with hydrochloric acid. After washing with deionized water for 5 to 8 times, allowed to stand and separated, the lower layer is rotary evaporated to obtain polytetrahydrofuran.

[0020] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0021] The bio-based fiber for fabric prepared by the present invention is prepared by introducing a moisture absorbent on the surface of polyamide ester fiber; the moisture absorbent is furan alcohol acid;

[0022] The polyamide polyester fiber is prepared by spinning polyamide polyester slices and then coating dopamine-modified silicone oil; the dopamine-modified silicone oil is prepared by reacting 3-isocyanate propyltrimethoxysilane with dopamine and then co-hydrolyzing with dimethyldimethoxysilane; the isocyanate group reacts with the amino group on the dopamine to form a urea bond, which not only forms a stable silicon-oxygen network on the surface of the polyamide polyester fiber during hydrolysis, but also forms hydrogen bonds, tightly connecting the dopamine-modified silicone oil to the surface of the polyamide polyester fiber, thereby enhancing the mechanical properties of the polyamide polyester fiber;

[0023] Furan alcohol acid is prepared by the reaction of polyhydroxy polytetrahydrofuran and pyromellitic acid dianhydride, and polyhydroxy polytetrahydrofuran is prepared by the ring-opening polymerization of polytetrahydrofuran and 3-hydroxymethyl-3-methyloxetane; polytetrahydrofuran reacts with pyromellitic acid dianhydride to form a long-chain diol having hydroxyl and carboxyl groups, and then undergoes ring-opening polymerization with 3-hydroxymethyl-3-methyloxetane to form a long-chain polyhydroxy furan alcohol acid with a branched structure. After a desiccant is introduced onto the surface of polyamide ester fiber, furan alcohol acid continues to react with the remaining amino groups on dopamine-modified silicone oil, and a large number of hydrophilic groups are introduced onto the surface of polyamide ester fiber, so that the bio-based fiber not only has excellent hydrophilicity, but also has strong wash resistance. DETAILED DESCRIPTION

[0024] The technical scheme in the embodiment of the present invention will be clearly and completely described below in conjunction with the embodiment of the present invention. Obviously, the described embodiment is only a part of the embodiment of the present invention, rather than all the embodiments. Based on the embodiment of the present invention, all other embodiments obtained by ordinary technicians in the field without creative work are within the scope of protection of the present invention. The trifluoro expanded ether complex in the embodiment of the present invention and the comparative example was purchased from Chengdu Kelong Chemical Reagent Factory, and the other reagents were all commercially available products.

[0025] In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe in detail the various index testing methods of the bio-based fibers for fabrics prepared in the examples and comparative examples as follows:

[0026] Mechanical properties: The bio-based fibers prepared in the examples and comparative examples were subjected to tensile strength tests according to GB / T2418.3;

[0027] Hydrophilicity: The fabrics prepared in the examples and comparative examples were tested for surface contact angle using bio-based fibers;

[0028] Washability: After the fabrics prepared in the examples and comparative examples were washed 50 times with bio-based fibers, the hydrophilicity test was performed again.

[0029] Example 1

[0030] (1) Terephthalic acid, ethylene glycol, antimony trioxide, triphenyl phosphite and water were mixed and slurried in a mass ratio of 1:1.2:0.003:0.02:3, heated to 220°C, adjusted the pressure to 150 kPa, reacted for 2 hours, then evacuated to 30 Pa, continued to react for 50 minutes, filled with nitrogen to adjust the pressure to atmospheric pressure, added bio-based polyamide 56 oligomer with a mass of 0.22 times that of terephthalic acid, evacuated to 20 Pa again, reacted for 30 minutes, heated to 260°C, reacted for 2 hours, and obtained polyamide polyester chips; the polyamide polyester chips were melt-spun, the spinning metering pump supply was controlled to 700 g / min, the spinning temperature was 280°C, the spinning speed was 800 m / min, and the draft ratio was 2.0 times, and polyamide polyester yarn was obtained;

[0031] (2) The saturated solution of dopamine hydrochloride in N,N-dimethylformamide was heated to 40°C, and 3-isocyanatepropyltrimethoxysilane (0.003 times the volume of the saturated solution of dopamine hydrochloride in N,N-dimethylformamide) was added dropwise at a rate of 3 ml / min under a nitrogen atmosphere. After reacting for 4 hours, the mixture was rotary evaporated to obtain dopamine alkoxysilane. Under a nitrogen atmosphere, dimethyldimethoxysilane, dopamine alkoxysilane, triethylamine and deionized water were mixed in a mass ratio of 1:2:1:8, heated to 80°C, reacted for 4 hours, cooled to 55°C, distilled under reduced pressure, heated to 110°C, balanced for 8 hours, and distilled under reduced pressure at 55°C again to obtain dopamine modified silicone oil.

[0032] (3) immersing the polyamide polyester fiber in dopamine-modified silicone oil, stirring the reaction at 100 rpm and room temperature for 1 hour, taking it out and washing it with deionized water for 3 times, and then drying it in a vacuum drying oven at 60°C, and then bundling, stretching, heat setting, curling, shaping, cutting, and packaging to obtain polyamide polyester fiber;

[0033] (4) Under a nitrogen atmosphere, tetrahydrofuran and acetic anhydride were mixed in a mass ratio of 2.4:0.3, placed in an ice bath and stirred evenly, and then perchloric acid (0.06 times the mass of tetrahydrofuran) was added, stirred evenly and reacted for 2 hours, and then deionized water was added to terminate the reaction. After stirring at 400 rpm for 20 minutes, the mixture was transferred to -10°C and frozen until no solidified product was generated. After removing the liquid, the solidified product was dissolved with dichloromethane, washed with deionized water, allowed to stand, and separated. After rotary evaporation of the lower layer of liquid, methanol (2 times the mass of tetrahydrofuran) and sodium hydroxide (0.01 times the mass of tetrahydrofuran) were added, the temperature was raised to 70°C, refluxed for 4 hours, rotary evaporation, dissolved with dichloromethane again, and the pH was adjusted to 6.8 with hydrochloric acid. After washing with deionized water 5 times, the mixture was allowed to stand and separated. After rotary evaporation of the lower layer, polytetrahydrofuran was obtained;

[0034] (5) After polytetrahydrofuran, dichloromethane and boron trifluoride·ether complex are mixed in a mass ratio of 1:15:0.08 and stirred evenly, the temperature is lowered to 0°C, and 3-hydroxymethyl-3-methyloxetane (1.8 times the mass of polytetrahydrofuran) is added dropwise at a rate of 1 ml / min. After the reaction is continued for 18 hours, the reaction is terminated with a 2% sodium carbonate solution, the solution is allowed to stand for separation and washed with water for 3 times, and distilled under reduced pressure to obtain polyhydroxy polytetrahydrofuran; under a nitrogen atmosphere, polyhydroxy polytetrahydrofuran is mixed with pyromellitic anhydride in a mass ratio of 1:9, the oil bath is heated to 95°C, and the reaction is stirred at 100 rpm for 4 hours to obtain furan alcohol acid;

[0035] (6) The polyamide ester fiber is immersed in furan alcohol acid, heated to 50°C, reacted at 50 rpm for 6 hours, then taken out, washed three times with deionized water, and dried to obtain a bio-based fiber for fabric.

[0036] Example 2

[0037] (1) Terephthalic acid, ethylene glycol, antimony trioxide, triphenyl phosphite and water were mixed and slurried in a mass ratio of 1:13:0.004:0.03:4, heated to 230°C, adjusted the pressure to 240 kPa, reacted for 2.5 hours, then evacuated to a pressure of 40 Pa, continued to react for 60 minutes, filled with nitrogen to adjust the pressure to atmospheric pressure, added bio-based polyamide 56 oligomer with a mass of 0.23 times that of terephthalic acid, evacuated again to 25 Pa, reacted for 40 minutes, heated to 268°C, reacted for 2.5 hours, and obtained polyamide polyester chips; the polyamide polyester chips were melt-spun, the spinning metering pump supply was controlled to 750 g / min, the spinning temperature was 290°C, the spinning speed was 900 m / min, and the drafting ratio was 2.5 times, and polyamide polyester yarn was obtained;

[0038] (2) The saturated solution of dopamine hydrochloride in N,N-dimethylformamide was heated to 43°C, and 3-isocyanatepropyltrimethoxysilane (0.0045 times the volume of the saturated solution of dopamine hydrochloride in N,N-dimethylformamide) was added dropwise at a rate of 4 ml / min under a nitrogen atmosphere. After reacting for 5 hours, the mixture was rotary evaporated to obtain dopamine alkoxysilane. Under a nitrogen atmosphere, dimethyldimethoxysilane, dopamine alkoxysilane, triethylamine and deionized water were mixed in a mass ratio of 2:3:1:9, heated to 85°C, reacted for 5 hours, cooled to 60°C, distilled under reduced pressure, heated to 115°C, balanced for 9 hours, and distilled under reduced pressure at 60°C again to obtain dopamine modified silicone oil.

[0039] (3) immersing the polyamide polyester fiber in dopamine-modified silicone oil, stirring and reacting at 150 rpm and room temperature for 2 hours, taking it out and washing it with deionized water for 4 times, and then drying it in a vacuum drying oven at 65°C, and then bundling, stretching, heat setting, curling, shaping, cutting, and packaging to obtain polyamide polyester fiber;

[0040] (4) Under a nitrogen atmosphere, tetrahydrofuran and acetic anhydride were mixed in a mass ratio of 2.6:0.4, placed in an ice bath and stirred evenly, and then perchloric acid (0.07 times the mass of tetrahydrofuran) was added, stirred evenly and reacted for 2.5 hours, and then deionized water was added to terminate the reaction. After stirring at 600 rpm for 30 minutes, the mixture was transferred to -15°C and frozen until no solidified product was generated. After removing the liquid, the solidified product was dissolved with dichloromethane, washed with deionized water, allowed to stand, and separated. After rotary evaporation of the lower layer of liquid, methanol (2.1 times the mass of tetrahydrofuran) and sodium hydroxide (0.015 times the mass of tetrahydrofuran) were added, the temperature was raised to 75°C, refluxed for 4.5 hours, rotary evaporation, dissolved with dichloromethane again, and the pH was adjusted to 7 with hydrochloric acid. After washing with deionized water 7 times, the mixture was allowed to stand and separated. After rotary evaporation of the lower layer, polytetrahydrofuran was obtained;

[0041] (5) After polytetrahydrofuran, dichloromethane and boron trifluoride·ether complex are mixed in a mass ratio of 3:17:0.08 and stirred evenly, the temperature is lowered to 1°C, 3-hydroxymethyl-3-methyloxetane (2 times the mass of polytetrahydrofuran) is added dropwise at a rate of 2 ml / min, and the reaction is continued for 21 hours. The reaction is terminated with a 3% sodium carbonate solution, the mixture is allowed to stand for separation and washed with water for 4 times, and distilled under reduced pressure to obtain polyhydroxy polytetrahydrofuran; under a nitrogen atmosphere, polyhydroxy polytetrahydrofuran is mixed with pyromellitic anhydride in a mass ratio of 1:10, the oil bath is heated to 100°C, and the mixture is stirred at 150 rpm for 5 hours to obtain furan alcohol acid;

[0042] (6) The polyamide ester fiber is immersed in furan alcohol acid, the temperature is raised to 60°C, and the reaction is carried out at 75 rpm for 7 hours. The fiber is then taken out, washed four times with deionized water, and dried to obtain a bio-based fiber for fabric.

[0043] Example 3

[0044] (1) Terephthalic acid, ethylene glycol, antimony trioxide, triphenyl phosphite and water were mixed and beaten in a mass ratio of 1:1.4:0.05:0.04:5, the temperature was raised to 240°C, the pressure was adjusted to 360 kPa, the reaction was carried out for 3 hours, and then the pressure was evacuated to 50 Pa, the reaction was continued for 70 minutes, the pressure was adjusted to atmospheric pressure by nitrogen, and a bio-based polyamide 56 oligomer with a mass of 0.24 times that of terephthalic acid was added, the temperature was again raised to 30 Pa, the reaction was carried out for 50 minutes, the temperature was raised to 275°C, the reaction was carried out for 3 hours, and polyamide polyester chips were obtained; the polyamide polyester chips were melt-spun, the spinning metering pump supply was controlled to 800 g / min, the spinning temperature was 300°C, the spinning speed was 1000 m / min, and the drafting ratio was 3.0 times, and polyamide polyester yarn was obtained;

[0045] (2) The saturated solution of dopamine hydrochloride in N,N-dimethylformamide was heated to 45°C, and 3-isocyanatepropyltrimethoxysilane (0.006 times the volume of the saturated solution of dopamine hydrochloride in N,N-dimethylformamide) was added dropwise at a rate of 5 ml / min under a nitrogen atmosphere. After reacting for 6 hours, the mixture was rotary evaporated to obtain dopamine alkoxysilane. Under a nitrogen atmosphere, dimethyldimethoxysilane, dopamine alkoxysilane, triethylamine and deionized water were mixed in a mass ratio of 3:4:1:10, heated to 90°C, reacted for 6 hours, cooled to 65°C, distilled under reduced pressure, heated to 120°C, balanced for 10 hours, and distilled under reduced pressure at 65°C again to obtain dopamine modified silicone oil.

[0046] (3) immersing the polyamide polyester fiber in dopamine-modified silicone oil, stirring and reacting at 200 rpm and room temperature for 3 hours, taking it out and washing it with deionized water for 5 times, and then drying it in a vacuum drying oven at 70°C, and then bundling, stretching, heat setting, curling, shaping, cutting, and packaging to obtain polyamide polyester fiber;

[0047] (4) Under a nitrogen atmosphere, tetrahydrofuran and acetic anhydride were mixed in a mass ratio of 2.8:0.5, placed in an ice bath and stirred evenly, and then perchloric acid (0.08 times the mass of tetrahydrofuran) was added, stirred evenly and reacted for 3 hours, and then deionized water was added to terminate the reaction. After stirring at 800 rpm for 40 minutes, the mixture was transferred to -20°C and frozen until no solidified product was generated. After removing the liquid, the solidified product was dissolved with dichloromethane, washed with deionized water, allowed to stand, and separated. After rotary evaporation of the lower layer of liquid, methanol (2.3 times the mass of tetrahydrofuran) and sodium hydroxide (0.02 times the mass of tetrahydrofuran) were added, the temperature was raised to 80°C, refluxed for 5 hours, rotary evaporation, dissolved with dichloromethane again, and the pH was adjusted to 7.2 with hydrochloric acid. After washing with deionized water 8 times, the mixture was allowed to stand and separated. After rotary evaporation of the lower layer, polytetrahydrofuran was obtained;

[0048] (5) After polytetrahydrofuran, dichloromethane and boron trifluoride·ether complex are mixed in a mass ratio of 5:20:0.08 and stirred evenly, the temperature is lowered to 2°C, 3-hydroxymethyl-3-methyloxetane (2.2 times the mass of polytetrahydrofuran) is added dropwise at a rate of 3 ml / min, and the reaction is continued for 24 hours. The reaction is terminated with a sodium carbonate solution with a mass fraction of 4%, and the mixture is allowed to stand for separation and washed with water for 5 times. The mixture is then distilled under reduced pressure to obtain polyhydroxy polytetrahydrofuran; under a nitrogen atmosphere, the polyhydroxy polytetrahydrofuran is mixed with pyromellitic anhydride in a mass ratio of 1:11, the oil bath is heated to 105°C, and the mixture is stirred at 200 rpm for 6 hours to obtain furan alcohol acid;

[0049] (6) The polyamide ester fiber was immersed in furan alcohol acid, heated to 70°C, reacted at 100 rpm for 8 hours, then taken out, washed with deionized water for 5 times, and dried to obtain a bio-based fiber for fabric.

[0050] Comparative Example 1

[0051] The formulation composition of Comparative Example 1 is the same as that of Example 2. The only difference between the method for preparing the bio-based fiber for fabric and Example 2 is that the preparation in step (2) is not performed, and step (3) is modified to: bundling, stretching, heat setting, crimping, shaping, cutting, and packing the polyamide polyester yarn to prepare the polyamide polyester fiber.

[0052] Comparative Example 2

[0053] The formulation composition of Comparative Example 2 is the same as that of Example 2. The only difference between the method for preparing the bio-based fiber for fabric and Example 2 is that the preparation of step (2) is not performed, and step (3) is modified as follows: immersing the polyamide polyester yarn in a saturated solution of dopamine hydrochloride in N,N-dimethylformamide, stirring and reacting for 2 hours at 150 rpm and room temperature, taking it out and washing it with deionized water for 4 times, and then drying it in a vacuum drying oven at 65°C, and then bundling, stretching, heat setting, curling, shaping, cutting, and packaging to obtain the polyamide polyester fiber.

[0054] Comparative Example 3

[0055] The formulation composition of Comparative Example 3 is the same as that of Example 2. The difference between the method for making the bio-based fiber for fabric and Example 2 is only in the difference of steps (5) and (6), and steps (5) and (6) are modified as follows:

[0056] (5) After mixing polytetrahydrofuran, dichloromethane and boron trifluoride·ether complex in a mass ratio of 5:20:0.08 and stirring evenly, the mixture was cooled to 2°C, and 3-hydroxymethyl-3-methyloxetane (2.2 times the mass of polytetrahydrofuran) was added dropwise at a rate of 3 ml / min. After the reaction was continued for 24 hours, the reaction was terminated with a 4% sodium carbonate solution, and the mixture was allowed to stand for separation and washed with water for 5 times. The mixture was then distilled under reduced pressure to obtain polyhydroxy polytetrahydrofuran.

[0057] (6) The polyamide ester fiber is immersed in polyhydroxy polytetrahydrofuran, the temperature is raised to 60°C, and the reaction is carried out at 75 rpm for 7 hours. The fiber is then taken out, washed four times with deionized water, and dried to obtain a bio-based fiber for fabric.

[0058] Comparative Example 4

[0059] The formulation composition of Comparative Example 4 is the same as that of Example 2. The only difference between the method for preparing bio-based fibers for fabric and Example 2 is that the treatment in step (5) is not performed, and step (6) is modified as follows: immersing the polyamide ester fiber in polytetrahydrofuran, heating to 60° C., reacting at 75 rpm for 7 h, then taking it out, washing it with deionized water 4 times, and drying it to prepare the bio-based fibers for fabric.

[0060] Effect example

[0061] Table 1 below shows the performance analysis results of the bio-based fibers for fabrics using Examples 1 to 3 of the present invention and Comparative Examples 1 to 5:

[0062] Table 1

[0063] Tensile strength (GPa) Surface contact angle (°) Surface contact angle after 50 water washings (°) Example 1 5.21 35 37 Example 2 5.29 31 33 Example 3 5.16 36 37 Comparative Example 1 4.23 38 40 Comparative Example 2 4.56 37 39 Comparative Example 3 5.01 54 63 Comparative Example 4 5.03 59 68

[0064] By comparing the experimental data of the examples and the comparative examples in Table 1, it can be clearly found that the bio-based fibers for fabrics prepared in Examples 1, 2, and 3 have excellent mechanical properties, hydrophilicity, and washability.

[0065] From the comparison of the experimental data of Example 1, Example 2, Example 3 and Comparative Example 1, Comparative Example 2, it can be found that after the reaction of 3-isocyanatepropyltrimethoxysilane and dopamine, the dopamine-modified silicone oil is co-hydrolyzed with dimethyldimethoxysilane. During the hydrolysis, not only a stable silicon-oxygen network is formed on the surface of the polyamide ester fiber, but also hydrogen bonds can be formed to tightly connect the dopamine-modified silicone oil to the surface of the polyamide ester fiber, thereby enhancing the mechanical properties of the polyamide ester fiber.

[0066] From the comparison of the experimental data of Example 1, Example 2, Example 3 and Comparative Example 3, Comparative Example 4, it can be found that the polyhydroxy polytetrahydrofuran is obtained by the ring-opening polymerization of polytetrahydrofuran and 3-hydroxymethyl-3-methyloxetane, and the furan alcohol acid obtained by the reaction of polyhydroxy polytetrahydrofuran with pyromellitic dianhydride has a long chain and mass structure, and also has a carboxyl group and a large number of hydroxyl groups, which can continue to react with the remaining amino groups on the dopamine-modified silicone oil, and introduce a large number of hydrophilic groups on the surface of the polyamide ester fiber, so that the bio-based fiber has not only excellent hydrophilicity, but also strong wash resistance.

[0067] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A bio-based fiber for fabric, characterized in that: The bio-based fiber for fabric is prepared by introducing a moisture absorbent on the surface of polyamide ester fiber; the moisture absorbent is furan alcohol acid; the polyamide ester fiber is prepared by spinning polyamide ester slices and then coating dopamine-modified silicone oil; the dopamine-modified silicone oil is prepared by reacting 3-isocyanate propyl trimethoxy silane with dopamine and then co-hydrolyzing with dimethyl dimethoxy silane; the furan alcohol acid is prepared by reacting polyhydroxy polytetrahydrofuran with pyromellitic acid anhydride; the polyhydroxy polytetrahydrofuran is prepared by ring-opening polymerization of polytetrahydrofuran and 3-hydroxymethyl-3-methyloxetane; the preparation method of the polyamide ester slice is as follows: terephthalic acid, ethylene glycol, dioxygen ester, Antimony, triphenyl phosphite and water are mixed and slurried in a mass ratio of 1:1.2~1.4:0.003~0.05:0.02~0.04:3~5, the temperature is raised to 220~240℃, the pressure is adjusted to 150~360kPa, the reaction is carried out for 2~3h, and then the pressure is evacuated to 30~50Pa, the reaction is continued for 50~70min, the pressure is adjusted to atmospheric pressure by nitrogen filling, and 0.22~0.24 times the mass of terephthalic acid bio-based polyamide 56 oligomer is added, the temperature is raised to 20~30Pa again, the reaction is carried out for 30~50min, the temperature is raised to 260~275℃, the reaction is carried out for 2~3h, and polyamide ester slices are obtained.

2. A method for preparing bio-based fibers for fabrics as claimed in claim 1, characterized in that: The method for preparing the bio-based fiber for fabric comprises the following specific steps: (1) melt spinning polyamide polyester slices to obtain polyamide polyester yarns; (2) Under a nitrogen atmosphere, dimethyldimethoxysilane, dopamine alkoxysilane, triethylamine and deionized water were mixed in a mass ratio of 1-3:2-4:1:8-10, heated to 80-90°C, reacted for 4-6 hours, cooled to 55-65°C, distilled under reduced pressure, then heated to 110-120°C, balanced for 8-10 hours, and distilled under reduced pressure at 55-65°C again to obtain dopamine-modified silicone oil; (3) immersing the polyamide polyester yarn in dopamine-modified silicone oil, stirring the reaction at 100-200 rpm and room temperature for 1-3 hours, taking it out and washing it with deionized water for 3-5 times, and then drying it in a vacuum drying oven at 60-70°C, and then bundling, stretching, heat setting, curling, shaping, cutting, and packaging to obtain polyamide polyester fiber; (4) Under a nitrogen atmosphere, polyhydroxy polytetrahydrofuran and pyromellitic anhydride are mixed in a mass ratio of 1:9-11, the oil bath is heated to 95-105°C, and the mixture is stirred at 100-200 rpm for 4-6 hours to obtain furan alcohol acid; (5) Immerse the polyamide ester fiber in furan alcohol acid, raise the temperature to 50-70°C, react at 50-100 rpm for 6-8 hours, remove the fiber, wash it with deionized water for 3-5 times, and dry it to obtain a bio-based fiber for fabric.

3. The method for preparing bio-based fibers for fabrics according to claim 2, characterized in that: In the above step (1): during melt spinning, the spinning metering pump supply is controlled to be 700-800 g / min, the spinning temperature is 280-300°C, the spinning speed is 800-1000 m / min, and the draft ratio is 2.0-3.0 times.

4. The method for preparing bio-based fibers for fabrics according to claim 2, characterized in that: In the above step (2): the preparation method of dopamine alkoxysilane is: heating a saturated solution of dopamine hydrochloride in N,N-dimethylformamide to 40-45°C, adding 3-isocyanatepropyltrimethoxysilane in an amount of 0.003-0.006 times the volume of the saturated solution of dopamine hydrochloride in N,N-dimethylformamide at a rate of 3-5 ml / min under a nitrogen atmosphere, reacting for 4-6 hours and then rotary evaporating to obtain dopamine alkoxysilane.

5. The method for preparing bio-based fibers for fabrics according to claim 2, characterized in that: In the above step (4), the preparation method of polyhydroxy polytetrahydrofuran is as follows: polytetrahydrofuran, dichloromethane and boron trifluoride·ether complex are mixed in a mass ratio of 1~5:15~20:0.08 and stirred evenly, then cooled to 0~2°C, 3-hydroxymethyl-3-methyloxetane in an amount of 1.8~2.2 times the mass of polytetrahydrofuran is added dropwise at a rate of 1~3 ml / min, the reaction is continued for 18~24 hours, and then the reaction is terminated with a sodium carbonate solution with a mass fraction of 2~4%, the solution is allowed to stand for separation and washed with water for 3~5 times, and then distilled under reduced pressure to obtain polyhydroxy polytetrahydrofuran.

6. The method for preparing bio-based fibers for fabrics according to claim 5, characterized in that: The preparation method of the polytetrahydrofuran is as follows: in a nitrogen atmosphere, tetrahydrofuran and acetic anhydride are mixed in a mass ratio of 2.4-2.8:0.3-0.5, placed in an ice bath and stirred evenly, then perchloric acid with a mass of 0.06-0.08 times of the mass of tetrahydrofuran is added, stirred evenly and reacted for 2-3 hours, deionized water is added to terminate the reaction, stirred at 400-800 rpm for 20-40 minutes, transferred to -10--20°C and frozen until no solidified product is generated, and the liquid is removed. After that, the solidified product was dissolved with dichloromethane, washed with deionized water, allowed to stand, and separated. After rotary evaporation of the lower layer of liquid, methanol 2 to 2.3 times the mass of tetrahydrofuran and sodium hydroxide 0.01 to 0.02 times the mass of tetrahydrofuran were added, the temperature was raised to 70 to 80°C, refluxed for 4 to 5 hours, rotary evaporated, dissolved with dichloromethane again, and the pH was adjusted to 6.8 to 7.2 with hydrochloric acid. After washing with deionized water for 5 to 8 times, allowed to stand and separated, the lower layer was rotary evaporated to obtain polytetrahydrofuran.