CN114934326A - Preparation method of bio-based degradable polyamide fiber - Google Patents
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- CN114934326A CN114934326A CN202210633261.1A CN202210633261A CN114934326A CN 114934326 A CN114934326 A CN 114934326A CN 202210633261 A CN202210633261 A CN 202210633261A CN 114934326 A CN114934326 A CN 114934326A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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Abstract
The invention discloses a preparation method of a bio-based degradable polyamide fiber, which comprises the following steps: 1) adding the fully dried polybutyrolactam resin into a mixed solvent of trifluoropropanol and hexafluoroisopropanol, heating and stirring for 3-5 hours to prepare a polybutyrolactam spinning solution; wherein the mass fraction of the polybutyrolactam in the spinning solution is 6-15 wt%; 2) transferring the spinning solution obtained in the step 1) into a feeding kettle, respectively controlling the temperature of the kettle, a metering pump and a spinning nozzle by using a circulating water bath and a heating device to keep the temperature of the kettle, the metering pump and the spinning nozzle at 30-35 ℃, extruding the spinning solution through the spinning nozzle under certain pressure, then feeding the extruded spinning solution into an air layer, continuously feeding the extruded spinning solution into a coagulating bath to be solidified into fibers, and winding and forming the fibers to obtain polybutyrolactam nascent fibers; 3) and (3) carrying out certain back drawing on the polybutyrolactam nascent fiber in hot air, cleaning and airing to obtain the bio-based degradable polybutyrolactam fiber. The fiber strength obtained by the method can reach more than 2cN/dtex, and the degradation performance is good.
Description
Technical Field
The invention relates to the technical field of biodegradable fibers, in particular to a degradable polybutyrolactam fiber and a preparation method thereof.
Background
Polyamide (commonly known as nylon) is one of the most important engineering plastics and fiber raw materials at present, the main varieties of the polyamide 6 and the polyamide 66 of the fiber can be obtained by melt spinning, the polyamide fiber has good wear resistance and excellent mechanical property, becomes chemical fiber with the yield second to that of terylene, and is widely applied in the fields of clothing and engineering. However, the generation of "white pollution" after use has become one of the great challenges facing human beings, and it is statistically estimated that about 900 ten thousand tons of plastic wastes flow into the ocean every year and form micro plastics, micro fibers and the like which enter human bodies through ingestion, thus threatening the ocean ecosystem and human health. Moreover, the problem of three wastes such as caprolactam and the oligomer thereof in the upstream and downstream production processes of polyamide also becomes a great problem which is faced by production enterprises; furthermore, the caprolactam monomer is produced by further synthesizing fossil fuel byproducts such as phenol, cyclohexane, toluene and the like, and belongs to a derivative product of non-renewable resources. The bio-based fiber is mainly derived from derivatives of plants and microorganisms (including cellulose, polysaccharide, seaweed, protein and the like), has wide sources, obvious renewable and degradable characteristics, is environment-friendly and good in biocompatibility, and is considered to be one of ideal substitute materials of the traditional chemical fiber.
The novel bio-based degradable polyamide (the monomer is from plants, is derived from sugar sources such as starch, molasses and the like, and is biodegradable) is developed to relieve the pollution to the environment, and the method has important significance for realizing the aims of energy conservation and emission reduction, carbon peak reaching and carbon neutralization and promoting the sustainable development of economy and society. The main component of the bio-based degradable polyamide is butyrolactam polymer, the production process is that starch or molasses are fermented to produce L-glutamic acid, under the action of glutamate decarboxylase, gamma-aminobutyric acid is formed, then butyrolactam monomer is obtained after high temperature hydrolysis and decompression rectification, and finally ring opening polymerization is carried out to obtain the butyrolactam. The polybutyrolactam (PA4) is derived from plant polysaccharide, and the whole production process is green and environment-friendly and produces no polluting substances. Among them, L-glutamic acid is commonly used as a food additive; the gamma-aminobutyric acid has the effects of calming, reducing blood pressure, promoting ethanol metabolism and the like; butyrolactam monomers are commonly used as intermediates for antibiotics. The polybutyrolactam structural unit has only 3 methylene groups, and the main chain has only 4C, so the polybutyrolactam structural unit is also called PA4, the amido link density is high, and strong polarity and hydrogen bond action exist among molecular chains, so the polybutyrolactam structural unit has excellent toughness, hygroscopicity and oxygen barrier property. The nylon material retains the good wear resistance and high mechanical property of nylon products, so that the nylon material receives the attention of scientists in the field of engineering plastics. When the molecular weight is 6-8 ten thousand, the melting point (Tm) can reach 268 ℃, and is close to the thermal decomposition temperature, so that the melt processing cannot be carried out, and the further application of the composite material is limited.
In order to solve the above problems, attention has been focused on the modified melting of polybutyrolactam. Tachibana and the like adopt an anion ring-opening polymerization method to synthesize two kinds of PA4 with acyl lactam groups at one end or both ends, acyl lactam at the single-chain tail end of low-molecular-weight PA4 is quantitatively converted into functional groups such as carboxyl, amine and the like, the terminal acyl lactam groups far away from both ends of PA4 are also modified into carboxyl and amino, the thermal decomposition point of the modified PA4 is increased compared with that of the original acyl lactam type PA4, so that the acyl lactam far-end low-molecular-weight PA4 mixed with diamine in a body is subjected to chain extension through addition reaction, and the thermal stability of the modified PA4 is obviously improved. This technique is disclosed in polymer science a: polymer chemistry 2011, volume 49, No. 11, pp 2495-2503, title: nylon 4 chain ends are chemically modified to increase their thermal stability, i.e., Chemical modification of chain end in nylon 4 and improvement of its thermal stability [ J ]. Journal of Polymer Science Part A: polymer Chemistry 2011; 49(11): 2495-2503. Kawasaki Norioki synthesizes novel branched PA4 by using poly-alkali chlorinated acid with a branched structure as an initiator, the melting point of the branched PA4 tends to be stable near 265 ℃ along with the increase of the molecular weight, different chain structures have no obvious difference, and the tensile strength and the tensile strain after the branched PA is pressed into a plate have positive molecular weight dependence in a measurement range. This technique is disclosed in Polymer 2005, volume 46, page 9987 and 9993, title: synthesis, thermal, mechanical and biodegradability of branched polyamide 4, Synthesis, thermal and mechanical properties and biodegradation of branched polyamide 4[ J ]. Polymer 2005; 46: 9987-9993. Wu et al dissolve PA4 and Chitosan (CS) in formic acid solution respectively, and the PA4/CS composite membrane is prepared by evaporation after the two are mixed uniformly. This technique is disclosed in applied polymer science 2018, volume 135, No. 28, No. 46511, titled: polybutyrolactam/chitosan composite films, i.e., Wu D, Wei W, Li H, Wang X, Wang T, Tang S, Li Q, Yao Y, Pan Y, Wei J.blended films connecting polybutyroactam and chips for porous surrounding applications [ J ]. Journal of Applied Polymer Science, 2018, 135 (28): 46511.
common methods for evaluating the degradation performance of materials include soil degradation, activated sludge degradation, seawater degradation, photoaging, and the like. Tachibana studied the degradation of PA4 membranes in a seawater environment: the Biochemical Oxygen Demand (BOD) in the degradation process is taken as a main test index, and the degradation rate in the seawater after 25 days is measured to reach 80%. The technology is disclosed in polymer degradation and stability, vol.98, No. 9, No. 1847, page 1851, 2013, title: biodegradability of Nylon 4 film in Marine Environment, namely Biodegradability of Nylon 4 film in a marine environment [ J]Polymer Degradation and Stability 2013; 98(9): 1847-1851. In another study on the degradation of PA4 in seawater, researchers isolated degrading bacteria (MND-1) from seawater that could be metabolized to produce PA4 degrading enzyme, which first acted on amide bond during degradation process, to gradually hydrolyze amide bond, and the resulting low molecular weight product was rapidly eliminated after dissolving in water phase. The nuclear magnetic resonance results show that the low molecular weight product of PA4 is first decomposed into gamma-aminobutyric acid oligomer as an intermediate and finally converted into carbon dioxide and water. The technology is disclosed in polymer degradation and stability, volume 166, page 230-236 of 2019, article: degradability of PA4 in seawater, i.e., Biodegradation of polyamine 4 in seawater [ J ]]Polymer Degradation and Stability 2019; 166: 230-236. Degradation of PA4 in soil environments has also been demonstrated. In order to deeply understand the degradation mechanism of PA4, Yamano Naoko screens and separates Pseudomonas (Pseudomonas sp.) ND-10 and ND-11 which have obvious degradation effect on PA4 from activated sludge, inoculates the Pseudomonas ND-10 and ND-11 on a minimal medium containing PA4 as a unique carbon source, and determines that the Pseudomonas ND-11 produces under the action of the strain through nuclear magnetic resonance analysisThe raw intermediate degradation product is gamma-aminobutyric acid, and the final degradation product is CO 2 And NO 3 - It is indicated that the strain degrades PA4 by its extracellular enzyme hydrolyzing amide bond. The method is disclosed in Polymer and Environment 2008, vol 16, No. 2, page 141-146, title: mechanism and Characterization of Pseudomonas degrading Polyamide 4, namely Mechanism and catalysis of Polyamide 4 Degradation by Pseudomonas sp [ J].Journal of Polymers and the Environment 2008；16(2)：141-146。
In conclusion, although there have been many studies on the degradation method of bio-based PA4, there has been no report on how to process polybutyrolactam into filament fibers due to the problems that PA4 cannot melt (melting point is higher than decomposition temperature) and is difficult to dissolve. At present, the processing technology of the polybutyrolactam only stays at the stage of processing the polybutyrolactam into a film by using formic acid as a solvent, however, the formic acid has extremely high corrosiveness, and the processing of the conventional spinning equipment cannot be realized. The development of the bio-based polyamide fiber not only accords with the concepts of green sustainable development and low carbon and environmental protection, but also can effectively relieve the shortage of non-renewable resources such as petroleum and the like and avoid subsequent white pollution, thereby becoming an important direction for the development of future fibers.
Disclosure of Invention
In order to relieve the increasingly serious problem of white pollution and overcome the problems that the conventional polyamide fiber is difficult to naturally degrade, the conventional degradable polyamide fiber is low in degradation efficiency and non-biological in source and the like, the invention provides a preparation technology of a biomass-source polybutyrolactam fiber.
In order to achieve the purpose, the invention is realized by the following technical scheme:
1) fully drying the polybutyrolactam resin, weighing the polybutyrolactam resin with certain mass, adding the polybutyrolactam resin into a mixed solvent of trifluoropropanol and hexafluoroisopropanol, heating and stirring for 3-5 hours in a water bath, and preparing to obtain uniform and transparent gel-like polybutyrolactam spinning solution; the trifluoropropanol accounts for 0-30% of the mass of the mixed solvent;
wherein the mass fraction of the polybutyrolactam resin in the spinning solution is 6-15 wt%;
2) transferring the spinning solution obtained in the step 1) into a feeding kettle, respectively controlling the temperature of the kettle, a metering pump and a spinneret by using a circulating water bath and a heating device to keep the temperature of the kettle, the metering pump and the spinneret at 30-35 ℃, enabling the spinning solution to flow through the spinneret to be extruded under certain pressure and then enter a section of air layer, and then continuously entering a coagulating bath to be solidified into fibers and wound for forming to obtain polybutyrolactam nascent fibers;
the coagulating bath comprises any one of water, methanol and ethanol;
3) and (3) performing a certain multiple of back drawing on the polybutyrolactam nascent fiber obtained in the step 2) in a hot air atmosphere, then soaking the polybutyrolactam nascent fiber in deionized water for washing, and airing at normal temperature to obtain the bio-based polybutyrolactam fiber.
Further, the drying condition in the step 1) is vacuum drying for more than 24 hours at the temperature of 60-90 ℃; the water bath heating temperature in the step 1) needs to be kept at 60-70 ℃.
Further, the certain pressure in the step 2) is controlled to be 0.4-1.2 Mpa, the length of the air layer is controlled to be 0.06-1 m, and the specification of the used metering pump is 6-36 mL r -1 The rotating speed is set between 3 rpm and 12 rpm; the number of holes of the spinning nozzle is 1 to 48, and the speed of the winding is controlled to 3.5 to 40 m.min -1 In the meantime.
Further, the hot air atmosphere in the step 3) is maintained at 110-120 ℃, the back drawing multiple is set at 2-4 times, and the drawing speed is set at 0.01-0.5 m.min -1 In the meantime.
The invention adopts bio-based polybutyrolactam as raw material to prepare spinning solution, and prepares polybutyrolactam nascent fiber on a wet spinning machine through dry-jet wet spinning-water/alcohol coagulating bath, and the polybutyrolactam fiber obtained has good mechanical property and biodegradation characteristic after hot air post-drafting. The preparation process is simple and easy for industrial implementation. In addition, three different degradation methods (including soil, seawater and ultraviolet irradiation environment) are adopted to represent the degradation performance of the obtained fiber, and the degradation capability of the polybutyrolactam fiber is comprehensively evaluated.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described below with reference to specific embodiments. It is to be understood that the examples described herein are for purposes of illustration only and are not intended to be limiting.
Example 1:
1) drying the polybutyrolactam resin in a vacuum oven at 60 ℃ for 24 hours, weighing a certain mass of polybutyrolactam resin, adding the polybutyrolactam resin into a mixed solvent of trifluoropropanol and hexafluoroisopropanol (mass ratio 10/90), stirring in a water bath at 60 ℃ for 5 hours, and preparing to obtain a uniform and transparent gel-like polybutyrolactam spinning solution with the mass fraction of the polybutyrolactam resin being 9%;
2) transferring the spinning solution obtained in the step 1) into a feeding kettle, respectively controlling the temperature of the kettle, a metering pump and a spinning nozzle by using a circulating water bath and a heating device to keep the temperature at 30 ℃, and jetting the spinning solution at 24 mL/min under the pressure of 0.6Mpa -1 Extruding at a speed through a 6-hole spinneret, introducing into an air layer with a length of 0.3m, continuing to enter into coagulating bath water for solidifying into fiber, and heating at a temperature of 3.5 m.min -1 Winding and forming at the speed of (2) to obtain the polybutyrolactam nascent fiber.
Example 2:
1) drying the polybutyrolactam resin in a vacuum oven at 60 ℃ for 24 hours, weighing a certain mass of polybutyrolactam resin, adding the polybutyrolactam resin into hexafluoroisopropanol, stirring in a water bath at 60 ℃ for 3 hours, and preparing a uniform and transparent gel-like polybutyrolactam spinning solution with the mass fraction of the polybutyrolactam resin being 10%;
2) transferring the spinning solution obtained in the step 1) into a feeding kettle, respectively controlling the temperature of the kettle, a metering pump and a spinning nozzle by using a circulating water bath and a heating device to keep the temperature at 30 ℃, and jetting the spinning solution at 24 mL/min under the pressure of 0.6Mpa -1 Extruding at a speed through a 6-hole spinneret, introducing into an air layer with a length of 0.5m, continuing to enter into a coagulating bath ethanol for solidifying into fibers, and performing at a speed of 8 m.min -1 Winding and forming at the speed of (1) to obtain a polybutyrolactam nascent fiber;
3) subjecting the polybutyrolactam nascent fiber obtained in the step 2) to air atmosphere at 110 ℃ for 0.01 m.min -1 The drafting speed is 1.5 times of the drafting speed, and then the fiber is immersed into deionized water for washing and dried at normal temperature to obtain the bio-based polybutyrolactam fiber.
Example 3:
1) drying the polybutyrolactam resin in a vacuum oven at 60 ℃ for 24 hours, weighing a certain mass of polybutyrolactam resin, adding the polybutyrolactam resin into a mixed solvent of trifluoropropanol and hexafluoroisopropanol (mass ratio 10/90), stirring in a water bath at 60 ℃ for 5 hours, and preparing to obtain a uniform and transparent gel-like polybutyrolactam spinning solution with the mass fraction of the polybutyrolactam resin being 11%;
2) transferring the spinning solution obtained in the step 1) into a feeding kettle, respectively controlling the temperature of the kettle, a metering pump and a spinning nozzle by using a circulating water bath and a heating device to keep the temperature at 30 ℃, and jetting the spinning solution at 18 mL/min under the pressure of 1Mpa -1 Extruding with 6-hole spinneret, introducing into air layer with length of 0.5m, further introducing into coagulating bath ethanol, solidifying, and forming fiber at 5 m.min -1 Winding and forming at the speed of (2) to obtain the primary fiber of the polybutyrolactam;
3) subjecting the polybutyrolactam nascent fiber obtained in the step 2) to air atmosphere at the temperature of 110 ℃ for 0.05 m-min -1 The drafting speed is 2 times of the drafting speed, then the fiber is immersed into deionized water for washing, and the fiber is dried at normal temperature to obtain the bio-based polybutyrolactam fiber.
Example 4:
1) drying the polybutyrolactam resin in a vacuum oven at 60 ℃ for 24h, weighing a certain mass of polybutyrolactam resin, adding the polybutyrolactam resin into a mixed solvent of trifluoropropanol and hexafluoroisopropanol (mass ratio 10/90), stirring for 5 h in a water bath at 60 ℃, and preparing to obtain a uniform and transparent gel-like polybutyrolactam spinning solution with the mass fraction of the polybutyrolactam resin being 10%;
2) transferring the spinning solution obtained in the step 1) into a feeding kettle, respectively controlling the temperature of the kettle, a metering pump and a spinning nozzle by using a circulating water bath and a heating device to keep the temperature at 30 ℃, and jetting the spinning solution at 48 mL/min under the pressure of 1.2Mpa -1 Speed spinning through 6 holesThe head is extruded and enters an air layer with the length of 0.5m, and then the head is continuously put into coagulating bath ethanol to be solidified into fibers, and the fiber is formed at the speed of 12 m.min -1 Winding and forming at the speed of (1) to obtain a polybutyrolactam nascent fiber;
3) subjecting the polybutyrolactam nascent fiber obtained in the step 2) to air atmosphere at the temperature of 110 ℃ for 0.2 m-min -1 The drafting speed is 2.5 times of the drafting speed, and then the fiber is immersed into deionized water for washing and dried at normal temperature to obtain the bio-based polybutyrolactam fiber.
Example 5:
1) drying the polybutyrolactam resin in a vacuum oven at 60 ℃ for 24h, weighing a certain mass of polybutyrolactam resin, adding the polybutyrolactam resin into a hexafluoroisopropanol solvent, stirring in a water bath at 60 ℃ for 5 h, and preparing a uniform and transparent gel-like polybutyrolactam spinning solution with the mass fraction of the polybutyrolactam resin being 10%;
2) transferring the spinning solution obtained in the step 1) into a feeding kettle, respectively controlling the temperature of the kettle, a metering pump and a spinning nozzle by using a circulating water bath and a heating device to keep the temperature at 35 ℃, and jetting the spinning solution at 48 mL/min under the pressure of 1Mpa -1 Extruding with 12-hole spinneret, introducing into air layer with length of 0.3m, further introducing into coagulating bath ethanol, solidifying, and forming fiber at 10 m/min -1 Winding and forming at the speed of (1) to obtain a polybutyrolactam nascent fiber;
3) subjecting the polybutyrolactam nascent fiber obtained in the step 2) to air atmosphere at the temperature of 110 ℃ for 0.05 m-min -1 The drafting speed is 2.5 times of the drafting speed, and then the fiber is immersed into deionized water for washing and dried at normal temperature to obtain the bio-based polybutyrolactam fiber.
The fiber samples prepared in the above examples were subjected to performance characterization, including:
1. tensile strength test of degradable fiber:
the tensile strength was tested by reference to the national standard GB/T14344-2008 chemical fiber filament tensile property test method, and the results are shown in Table 1.
TABLE 1 polybutyrolactam fiber breaking strength
2. Acid and alkali resistance test of polybutyrolactam fiber:
placing the fiber sample obtained in the example 4 in nitric acid, hydrochloric acid and sulfuric acid solutions with the mass fractions of 10% and 20 wt% respectively, standing for half an hour, and observing that the fiber is dissolved when the concentration of the acid is 20%; the fiber is placed in sodium hydroxide solution with the mass fractions of 10 percent, 20 percent, 30 percent and 40 percent by weight, the solution is heated for different times (2h, 4h and 6h) at 60 ℃, and the strength change is measured, and the result is shown in table 2.
TABLE 2 retention of breaking strength after alkali treatment of polybutyrolactam fibers
Fracture strength retention ═ fracture strength after treatment/original fracture strength%
3. The degradation properties of the polybutyrolactam fiber were tested as follows:
and (3) soil degradation test:
the fiber prepared in example 4 is buried in an outdoor soil environment, samples are taken out every 20 days, the weight loss condition of the samples is measured, and the weight loss rate of the polybutyrolactam fiber reaches 52.15 percent after the polybutyrolactam fiber is degraded in soil for 80 days.
Ultraviolet light degradation test:
the fiber obtained in example 4 was placed under the irradiation of UVA-340 lamp at 60 ℃ and at an irradiation intensity of 1.2W/m 2 A set of test fibers were removed for weight loss and strength change at 24 hours per exposure. Weight lossThe results show that the fiber mass loss is 27.55% after 120 hours of uv irradiation, while the break strength decreases to 14% after 72 hours of uv irradiation.
Seawater degradation test:
the fiber prepared in example 4 was placed in natural seawater in a laboratory environment and tested for changes in the concentration of carbon dioxide produced and for fiber weight loss. The biodegradation rate in 60 days was 1.16% and the fiber mass loss was 7.53% as measured by the change in carbon dioxide concentration. The low efficiency of degradation in seawater may be associated with low activity of microorganisms in water in a laboratory environment.
From the results, the bio-based polyamide fiber prepared by the method has good mechanical property which is as high as 2.1cN/dtex, can completely meet the application requirements of normal textile fiber, has good alkali resistance, and shows obvious degradable characteristics in soil, seawater and ultraviolet irradiation environments.
Claims (5)
1. A preparation method of a bio-based degradable polyamide fiber is characterized by comprising the following steps:
1) fully drying the polybutyrolactam resin, weighing the polybutyrolactam resin with certain mass, adding the polybutyrolactam resin into a mixed solvent of trifluoropropanol and hexafluoroisopropanol, heating and stirring in a water bath for 3-5 hours, and preparing to obtain uniform and transparent gel-like polybutyrolactam spinning solution; the trifluoropropanol accounts for 0-30% of the mass of the mixed solvent;
wherein the mass fraction of the polybutyrolactam resin in the spinning solution is 6-15 wt%;
2) transferring the spinning solution obtained in the step 1) into a feeding kettle, respectively controlling the temperature of the kettle, a metering pump and a spinning nozzle by using a circulating water bath and a heating device to keep the temperature of the kettle, the metering pump and the spinning nozzle at 30-35 ℃, enabling the spinning solution to flow through the spinning nozzle to be extruded under certain pressure and enter a section of air layer, and then continuing entering a coagulating bath to be solidified into fibers and wound for forming to obtain polybutyrolactam nascent fibers;
the coagulating bath comprises any one of water, methanol and ethanol;
3) and 3) performing back drawing on the polybutyrolactam nascent fiber obtained in the step 2) by a certain multiple in a hot air atmosphere, then soaking the polybutyrolactam nascent fiber in deionized water for washing, and airing at normal temperature to obtain the bio-based polybutyrolactam fiber.
2. The method for preparing a biodegradable polyamide fiber as claimed in claim 1, wherein: the drying condition in the step 1) is vacuum drying for more than 24 hours at the temperature of 60-90 ℃.
3. The method for preparing a biodegradable polyamide fiber as claimed in claim 1, wherein: the water bath heating temperature in the step 1) is kept at 60-70 ℃.
4. The method for preparing a biodegradable polyamide fiber as claimed in claim 1, wherein: the certain pressure in the step 2) is controlled to be 0.4-1.2 Mpa, the length of an air layer is controlled to be 0.06-1 m, and the specification of a metering pump is 6-36 mL r -1 The rotating speed is set between 3 rpm and 12 rpm; the number of holes of the spinning nozzle is 1 to 48, and the speed of the winding is controlled to 3.5 to 40 m.min -1 In the meantime.
5. The method for preparing a biodegradable polyamide fiber as claimed in claim 1, wherein: maintaining the hot air atmosphere in the step 3) at 110-120 ℃, setting the back drawing multiple at 2-4 times, and setting the back drawing speed at 0.01-0.5 m.min -1 In the meantime.
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| JP2021130894A (en) * | 2020-02-21 | 2021-09-09 | 株式会社クラレ | Nylon 4 fiber and method for producing the same |
| WO2021255957A1 (en) * | 2020-06-19 | 2021-12-23 | 国立大学法人京都工芸繊維大学 | Method for producing polyamide 4 fiber |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140275439A1 (en) * | 2011-10-21 | 2014-09-18 | National Institute Of Advanced Industrial Science And Technology | Biodegradable polymer with controlled biodegradability |
| CN109338497A (en) * | 2018-09-28 | 2019-02-15 | 华东理工大学 | A kind of preparation method of hydrophily degradable poly butyrolactam superfine fibre |
| JP2021130894A (en) * | 2020-02-21 | 2021-09-09 | 株式会社クラレ | Nylon 4 fiber and method for producing the same |
| WO2021255957A1 (en) * | 2020-06-19 | 2021-12-23 | 国立大学法人京都工芸繊維大学 | Method for producing polyamide 4 fiber |
| TW202200860A (en) * | 2020-06-19 | 2022-01-01 | 國立大學法人京都工藝纖維大學 | Method for producing polyamide 4 fiber by using a wet spinning method without carrying out a procedure for removing residual components |
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