A phenanthroline complex and polyamide 6 composite fiber and its preparation method

Abstract

This invention belongs to the field of polymer materials technology, specifically relating to a phenanthroline complex and polyamide 6 composite fiber and its preparation method. The invention prepares spinning raw materials from phenanthroline complex powder and polyamide 6 powder; the spinning raw materials are then subjected to drying and spinning processes to obtain nascent fibers; the nascent fibers are then subjected to drawing processes to obtain the phenanthroline complex and polyamide 6 composite fiber. This invention prepares a phenanthroline complex and polyamide 6 composite fiber with excellent tensile strength and toughness by combining the phenanthroline complex with polyamide 6. Furthermore, this invention uses a phenanthroline complex combined with PA6, which exhibits good compatibility, and the preparation method is simple, easy to operate, and suitable for large-scale production.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a phenanthroline complex and polyamide 6 composite fiber and its preparation method. Background Technology

[0002] Polyamide 6 (PA6), also known as Nylon 6, is a very important polymer material due to the large number of repeating amide groups (−CONH−) in its molecular chain, which can form hydrogen bonds. Because of its advantages such as easy processing, flame retardancy, and wear resistance, polyamide 6 is widely used in the preparation of films, engineering plastics, and fibers. Among them, polyamide 6 fiber is an important polyamide product. Due to its excellent tensile strength, toughness, oxidation resistance, and heat resistance, it has a wide range of applications in electronics and communications, aerospace, medical protection, defense technology, and transportation. However, the tensile strength of traditional polyamide 6 fibers still cannot meet the requirements of current applications, limiting its use. Therefore, exploring polyamide 6 fibers with high tensile strength and high toughness is urgently needed.

[0003] A related technology discloses a method for preparing graphene and polyamide 6 composite fibers. This patent describes a method for preparing a graphene and polyamide 6 composite material using in-situ polymerization. Formic acid is added to dissolve the resulting composite material, forming a solution. Then, wet spinning is used to prepare the graphene and polyamide 6 composite fibers, which exhibit high tensile strength. However, the in-situ polymerization process in this technology is complex, and the production cost is high, making large-scale production difficult. Summary of the Invention

[0004] The purpose of this invention is to provide a phenanthroline complex and polyamide 6 composite fiber and its preparation method. This invention can prepare a phenanthroline complex and polyamide 6 composite fiber with excellent tensile properties and toughness. Moreover, the preparation method is simple, easy to operate, and suitable for large-scale production.

[0005] To achieve the above objectives, the present invention provides the following technical solution:

[0006] This invention provides a method for preparing a composite fiber of phenanthroline complex and polyamide 6, comprising the following steps:

[0007] A spinning raw material was prepared by using phenanthroline complex powder and polyamide 6 powder. The structural formula of the phenanthroline complex is shown in Formula 1.

[0008] Formula 1;

[0009] The spinning raw material is subjected to drying and spinning processes in sequence to obtain nascent fibers.

[0010] The nascent fibers are stretched to obtain the phenanthroline complex and polyamide 6 composite fiber.

[0011] Preferably, the mass ratio of the phenanthroline complex powder to the polyamide 6 powder is (0.03~0.2):10.

[0012] Preferably, the mass ratio of the phenanthroline complex powder to the polyamide 6 powder is (0.05~0.1):10.

[0013] Preferably, the preparation of the spinning raw material includes sequential mixing and ball milling.

[0014] Preferably, the ball milling is a dry ball milling process, the grinding beads used in the dry ball milling are zirconium beads, and the ratio of the total mass of the phenanthroline complex powder and the polyamide 6 powder to the mass of the grinding beads is 1~2:1.

[0015] Preferably, the ball mill rotates at a speed of 500-700 rpm for 1-3 hours.

[0016] Preferably, the drying process is carried out at a temperature of 80-100°C for 18-24 hours.

[0017] Preferably, the spinning process is melt spinning, and the spinning temperature is 230~240℃.

[0018] Preferably, the stretching process includes: stretching the nascent fibers using a hot roller, wherein the temperature of the hot roller is 100~140℃.

[0019] The present invention provides a phenanthroline complex and polyamide 6 composite fiber prepared by the preparation method described above.

[0020] This invention provides a method for preparing a composite fiber of phenanthroline complex and polyamide 6, comprising the following steps: preparing a spinning raw material by preparing phenanthroline complex powder and polyamide 6 powder, wherein the structural formula of the phenanthroline complex is shown in Formula 1; subjecting the spinning raw material to drying and spinning treatment in sequence to obtain nascent fiber; subjecting the nascent fiber to stretching treatment to obtain the composite fiber of phenanthroline complex and polyamide 6. This invention prepares composite fibers of phenanthroline complexes and polyamide 6 (PA6) with excellent tensile strength and toughness by combining phenanthroline complexes with polyamide 6. The invention improves the condensed state of the polyamide 6 molecular chains by adding phenanthroline complexes, reducing intermolecular defects present when polyamide 6 molecules form fibers alone, thereby enhancing the tensile strength and toughness of the composite fibers. Simultaneously, the phenanthroline complex structure contains NH bonds and benzene rings; its NH bonds can form numerous hydrogen bonds with the polyamide 6 molecular chains, resulting in strong intermolecular interactions and further improving the tensile strength and toughness of the fibers. Furthermore, the phenanthroline complex contains four amine groups (-NH2), which can undergo amide exchange reactions with numerous amide bonds (-CONH-) in the linear structure of the polyamide 6 molecular chains under high temperatures, forming a network structure. This interlocking structure in the amorphous regions of polyamide 6 acts as a clamp, effectively embedding the polyamide 6 molecular chains into the molecular structure of the phenanthroline complex, creating a nano-confined effect that enhances the interactions between polyamide 6 molecular chains, thus improving the tensile strength and toughness of the composite fibers. Meanwhile, this invention uses phenanthroline complexes to compound PA6, which has good compatibility, and the preparation method is simple, easy to operate, and suitable for large-scale production. Attached Figure Description

[0021] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0022] Figure 1 This is a SEM image of the phenanthroline complex and polyamide 6 composite fiber in Example 3 of the present invention;

[0023] Figure 2 This is a SEM image of the polyamide 6 fiber in Comparative Example 1 of the present invention. Detailed Implementation

[0024] This invention provides a method for preparing a composite fiber of phenanthroline complex and polyamide 6, comprising the following steps:

[0025] A spinning raw material was prepared by using phenanthroline complex powder and polyamide 6 powder. The structural formula of the phenanthroline complex is shown in Formula 1.

[0026] Formula 1;

[0027] The spinning raw material is subjected to drying and spinning processes in sequence to obtain nascent fibers.

[0028] The nascent fibers are stretched to obtain the phenanthroline complex and polyamide 6 composite fiber.

[0029] In this invention, unless otherwise specified, all raw materials / components used in the preparation are commercially available products well known to those skilled in the art.

[0030] This invention prepares spinning raw materials from phenanthroline complex powder and polyamide 6 powder, wherein the structural formula of the phenanthroline complex is shown in Formula 1:

[0031] Formula 1.

[0032] In this invention, the phenanthroline complex is a compound synthesized by using phenanthroline or its derivatives as ligands and coordinating with metal ions through coordinate bonds. Its structure is mainly composed of elements such as carbon, hydrogen, nitrogen and metal ions, and it has outstanding characteristics such as high chemical stability and high rigidity planar structure. The phenanthroline structure contains NH bonds and benzene rings.

[0033] The phenanthroline complex described in this invention has the structure shown in Formula 1, denoted as Cu(PDA)2(BF4).

[0034] In this invention, the phenanthroline complex is prepared according to the method disclosed in "Divergent Chemistry Paths for 3D and 1D Metallo-Covalent Organic Frameworks (COFs)" (Hai-Sen Xu, Yi Luo, Pei ZhenSee, Xing Li, Zhongxin Chen, Yi Zhou, Xiaoxu Zhao, Kai Leng, In-Hyeok Park, Runlai Li, Cuibo Liu, Fangzheng Chen, Shibo Xi, Junliang Sun, and Kian PingLoh, Angew. Chem. Int. Ed. 2020, 59, 11527–11532).

[0035] In this invention, the mass ratio of the phenanthroline complex powder to the polyamide 6 powder is preferably (0.03~0.2):10, more preferably (0.05~0.18):10, and most preferably 0.15:10; in the embodiments, it can be 0.03:10, 0.04:10, 0.05:10, 0.06:10, 0.07:10, 0.08:10, 0.09:10, 0.1:10, 0.15:10 or 0.2:10.

[0036] The present invention preferably sets the mass ratio of the phenanthroline complex powder to the polyamide 6 powder within the above range, which can achieve uniform dispersion of the phenanthroline complex powder in the polyamide 6 powder and further optimize the mechanical properties of the phenanthroline complex and polyamide 6 composite fiber.

[0037] In this invention, the preparation of the spinning raw material preferably includes sequential mixing and ball milling. The mixing preferably involves mixing the phenanthroline complex powder and the polyamide 6 powder to obtain a mixture; the ball milling preferably involves ball milling the mixture. The ball milling is preferably performed in a ball mill. The ball milling is preferably dry ball milling. The grinding beads used in the dry ball milling are preferably zirconium beads. The ratio of the total mass of the phenanthroline complex powder and the polyamide 6 powder to the mass of the grinding beads is preferably 1~2:1, and in the examples, it can be 1:1. This invention preferably achieves more thorough mixing of the phenanthroline complex powder and the polyamide 6 powder through ball milling, resulting in a more uniform composition of the spinning raw material. This allows the two materials to interact better during subsequent spinning processing, which is beneficial for the subsequent preparation of composite fibers of phenanthroline complex and polyamide 6 with both excellent tensile strength and toughness.

[0038] In this invention, the ball milling speed is preferably 500~700 rpm, more preferably 550~650 rpm. The ball milling time is preferably 1~3 hours.

[0039] After obtaining the spinning raw material, the present invention sequentially performs drying and spinning treatments on the spinning raw material to obtain nascent fibers. In the present invention, the drying treatment is preferably vacuum drying. The drying treatment is preferably carried out in a vacuum oven. The drying temperature is preferably 80~100℃, more preferably 85~95℃. The drying time is preferably 18~24h, more preferably 20~22h. Through this drying treatment, the present invention can remove any moisture or solvents that may be present in the spinning raw material, preventing adverse effects on the formation of composite fibers caused by moisture or solvents during subsequent spinning processes, thus avoiding uneven composition of the composite fibers. By optimizing the temperature and time of the drying treatment, the present invention can effectively remove any moisture or solvents that may be present in the spinning raw material.

[0040] In this invention, the spinning process is preferably melt spinning. The preferred temperature for the spinning process is 230-240°C. In this invention, the spinning process is used to transform the dried spinning raw material into a fibrous material. By optimizing the spinning process temperature, this invention can effectively melt the spinning raw material and achieve good fluidity, allowing the phenanthroline complex and polyamide 6 in the spinning raw material to better form a composite structure during the spinning process. This promotes the interaction between the phenanthroline complex and polyamide 6, facilitates the formation of composite fibers, and reduces structural defects in the fibers. This is beneficial for the subsequent preparation of composite fibers containing phenanthroline complex and polyamide 6 with excellent tensile strength and toughness.

[0041] After obtaining the initial fibers, the present invention performs a drawing process on the nascent fibers to obtain the phenanthroline complex and polyamide 6 composite fibers. The drawing process of the nascent fibers causes the molecular chains of the nascent fibers to align in a specific direction, resulting in phenanthroline complex and polyamide 6 composite fibers with excellent tensile strength and toughness. In the present invention, the drawing process preferably includes drawing the nascent fibers using a hot roller. The temperature of the hot roller is preferably 100~140℃. When the present invention uses a hot roller at a temperature of 100~140℃ to draw the nascent fibers, the molecular chains of the nascent fibers can be arranged more orderly. This reduces fiber defects and is beneficial for obtaining phenanthroline complex and polyamide 6 composite fibers with excellent tensile strength and toughness.

[0042] The present invention provides a phenanthroline complex and polyamide 6 composite fiber prepared by the preparation method described above.

[0043] The phenanthroline complex and polyamide 6 composite fiber provided by this invention have both excellent tensile strength and toughness.

[0044] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0045] Example 1

[0046] The method for preparing phenanthroline complex and polyamide 6 composite fibers provided in this embodiment includes the following steps:

[0047] 50 mg Cu(PDA)2(BF4) (structural formula as shown in Formula 1) and 10 g polyamide 6 powder were mixed and added to a zirconia ball mill jar at room temperature along with 40 g zirconia ball milling beads. The mixture was then ball milled at 600 rpm for 2 h to obtain a uniform spinning raw material.

[0048] The uniform spinning raw material was placed in a vacuum oven at 100℃ for 24 hours to dry it, and the dried spinning raw material was obtained.

[0049] Primary fibers were obtained by spinning the dried spinning raw material at 235°C using a melt spinning method.

[0050] Nascent fibers are stretched using a 140℃ hot roller to obtain phenanthroline complex and polyamide 6 composite fibers.

[0051] Example 2

[0052] The preparation method of the phenanthroline complex and polyamide 6 composite fiber provided in this embodiment is the same as that in Example 1, except that:

[0053] Replace 50mg Cu(PDA)2(BF4) with 100mg Cu(PDA)2(BF4).

[0054] Example 3

[0055] The preparation method of the phenanthroline complex and polyamide 6 composite fiber provided in this embodiment is the same as that in Example 1, except that:

[0056] Replace 50mg Cu(PDA)2(BF4) with 150mg Cu(PDA)2(BF4).

[0057] Example 4

[0058] The preparation method of the phenanthroline complex and polyamide 6 composite fiber provided in this embodiment is the same as that in Example 1, except that:

[0059] Replace 50mg Cu(PDA)2(BF4) with 200mg Cu(PDA)2(BF4).

[0060] Comparative Example 1 (without Cu(PDA)2(BF4))

[0061] The method for preparing polyamide 6 fibers provided in this comparative example includes the following steps:

[0062] 10g of polyamide 6 powder was added to a zirconia ball mill jar and 40g of zirconia ball milling beads were added. The mixture was then ball milled at 600 rpm for 2 hours to obtain a uniform spinning raw material.

[0063] The uniform spinning raw material was placed in a vacuum oven at 100℃ for 24 hours to dry it, and the dried spinning raw material was obtained.

[0064] Primary fibers were obtained by spinning the dried spinning raw material at 235°C using a melt spinning method.

[0065] Polyamide 6 fiber is obtained by stretching the nascent fiber using a 140℃ hot roller.

[0066] Table 1. Mass of Cu(PDA)2(BF4) and polyamide 6 in each example and comparative example

[0067]

[0068] Test Example 1

[0069] This test example provides a morphological characterization experiment of phenanthroline complex and polyamide 6 composite fibers:

[0070] Scanning electron microscopy (SEM) was performed on the phenanthroline complex and polyamide 6 composite fiber in Example 3 of the present invention and the polyamide 6 fiber in Comparative Example 1, respectively. The test results are as follows: Figure 1 and Figure 2 As shown.

[0071] Depend on Figure 1 and Figure 2 It can be seen that the surface morphology of the phenanthroline complex material and the polyamide 6 composite fiber is similar to that of the polyamide 6 fiber. Both have a smooth and regular surface morphology and no obvious pores, exhibiting obvious fiber characteristics, indicating that the fiber is uniformly formed during the spinning process.

[0072] Test Example 2

[0073] This test example provides a performance characterization experiment for phenanthroline complexes and polyamide 6 composite fibers:

[0074] The phenanthroline complex and polyamide 6 composite fiber in Examples 1-4 of the present invention and the polyamide 6 fiber in Comparative Example 1 were used as the test fibers and the following tests were performed. The test results are shown in Table 2.

[0075] Tensile strength / MPa: Take a 5cm fiber to be tested, apply anti-slip tape to 1cm at both ends, and perform tensile testing through a universal testing machine, with a tensile speed of 50 mm / min.

[0076] Toughness / MJ·m -3 Toughness is obtained by integrating the stress-strain tensile curve of the fiber.

[0077] Table 2 Test Results

[0078]

[0079] As shown in Table 2, compared with the polyamide 6 fiber in Comparative Example 1, the tensile strength of the phenanthroline complex and polyamide 6 composite fibers in Examples 1-4 of this invention is significantly improved. Compared with the polyamide 6 fiber in Comparative Example 1, the phenanthroline complex and polyamide 6 composite fibers in Examples 1-4 of this invention exhibit both excellent tensile strength and excellent toughness, which can meet the requirements of ultra-high-end application fields for the toughness performance of fiber materials.

[0080] As shown in the above embodiments, the present invention uses phenanthroline complex powder with the structure shown in Formula 1 and polyamide 6 powder, which are then mixed and added to a ball mill jar, and then ball-milled to obtain spinning raw material. The spinning raw material is then dried and spun sequentially to obtain nascent fibers. The nascent fibers are then drawn to obtain phenanthroline complex and polyamide 6 composite fibers. The present invention can prepare phenanthroline complex and polyamide 6 composite fibers with both excellent tensile properties and toughness, and the preparation method is simple, easy to operate, and suitable for large-scale production.

[0081] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a composite fiber of phenanthroline complex and polyamide 6, characterized in that, Includes the following steps: A spinning raw material was prepared by using phenanthroline complex powder and polyamide 6 powder, wherein the mass ratio of phenanthroline complex powder to polyamide 6 powder was (0.03~0.2):10; the structural formula of the phenanthroline complex is shown in Formula 1. Formula 1; The spinning raw material is subjected to drying and spinning processes in sequence to obtain nascent fibers. The nascent fibers are stretched to obtain the phenanthroline complex and polyamide 6 composite fiber.

2. The preparation method according to claim 1, characterized in that, The mass ratio of the phenanthroline complex powder to the polyamide 6 powder is (0.05~0.1):

10.

3. The preparation method according to claim 1, characterized in that, The preparation method of the spinning raw material includes sequential mixing and ball milling.

4. The preparation method according to claim 3, characterized in that, The ball milling is a dry ball milling process, and the grinding beads used in the dry ball milling process are zirconium beads. The ratio of the total mass of the phenanthroline complex powder and the polyamide 6 powder to the mass of the grinding beads is 1~2:

1.

5. The preparation method according to claim 3 or 4, characterized in that, The ball mill operates at a speed of 500-700 rpm for 1-3 hours.

6. The preparation method according to claim 1, characterized in that, The drying process is carried out at a temperature of 80~100℃ for 18~24 hours.

7. The preparation method according to claim 1, characterized in that, The spinning process is melt spinning, and the spinning temperature is 230~240℃.

8. The preparation method according to claim 1, characterized in that, The stretching process includes: stretching the nascent fibers using a hot roller, wherein the temperature of the hot roller is 100~140℃.

9. The phenanthroline complex and polyamide 6 composite fiber prepared by the preparation method according to any one of claims 1 to 8.

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