Preparation method and application of long-lasting antibacterial polyester fiber for marine engineering

Abstract

The invention discloses a preparation method and application of a long-lasting antibacterial polyester fiber for marine engineering. Using dimethyl terephthalate, diol, and imidazole diol monomer as raw materials, an ester exchange reaction occurs under the action of a catalyst to obtain an esterification product; a stabilizer, an antioxidant, and a catalyst are added to the esterification product to perform a polycondensation reaction to obtain a functionalized polyester containing imidazole functional groups on the side groups; the functionalized polyester is immersed in a copper ion solution, taken out and dried to obtain a functionalized polyester loaded with copper ions; and then blended with polyester chips and melt-spun to obtain a long-lasting antibacterial polyester fiber. The invention obtains a functionalized modified polyester by introducing an imidazole group on the side groups of polyester macromolecules; then, the copper ions are stably adsorbed on the polyester molecules by utilizing the strong coordination effect between imidazole and copper ions to prepare a functional masterbatch loaded with copper ions; finally, a polyester fiber loaded with copper ions is obtained by melt blending and spinning, and the polyester fiber can be used in marine engineering and has a long-lasting antibacterial effect.

Description

Technical Field

[0001] The invention relates to the technical field of functional fibers, and in particular to a preparation method and application of long-acting antibacterial polyester fibers for marine engineering. Background Art

[0002] Polyester fiber, represented by polyester, is the synthetic fiber with the largest production scale and output in my country. It has excellent comprehensive properties, such as high strength, high elasticity, good heat resistance, corrosion resistance, etc., and is widely used in clothing and various textile fields. Although my country's textile industry has developed rapidly in recent years and product quality has been continuously improved, the product homogeneity is serious and the added value is low. Therefore, the development and production of functional fibers has become a hot research direction at present, with huge market prospects. In addition, with the development of my country's marine engineering, the demand for industrial textiles for marine use has steadily increased year by year. Polyester fiber has good application prospects in ship cables, protective nets, filter nets and other navigation fields due to its good anti-aging, good wear resistance and good chemical corrosion resistance. However, polyester fiber is easily contaminated and breeds bacteria due to seawater impact, erosion, aging and surface friction during use, which leads to damage to human health. Therefore, functional modified polyester fiber can further expand the application scope of polyester fiber in the field of marine engineering.

[0003] Functionalized polyester fibers can be obtained through chemical, physical or biotechnological modification. Compared with conventional polyester fibers, they have a series of functionalities, such as flame retardant, antibacterial, antistatic, and UV protection. There are several main means to produce functionalized polyester fibers: first, chemically modify the polyester macromolecules, introduce new functional groups, and then spin them into shape; second, surface modify and finish the polyester fibers or fabrics; third, add functionalized masterbatches to the polyester, and then obtain functionalized polyester fibers through melt blending and spinning. However, the chemical modification process is complicated and costly, and the introduction of modified groups usually causes a loss of mechanical strength; surface modification and finishing usually results in poor washing fastness due to the inert surface of the polyester fibers. Relatively speaking, adding functional masterbatches has the advantages of good flexibility, lasting functions, and simple processes, and is the current mainstream direction for developing functionalized products. However, due to the high rigidity, high crystallinity, high viscosity, and lack of intermolecular forces with the functional components of the polyester matrix, it is difficult to evenly disperse the functional components in the polyester matrix.

[0004] At present, inorganic antibacterial materials used in the market mostly contain silver, zinc or copper. Although silver antibacterial agents have good antibacterial effects, nanosilver is not easily metabolized after being absorbed by the human body and has a high cost, while zinc-containing antibacterial materials have weak antibacterial effects. The use of copper ions is relatively safe, and copper ions have spectral antibacterial properties. Therefore, the development of copper ion antibacterial fibers is a trend of future development. However, how to evenly disperse copper ions in a polymer matrix at nanoscale is still a difficulty. For polyester, due to its high crystallinity, poor solubility and lack of functional groups, it is a huge challenge to prepare copper ion-loaded polyester fibers without affecting spinning and mechanical strength. In addition, due to the lack of intermolecular forces between copper ions and polyester molecules, weather resistance and washing fastness are poor, and copper ions are easily lost during long-term use or seawater immersion, thereby losing their antibacterial effects. How to improve the washing fastness of copper ions to achieve a long-lasting antibacterial effect is also a problem that copper ion antibacterial fibers urgently need to solve. Summary of the invention

[0005] In view of the above-mentioned prior art, the purpose of the present invention is to provide a method for preparing and applying a long-acting antibacterial polyester fiber for marine engineering. The present invention introduces imidazole groups on the side groups of polyester macromolecules to obtain functional modified polyester; then utilizes the strong coordination effect between imidazole and copper ions to stably adsorb copper ions on polyester molecules to prepare functional masterbatch loaded with copper ions; finally, obtains polyester fiber loaded with copper ions by melt blending and spinning, and the polyester fiber can be used in marine engineering and has a long-acting antibacterial effect.

[0006] To achieve the above object, the present invention adopts the following technical solution:

[0007] In a first aspect of the present invention, a functionalized polyester loaded with copper ions is provided, which is prepared by the following method:

[0008] (1) Using dimethyl terephthalate, diol, and imidazole diol monomer as raw materials, an ester exchange reaction occurs under the action of a metal acetate catalyst to obtain an esterification product;

[0009] (2) adding a stabilizer, an antioxidant and a catalyst to the esterification product to carry out a polycondensation reaction to obtain a functionalized polyester having a side imidazole functional group;

[0010] (3) Soaking the functionalized polyester in a copper ion solution, taking it out and drying it to obtain the functionalized polyester loaded with copper ions.

[0011] Preferably, in step (1), the mass ratio of dimethyl terephthalate, diol, imidazole diol-containing monomer and catalyst is (25-35): (25-50): (25-50): (0.03-0.05);

[0012] The transesterification reaction conditions are: temperature 180-210° C., reaction time 2-3 h; cooling to room temperature after the reaction is completed.

[0013] Preferably, the structural formula of the imidazole diol-containing monomer is:

[0014] ;

[0015] More preferably, the imidazole diol-containing monomer is prepared by the following method:

[0016] Add 3-amino-1,2-propanediol, a water absorbent and glacial acetic acid to a solvent, cool to 0°C, add 4-imidazolecarboxaldehyde after it is completely dissolved, stir to react for 1-2 hours, then add sodium borohydride to react for 1 hour; after the reaction is completed, remove the solvent by distillation under reduced pressure, adjust the pH in deionized water, precipitate, wash and dry to obtain the product.

[0017] Preferably, the diol is selected from at least one of ethylene glycol, propylene glycol and butylene glycol;

[0018] Preferably, the metal acetate is selected from zinc acetate, magnesium acetate or calcium acetate.

[0019] Preferably, in step (2), the mass ratio of the esterification product, stabilizer, antioxidant and catalyst is (99-100): (0.2-0.3): (0.1-0.3): (0.2-0.3); the conditions of the polycondensation reaction are: temperature 220-280 °C, reaction time 2-3 h, vacuum degree less than 100 kPa; after the reaction is completed, the mixture is cooled to 200 °C and discharged.

[0020] Preferably, the stabilizer is at least one of triphenyl phosphite, trimethyl phosphate, alkyl phosphate diester and tris(nonylphenyl)phosphite;

[0021] Preferably, the antioxidant is at least one of antioxidant 168, antioxidant 616, antioxidant 1010 and antioxidant 1098;

[0022] Preferably, the catalyst is antimony oxide or antimony acetate.

[0023] Preferably, in step (3), the concentration of the copper ion solution is 1-10 g / L; and the soaking time is 12-48 h.

[0024] Preferably, the copper ion source is one of copper chloride, copper sulfate, copper nitrate and copper acetate. The solvent used to prepare the copper ion solution is ethanol, acetone, tetrahydrofuran or N'N-dimethylformamide.

[0025] The second aspect of the present invention provides the use of functionalized polyester loaded with copper ions in the preparation of long-lasting antibacterial fibers.

[0026] The third aspect of the present invention provides a long-lasting antibacterial polyester fiber, which is prepared by the following method:

[0027] Functionalized polyester loaded with copper ions was prepared into masterbatch, which was then blended with polyester chips and melt-spun to produce long-lasting antibacterial polyester fibers.

[0028] Preferably, the mass ratio of the masterbatch to the polyester chips is (5-15): (85-95);

[0029] Preferably, the melt spinning conditions are: melt temperature 280-300°C, one roller spinning speed 800-1000 m / min, hot roller drafting multiple 3.5-6 times, ring blowing temperature 15-25°C, blowing speed 0.5-1.0 m / s.

[0030] Preferably, the polyester chips are at least one of PET chips, PPT chips and PBT chips.

[0031] The fourth aspect of the present invention provides the use of long-lasting antibacterial polyester fiber in underwater antibacterial treatment.

[0032] Beneficial effects of the present invention:

[0033] (1) The present invention introduces imidazole diol monomers into polyester molecules, which can destroy the regularity and crystallinity of polyester molecules and make it easier for copper ions to diffuse into the interior of polyester macromolecules.

[0034] (2) The introduction of imidazole groups in the present invention allows copper ions to be evenly dispersed in the polymer molecular chain in the form of single molecules, which will not affect the spinning and mechanical strength of the polyester fiber. The strong coordination between imidazole and copper ions also allows copper ions to be stably loaded in the polyester fiber, which has good water washing fastness and good durability in seawater.

[0035] (3) The present invention does not change the spinning process of the original polyester fiber, making it easier to achieve large-scale production of the product.

[0036] (4) The imidazole diol-containing monomer provided by the present invention can be extended to other polymers or polymer fibers for preparing other metal ion-loaded hybrid materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 is the H NMR spectrum of the imidazole diol monomer;

[0038] Figure 2 is the infrared spectrum of the functionalized polyester containing imidazole side groups;

[0039] Figure 3 This is the distribution of copper ions in copper ion-loaded polyester fiber. DETAILED DESCRIPTION

[0040] It should be noted that the following detailed descriptions are illustrative and are intended to provide further explanation of the present application. Unless otherwise specified, all technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art to which the present application belongs.

[0041] As introduced in the background technology section, copper ion-loaded polyester fibers have high requirements for the uniform dispersion of copper ions and the interaction force between copper ions and polyester molecules. Existing polyester functionalization methods are difficult to achieve these two requirements.

[0042] Based on this, the purpose of the present invention is to provide a method for preparing a long-lasting antibacterial polyester fiber for marine engineering and its application. The present invention introduces a diol monomer containing an imidazole functional group into a polyester molecule for copolymerization to obtain a functionalized polyester containing an imidazole group on the side, and the functionalized polyester has the following structural characteristics:

[0043]

[0044] Then, the prepared functionalized polyester is immersed in a copper ion solution, and the copper ions are adsorbed on the polyester molecular chain through diffusion and the coordination between imidazole and copper ions to obtain a functionalized masterbatch. The interaction force between imidazole and copper ions is as follows:

[0045]

[0046] The copper ion loaded polyester fiber was prepared by melt blending and spinning of functionalized masterbatch and polyester chips.

[0047] The present invention can realize copper ion loading without affecting the spinnability of polyester melt and the mechanical strength of polyester fiber, and the copper ions have a strong binding force with polyester molecules, so that the copper ion-loaded polyester fiber has good water washing fastness and still has good antibacterial effect after long-term seawater immersion, and has broad application prospects in the fields of marine engineering and functional polyester fabrics.

[0048] In order to enable those skilled in the art to more clearly understand the technical solution of the present application, the technical solution of the present application will be described in detail below in conjunction with specific embodiments.

[0049] The test materials used in the examples of the present invention are all conventional test materials in the art and can be purchased through commercial channels.

[0050] Example 1: Preparation of imidazole diol-containing monomer

[0051] Take 1 L of methanol, add 0.5 mol of 3-amino-1,2-propanediol, 25 g of anhydrous sodium acetate and 3 mL of glacial acetic acid, cool the solution to 0 °C in an ice-water bath and stir, add 0.5 mol of 4-imidazole carboxaldehyde in three batches after complete dissolution, stir and react for 1 hour; then add 0.5 mol of sodium borohydride in three batches, and continue to react for 1 hour. After the reaction is completed, remove the solvent by vacuum distillation to obtain a light yellow solid, add deionized water to the solid, adjust the pH to neutral, filter and wash 3 times, and dry in a vacuum oven at 60 °C to obtain an imidazole diol monomer (yield 77%), and its nuclear magnetic hydrogen spectrum is as follows Figure 1 shown.

[0052] Example 2: Preparation of imidazole functionalized polyester

[0053] Dimethyl terephthalate (200 mmol, 38.8 g) was added to the flask and heated to 160 °C under a nitrogen atmosphere. After complete melting, ethylene glycol (280 mmol, 17.56 g), imidazole diol monomer (240 mmol, 34.2 g) and zinc acetate (0.3 g) were added. The resulting reaction mixture was gradually heated to 190 °C and stirred for 3 h. After the reaction was completed, it was cooled to room temperature, and triphenylphosphite (0.6 g), antioxidant 1098 (0.6 g) and antimony oxide (0.5 g) were added under nitrogen protection. The system was then placed under vacuum (~90 kPa) for 2 h. During this process, the temperature gradually increased from 220 °C to 270 °C. After the reaction was completed, it was cooled to room temperature to obtain imidazole functionalized polyester, and its infrared spectrum is shown as follows: Figure 2 As shown, the molecular weight is 17900.

[0054] Example 3: Preparation of copper ion loaded polyester fiber

[0055] A copper acetate ethanol solution with a concentration of 5 g / L was prepared. The functionalized polyester solid in Example 2 was ground and added to the copper acetate solution. After soaking for 36 hours, the polyester solid was taken out. After washing with deionized water three times, it was placed in a 60 ℃ vacuum oven and dried for 3 hours to obtain a copper ion-loaded functional masterbatch. The functionalized masterbatch was melt-blended with PET chips for spinning, and the mass fraction of the functionalized masterbatch of the blended species was 8%; the process parameters of melt-blending spinning were: melt temperature 290 ℃, one roller spinning speed 1000 m / min, hot roller drafting multiple 4.5 times, ring blowing temperature 20 ℃, and blowing speed 0.7 m / s.

[0056] The copper ion loaded polyester fiber prepared in this example was tested for performance, and the relevant properties were as follows: single fiber fineness 10 dtex, breaking strength 6.5 cN / dtex, and breaking elongation 31%.

[0057] The fiber interface in this embodiment is observed, as shown in FIG. Figure 3 It can be found that the copper ions are uniformly dispersed in the cross section, indicating that the method of the present invention can effectively disperse the copper ions in the polyester fiber matrix.

[0058] Comparative Example 1

[0059] The PET chips were melt-spun, and the process parameters of melt spinning were: melt temperature 290 °C, one roller spinning speed 1000 m / min, hot roller drafting multiple 4.5 times, ring blowing temperature 20 °C, blowing speed 0.7 m / s. Polyester fibers were obtained.

[0060] The polyester fiber was tested for performance, and the relevant properties were as follows: single fiber fineness 10 dtex, breaking strength 6.3 cN / dtex, and breaking elongation 30%.

[0061] Comparative Example 2

[0062] A 5 g / L copper acetate ethanol solution was prepared, and the polyester (PET) solid was ground and added into the copper acetate solution. After soaking for 36 h, the PET solid was taken out. After washing with deionized water for 3 times, it was placed in a 60 ℃ vacuum oven and dried for 3 h to obtain the copper ion loaded functional masterbatch. The functional masterbatch was melt blended with PET chips for spinning, and the mass fraction of the functional masterbatch of the blending species was 8%. The process parameters of melt blending spinning were as follows: melt temperature 290 ℃, one roller spinning speed 1000 m / min, hot roller drafting multiple 4.5 times, ring blowing temperature 20 ℃, blowing speed 0.7 m / s, and the copper ion loaded polyester fiber was obtained.

[0063] The polyester fiber was tested for performance, and the relevant properties were as follows: single fiber fineness 10 dtex, breaking strength 6.0 cN / dtex, and breaking elongation 24%.

[0064] It can be seen from Comparative Examples 1 and 2 that the antibacterial fiber prepared in Example 3 not only has a good antibacterial effect, but also has physical and mechanical properties that are not inferior to those of conventional polyester fibers.

[0065] Test example

[0066] The copper ion-loaded polyester fibers prepared in Example 3 and Comparative Example 2 were tested for antibacterial effect according to the standard "FZ / T01021-92 Test Method for Antibacterial Performance of Fabrics", and recorded as the normal antibacterial rate; then the copper ion-loaded polyester fibers were immersed in seawater for 30 days (25°C ± 2°C), and their antibacterial effect was tested, and recorded as the seawater antibacterial rate; and the copper ion-loaded polyester fibers were washed 30 times conventionally, and the antibacterial effect was tested, and recorded as the washing antibacterial rate. The results are shown in Table 1.

[0067] Table 1

[0068]

[0069] As can be seen from Table 1, the copper ion-loaded polyester fiber prepared by the present invention has a long-lasting underwater antibacterial effect, and can effectively inhibit common bacteria such as Staphylococcus aureus, Escherichia coli and Candida albicans. However, the copper ion-loaded polyester fiber prepared in Comparative Example 2 has a significantly reduced antibacterial effect after being soaked and washed in seawater, indicating that there is a lack of intermolecular force between copper ions and polyester molecules in the copper ion-loaded polyester fiber prepared in Comparative Example 2, and the weather resistance and washing resistance are poor.

[0070] The above description is only the preferred embodiment of the present application and is not intended to limit the present application. For those skilled in the art, the present application may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A functionalized polyester loaded with copper ions, characterized in that: Prepared by the following method: (1) Using dimethyl terephthalate, diol, and imidazole diol monomer as raw materials, an ester exchange reaction occurs under the action of a metal acetate catalyst to obtain an esterification product; (2) adding a stabilizer, an antioxidant and a catalyst to the esterification product to carry out a polycondensation reaction to obtain a functionalized polyester having a side imidazole functional group; (3) Soaking the functionalized polyester in a copper ion solution, taking it out and drying it to obtain the functionalized polyester loaded with copper ions.

2. The functionalized polyester according to claim 1, characterized in that In step (1), the mass ratio of dimethyl terephthalate, diol, imidazole diol monomer and catalyst is (25-35): (25-50): (25-50): (0.03-0.05); The transesterification reaction conditions are: temperature 180-210° C., reaction time 2-3 h; cooling to room temperature after the reaction is completed.

3. The functionalized polyester according to claim 2, characterized in that The structural formula of the imidazole diol-containing monomer is: ； The diol is selected from at least one of ethylene glycol, propylene glycol and butylene glycol; The metal acetate is selected from zinc acetate, magnesium acetate or calcium acetate.

4. The functionalized polyester according to claim 1, characterized in that In step (2), the mass ratio of the esterification product, stabilizer, antioxidant and catalyst is (99-100): (0.2-0.3): (0.1-0.3): (0.2-0.3); the conditions of the polycondensation reaction are: temperature 220-280 °C, reaction time 2-3 h, vacuum degree less than 100 kPa; after the reaction is completed, the mixture is cooled to 200 °C and discharged.

5. The functionalized polyester according to claim 4, characterized in that The stabilizer is at least one of triphenyl phosphite, trimethyl phosphate, alkyl phosphate diester and tris(nonylphenyl)phosphite; The antioxidant is at least one of antioxidant 168, antioxidant 616, antioxidant 1010 and antioxidant 1098; The catalyst is antimony oxide or antimony acetate.

6. The functionalized polyester according to claim 1, characterized in that In step (3), the concentration of the copper ion solution is 1-10 g / L; and the soaking time is 12-48 h.

7. Use of the copper ion-loaded functionalized polyester according to any one of claims 1 to 6 in the preparation of long-lasting antibacterial fibers.

8. A long-lasting antibacterial polyester fiber, characterized in that: Prepared by the following method: The copper ion-loaded functionalized polyester according to any one of claims 1 to 6 is prepared into a master batch, which is then blended with polyester chips and melt-spun to obtain a long-lasting antibacterial polyester fiber.

9. The long-lasting antibacterial polyester fiber according to claim 8, characterized in that: The mass ratio of the masterbatch to the polyester chips is (5-15): (85-95); The melt spinning conditions are as follows: melt temperature 280-300°C, one roller spinning speed 800-1000 m / min, hot roller drafting multiple 3.5-6 times, ring blowing temperature 15-25°C, blowing speed 0.5-1.0 m / s.

10. Use of the long-lasting antibacterial polyester fiber according to claim 8 or 9 in antibacterial treatment under seawater.

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