An antibacterial bio-based polyamide elastomer and a method of making the same

Abstract

The application discloses an antibacterial bio-based polyamide elastomer and a preparation method thereof. The preparation method comprises the following steps: preparing a polyamide prepolymer containing a tertiary amine structure through ring-opening polymerization reaction of caprolactam, N-diethyl-aminocaprolactam and sebacic acid, then reacting with polytetramethylene ether glycol to form a polyamide-polyether block copolymer elastomer, and further modifying the polyamide-polyether block copolymer elastomer through reaction with a halogenated hydrocarbon to realize quaternary ammonium modification, so that the quaternary ammonium salt antibacterial group is stably introduced into the polymer molecular structure in a covalent manner. The bio-based polyamide elastomer prepared by the application has excellent elastic properties and persistent and stable quaternary ammonium antibacterial properties, the antibacterial components are not easy to migrate and lose, the preparation process is simple and controllable, is suitable for the field of functional materials, and has a good application prospect.

Description

Technical Field

[0001] This invention belongs to the field of functional polymers and antibacterial materials technology, specifically relating to a non-migratory quaternary ammonium salt antibacterial polymer that is constructed by embedding quaternizable reaction sites in the polyamide backbone and forming a block structure with polyether soft segments, as well as the preparation method and application of the polymer. Background Technology

[0002] Nylon elastomers, also known as polyamide elastomers (TPAEs), are a typical type of multi-block copolymer. Their molecular structure consists of high-melting-point, crystalline polyamide (PA) hard segments and flexible soft segments with low glass transition temperatures. The polyamide hard segments impart good mechanical strength, thermal stability, and structural support, while the soft segments, such as polyethers, polyesters, or polysiloxanes, provide excellent elasticity, flexibility, and resilience. Through the synergistic effect of the hard and soft segments, polyamide elastomers achieve a good balance between strength, toughness, and processability, possessing excellent wear resistance, chemical corrosion resistance, and ease of processing. They are widely used in engineering plastics and functional materials.

[0003] With the continuous expansion of applications for polyamide elastomers, the demand for functionalized materials is becoming increasingly prominent, among which antibacterial properties have become one of the important development directions. Quaternary ammonium salt antibacterial agents have received widespread attention in the field of polymeric antibacterial materials due to their broad-spectrum antibacterial activity, clear mechanism of action, and low tendency to induce bacterial resistance. Their antibacterial mechanism mainly relies on the electrostatic interaction between the positively charged quaternary ammonium salt groups and the negatively charged bacterial cell membrane surface, thereby disrupting the cell membrane structure and achieving efficient sterilization. However, existing quaternized antibacterial nylon elastomers mostly introduce quaternary ammonium salt structures through surface modification or physical blending. The quaternary ammonium salt groups and the polyamide matrix mainly rely on physical adsorption or weak interaction forces for bonding, lacking a stable chemical bond relationship. During long-term use, migration, precipitation, or loss can easily occur, leading to a decline in antibacterial performance and making it difficult to achieve a long-lasting and stable quaternized antibacterial effect.

[0004] Therefore, addressing the shortcomings of the existing technologies, this patent proposes an antibacterial bio-based polyamide elastomer and its preparation method. Through molecular structure design, quaternizable sites are introduced into the polyamide elastomer, and stable quaternary ammonium salt antibacterial groups are further constructed. This allows the antibacterial active groups to be covalently fixed within the polymer molecular chain, achieving integration of antibacterial function and the material's bulk structure. Compared to existing surface-modified or physically blended antibacterial materials, the polyamide elastomer described in this patent maintains excellent mechanical properties, thermal stability, and processing performance while possessing significant advantages such as high antibacterial efficiency, strong antibacterial durability, and resistance to migration and loss. Summary of the Invention

[0005] Objective of the Invention: To address the problems of poor antibacterial effect and insufficient antibacterial durability in the application of polyamides in the prior art, this invention provides an antibacterial bio-based polyamide elastomer and its preparation method. The antibacterial polyamide elastomer of this invention maintains excellent mechanical properties, thermal stability, and processing performance, while possessing significant advantages such as high antibacterial efficiency, strong antibacterial durability, and resistance to migration and loss.

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

[0007] In a first aspect, the present invention provides an antibacterial bio-based polyamide elastomer having the following structural units:

[0008]

[0009] Wherein, the group of R1 is any one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl;

[0010] R2 is selected from any one of fluoride ions, chloride ions, bromide ions, and iodide ions;

[0011] x is 0-100, y is 0-100, z is 8-78, m is 0-100, and n is 0-100.

[0012] Secondly, the invention provides a method for preparing an antibacterial bio-based polyamide elastomer, the method comprising the following steps: mixing caprolactam, N-diethyl-aminocaprolactam, and sebacic acid together to obtain a polyamide with quaternizable sites; then polycondensing polytetramethylene ether glycol and a reaction catalyst to obtain a polyamide elastomer with quaternizable sites; and finally dissolving the polyamide elastomer with quaternizable sites in a solvent and reacting it with a haloalkane to obtain an antibacterial polyamide elastomer.

[0013] Thirdly, this invention discloses a method for preparing the above-mentioned N-diethyl-aminocaprolactam. The method includes the following steps:

[0014] (1) In a reactor equipped with a water separator and a condenser, lysine and n-hexanol were added, and nitrogen gas was introduced for protection. The reactor was heated with a heating mantle, and the mixture was mechanically stirred and refluxed to separate the water until no more water was discharged. Heating was then stopped, and concentrated hydrochloric acid was added dropwise to adjust the pH until a large amount of solid precipitated. The mixture was filtered, and the solid was collected and washed with anhydrous ethanol until decolorized to obtain a white solid aminocaprolactam hydrochloride with a yield of 96%.

[0015] (2) In a three-necked flask, α-amino-ε-caprolactam hydrochloride, sodium carbonate, and isopropanol were added and stirred to dissolve. Iodoethane was added, and the mixture was refluxed under N2 protection. After the reaction was complete, the mixture was filtered, and the filtrate was suspended to remove isopropanol. Dichloromethane was added to dissolve the filtrate, and distilled water was used for extraction. The organic phase was dried over anhydrous Na2SO4, and the crude product was obtained by suspending the DCM. N-Diethyl-aminocaprolactam was obtained by recrystallization from ethanol multiple times, with a yield of 90%.

[0016] The bio-based polyamide thermoplastic elastomer prepared by this invention has excellent thermal and mechanical properties, and the 5% thermal decomposition temperature (T) is... d,5％ The maximum thermal decomposition temperature is 380–400℃. d,max The melting temperature is 430–450℃, and the melting temperature (T) is 430–450℃. m The temperature range is 169–220℃, and the crystallization temperature (Tc) is 115–150℃. The strength is 8–40 MPa, the elongation at break is 350–1000%, and the toughness of the material was evaluated by notched cantilever beam impact test. The bio-based polyamide-polyether quaternary ammonium salt antibacterial polymer elastomer showed no fracture at room temperature, and the impact strength far exceeded that of ordinary engineering plastics. The elastic recovery rate was >90%, the Shore hardness was D30–70D, and the melt index was 5–70 g / 10 min (235℃).

[0017] Fourthly, the bio-based polyamide thermoplastic elastomer obtained by this invention, after quaternization modification, possesses intrinsic antibacterial properties; tested according to GB / T31402 standard, its antibacterial rate against both *Escherichia coli* and *Staphylococcus aureus* is greater than 99%. Furthermore, the polyamide-polyether quaternary ammonium salt antibacterial polymer material of this invention can be applied to:

[0018] 1) Medical catheters, dressings, and surgical consumables;

[0019] 2) Flexible electronic device packaging materials;

[0020] 3) Antibacterial films and coatings;

[0021] 4) Sensor interface layer and biological contact materials.

[0022] Beneficial effects:

[0023] (1) The content of antibacterial groups in the polyamide-polyether quaternary ammonium salt antibacterial polymer synthesized in this invention can be precisely controlled. By adjusting the proportion of aminocaprolactam, the density of quaternary ammonium salt can be designed, thus solving the problem of uncontrollable antibacterial components in traditional antibacterial materials.

[0024] (2) The antibacterial groups of the polyamide-polyether quaternary ammonium salt antibacterial polymer synthesized in this invention are covalently fixed and durable. The quaternary ammonium salt structure is fixed on the polymer chain by chemical bonds, which is not easy to migrate or be lost, thus significantly improving the antibacterial durability and safety.

[0025] (3) The polyamide-polyether quaternary ammonium salt antibacterial polymer prepared by this invention has excellent mechanical properties and flexibility, which comes from the introduction of PTMEG soft segments, so that the material has high elasticity, low modulus and good fatigue durability, making it suitable for flexible and dynamic application scenarios.

[0026] (4) The antibacterial properties and mechanical properties of the polyamide-polyether quaternary ammonium salt antibacterial polymer synthesized in this invention can be synergistically optimized. By controlling the molecular weight and amino content, the optimal balance between antibacterial properties and mechanical properties can be achieved, avoiding the problem of "strong antibacterial but brittle".

[0027] (5) The synthesis method provided by the present invention has strong process versatility and is easy to industrialize. The method adopts conventional polyamide synthesis and quaternization process, which is applicable to the existing polymer industrial system and has good feasibility for scale-up production. Attached Figure Description

[0028] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments, and the advantages of the present invention in the above and other aspects will become clearer.

[0029] Table 1 shows the antimicrobial performance tests for all polymer examples and comparative examples.

[0030] Table 2 shows the mechanical and thermal properties of all polymer examples and comparative examples.

[0031] Figure 1 Monomer of Example 1 1 HNMR image.

[0032] Figure 2 Polymer of Example 2 1 HNMR image.

[0033] Figure 3 This is a TGA diagram of the polymer from Example 2.

[0034] Figure 4 The image shows the DSC diagram of the polymer in Example 2.

[0035] Figure 5 The image shows the XRD pattern of the polymer in Example 2.

[0036] Figure 6 This is a polymer cyclic stretching diagram from Example 2. Detailed Implementation

[0037] The present invention can be better understood from the following embodiments. However, those skilled in the art will readily understand that the descriptions in the embodiments are for illustrative purposes only and should not, and will not, limit the invention as detailed in the claims.

[0038] Unless otherwise specified, the experimental methods described in the following examples are conventional methods; unless otherwise specified, the reagents and materials are commercially available.

[0039] In the following examples, the products were measured using a 400MHz Bruker nuclear magnetic resonance instrument: the deuteration reagent was tetramethylsilane (TMS) as an internal standard, the concentration of which was approximately 8 mg / mL for 1H NMR and approximately 20 mg / mL for 1C NMR; the deuteration reagents were deuterated chloroform and deuterated trifluoroacetic acid.

[0040] The thermal stability (T) of the polymer in this invention d,5％ T d,max The results were measured using a TGA-550 instrument. 4–8 mg of the polymerization product was weighed and placed in a platinum dish, and then heated under a nitrogen atmosphere (gas flow rate of 50 mL / min). -1 ), at 20℃min -1 The heating rate increases to 800℃.

[0041] In this invention, the melt temperature (Tm) and crystallization temperature (Tc) of the polymer were measured using a DSC-250 instrument. The heating and cooling processes of the polymer were measured under a nitrogen protective atmosphere with a gas flow rate of 50 mL / min. -1 Weigh 4–8 mg of sample into a sample pan, raise the temperature from -30°C to 250°C at a rate of 10°C / min, hold for 3 minutes, then cool from 250°C to -30°C at a rate of 10°C / min, and finally raise the temperature back to 250°C.

[0042] In this invention, polymer WAXD data is generated using a filtered CuKα radiation source (wavelength...). The diffraction patterns were collected using a D / max-2550VB X-ray diffractometer and recorded in the range of 2θ from 5° to 60°.

[0043] In this invention, the antibacterial properties of the material are tested using the covering film contact method according to the national standard GB / T31402-2015. The testing process first involves preparing a standard bacterial suspension, culturing it in a constant-temperature shaker, and then adjusting the concentration to 10. 8 CFU / mL; The sample to be tested (including sterilized samples, and the matching cover film, after being disinfected by soaking in alcohol, cut into 1cm diameter round pieces for later use). Testing stage: The bacterial solution is dropped onto the sample surface, and immediately covered with a sterile film to ensure uniform contact of the bacterial solution and prevent overflow. Then, it is placed in a sterile Petri dish and incubated at 37℃ or 28℃ respectively. After incubation, the sample and cover film are rinsed with sterile physiological saline. The colony count of the collected solution is performed by plate coating method. Finally, the antibacterial efficacy is calculated according to the formula: inhibition rate = (concentration of bacterial solution in blank group - concentration in experimental group) / concentration in blank group × 100%.

[0044] In this invention, the mechanical properties of the samples were tested using an electronic universal testing machine (TMG104). The tensile test conditions were in accordance with the national standard GB / T1040.1-2006, with a tensile rate of 50 mm / min and a test temperature of room temperature.

[0045] Melt Index Test: After thoroughly drying the sample, preheat the melt indexer barrel to the standard temperature of 235℃ and maintain a constant temperature. Weigh 3-8g of the dried sample and add it to the barrel. Compact the material using the piston rod within 1 minute to remove residual air bubbles. Then apply a 2.16kg weight to extrude the melt through the die, discarding any sample strips containing air bubbles in the initial stage. After the extrusion stabilizes, cut the sample strips at 30-60s intervals, controlling the length to be between 10-20mm. Accurately weigh at least 3 air-free sample strips, calculate the melt index, and express the final result in g / 10min.

[0046] Example 1:

[0047] In a 2L reactor equipped with a water separator and condenser, 0.28 mol of lysine and 1.2 L of n-hexanol were added, and nitrogen was purged for protection. The reactor was heated under a heating mantle, mechanically stirred, and refluxed to separate water, maintaining a reaction temperature of 150°C. After 20 hours of reaction, with no water precipitated, heating was stopped. Concentrated hydrochloric acid was added dropwise to adjust the pH to weakly acidic, resulting in the precipitation of a large amount of solid. The solid was filtered, collected, and washed with anhydrous ethanol until decolorized, yielding a white solid, aminocaprolactam hydrochloride, with a yield of 96%. In a 1000 mL three-necked flask, 0.2 mol of aminocaprolactam hydrochloride, 0.6 mol of sodium carbonate, and 500 mL of isopropanol were added, stirred to dissolve, and 0.6 mol of iodoethane was added. The mixture was then refluxed at 80°C under nitrogen protection. After 24 hours of reaction, the mixture was filtered, and the filtrate was suspended and evaporated to remove isopropanol. The solution was dissolved in 600 mL of dichloromethane and extracted with 50 mL of distilled water. The target product was dissolved in the organic phase, which was dried over anhydrous Na₂SO₄. The crude product was obtained by evaporation of DCM. N-Diethyl-Aminocaprolactam was obtained by recrystallization from ethanol multiple times, with a yield of 90%.

[0048] Example 2:

[0049] 69.9329 g of caprolactam, 0.8722 g of N-diethyl-aminocaprolactam, 5.0285 g of sebacic acid, and 10 mL of deionized water were sequentially added to a high-pressure reactor, which was then sealed. After purging with nitrogen for 10 minutes at room temperature, the reactor was heated to 250°C and maintained at this temperature for 3 hours for polymerization. The pressure was then gradually reduced to atmospheric pressure. Next, 29.81 g of polytetramethylene ether glycol (molecular weight 1000 g / mol) and 0.3480 g of zirconium butoxide were added to the high-pressure reactor, which was then sealed. After purging with nitrogen at room temperature, the mixture was stirred at atmospheric pressure for 10 minutes. Finally, the reactor was heated to 260°C and stirred under negative pressure for 6 hours. After polycondensation was complete, stirring was stopped, and the polymer product was drained into cooling water, washed three times with anhydrous ethanol, and then placed in a vacuum drying oven at 60°C for 12 hours to obtain a polyamide-polyether block copolymer.

[0050] 10g of TPAE elastomer was weighed and dissolved in 100mL of hexafluoroisopropanol. 0.1mL of iodoethane was added, and the mixture was refluxed at 80℃ for 38 hours. Most of the HFIP was removed by rotary evaporation. The precipitate was poured into a 1:1 mixture of isopropyl ether and petroleum ether, vacuum filtered, and dried to obtain the polyamide-polyether quaternary ammonium salt antibacterial polymer.

[0051] Example 3:

[0052] 59.6772 g of caprolactam, 4.2541 g of N-diethyl-aminocaprolactam, 5.8653 g of sebacic acid, and 6 mL of deionized water were sequentially added to a high-pressure reactor, which was then sealed. After purging with nitrogen at room temperature for 10 minutes, the reactor was heated to 250°C and maintained at this temperature for 3 hours for polymerization. The pressure was then gradually reduced to atmospheric pressure. Next, 29 g of polytetramethylene ether glycol (molecular weight 1000 g / mol) and 0.3561 g of zirconium n-butoxide were added to the high-pressure reactor, which was then sealed. After purging with nitrogen at room temperature, the mixture was stirred at atmospheric pressure for 10 minutes. Finally, the reactor was heated to 260°C and stirred under negative pressure for 6 hours. After polycondensation was complete, stirring was stopped, and the polymer product was drained into cooling water, washed three times with anhydrous ethanol, and then dried in a vacuum drying oven at 60°C for 12 hours to obtain the polyamide-polyether block copolymer.

[0053] 10g of TPAE elastomer was weighed and dissolved in 100mL of hexafluoroisopropanol. 0.5mL of iodoethane was added, and the mixture was refluxed at 80℃ for 38 hours. Most of the HFIP was removed by rotary evaporation. The precipitate was poured into a 1:1 mixture of isopropyl ether and petroleum ether, vacuum filtered, and dried to obtain the polyamide-polyether quaternary ammonium salt antibacterial polymer.

[0054] Example 4:

[0055] 45.6714 g of caprolactam, 8.9207 g of N-diethyl-aminocaprolactam, 5.6630 g of sebacic acid, and 6 mL of deionized water were sequentially added to a high-pressure reactor, which was then sealed. After purging with nitrogen for 10 minutes at room temperature, the reactor was heated to 250°C and maintained at this temperature for 3 hours for polymerization. The pressure was then gradually reduced to atmospheric pressure. Next, 28 g of polytetramethylene ether glycol (1000 g / mol) and 0.356 g of zirconium n-butoxide were added to the high-pressure reactor, which was then sealed. After purging with nitrogen at room temperature, the reactor was stirred at atmospheric pressure for 10 minutes. Finally, the reactor was heated to 260°C and stirred under negative pressure for 6 hours. After polycondensation was complete, stirring was stopped, and the polymer product was drained into cooling water, washed three times with anhydrous ethanol, and then dried in a vacuum drying oven at 60°C for 12 hours to obtain the polyamide-polyether block copolymer.

[0056] 10g of TPAE elastomer was weighed and dissolved in 100mL of hexafluoroisopropanol. 1mL of iodoethane was added, and the mixture was refluxed at 80℃ for 38 hours. Most of the HFIP was removed by rotary evaporation. The precipitate was then poured into a 1:1 mixture of isopropyl ether and petroleum ether, vacuum filtered, and dried to obtain the polyamide-polyether quaternary ammonium salt antibacterial polymer.

[0057] Example 5:

[0058] 41.9031 g of caprolactam, 12.0330 g of N-diethyl-aminocaprolactam, 5.4 g of sebacic acid, and 6 mL of deionized water were sequentially added to a high-pressure reactor, which was then sealed. After purging with nitrogen for 10 minutes at room temperature, the reactor was heated to 250°C and maintained at this temperature for 3 hours for polymerization. The pressure was then gradually reduced to atmospheric pressure. Next, 26.7 g of polytetramethylene ether glycol (molecular weight 1000 g / mol) and 0.3444 g of zirconium butoxide were added to the high-pressure reactor, which was then sealed. After purging with nitrogen at room temperature, the mixture was stirred at atmospheric pressure for 10 minutes. Finally, the reactor was heated to 260°C and stirred under negative pressure for 6 hours. After polycondensation was complete, stirring was stopped, and the polymer product was drained into cooling water, washed three times with anhydrous ethanol, and then placed in a vacuum drying oven at 60°C for 12 hours to obtain a polyamide-polyether block copolymer.

[0059] 10g of TPAE elastomer was weighed and dissolved in 100mL of hexafluoroisopropanol. 1.5mL of iodoethane was added, and the mixture was refluxed at 80℃ for 38 hours. Most of the HFIP was removed by rotary evaporation. The precipitate was poured into a 1:1 mixture of isopropyl ether and petroleum ether, vacuum filtered, and dried to obtain the polyamide-polyether quaternary ammonium salt antibacterial polymer.

[0060] Example 6:

[0061] 38.3386 g of caprolactam, 15.5965 g of N-diethyl-aminocaprolactam, 5.3799 g of sebacic acid, and 7 mL of deionized water were sequentially added to a high-pressure reactor, which was then sealed. After purging with nitrogen for 10 minutes at room temperature, the reactor was heated to 250°C and maintained at this temperature for 3 hours for polymerization. The pressure was then gradually reduced to atmospheric pressure. Next, 26.6 g of polytetramethylene ether glycol (2000 g / mol) and 0.3424 g of zirconium butoxide were added to the high-pressure reactor, which was then sealed. After purging with nitrogen at room temperature, the mixture was stirred at atmospheric pressure for 10 minutes. Finally, the reactor was heated to 260°C and stirred under negative pressure for 6 hours. After polycondensation was complete, stirring was stopped, and the polymer product was drained into cooling water, washed three times with anhydrous ethanol, and then dried in a vacuum drying oven at 60°C for 12 hours to obtain the polyamide-polyether block copolymer.

[0062] 10g of TPAE elastomer was weighed and dissolved in 100mL of hexafluoroisopropanol. 2mL of iodoethane was added, and the mixture was refluxed at 80℃ for 38 hours. Most of the HFIP was removed by rotary evaporation. The precipitate was then poured into a 1:1 mixture of isopropyl ether and petroleum ether, vacuum filtered, and dried to obtain the polyamide-polyether quaternary ammonium salt antibacterial polymer.

[0063] Example 7:

[0064] 34.9653 g of caprolactam, 8.9677 g of N-diethyl-aminocaprolactam, 5.2383 g of sebacic acid, and 5 mL of deionized water were sequentially added to a high-pressure reactor, which was then sealed. After purging with nitrogen for 10 minutes at room temperature, the reactor was heated to 250°C and maintained at this temperature for 3 hours for polymerization. The pressure was then gradually reduced to atmospheric pressure. Next, 25.9 g of polytetramethylene ether glycol (2000 g / mol) and 0.3396 g of zirconium n-butoxide were added to the high-pressure reactor, which was then sealed. After purging with nitrogen at room temperature, the reactor was stirred at atmospheric pressure for 10 minutes. Finally, the reactor was heated to 260°C and stirred under negative pressure for 6 hours. After polycondensation was complete, stirring was stopped, and the polymer product was drained into cooling water, washed three times with anhydrous ethanol, and then dried in a vacuum drying oven at 60°C for 12 hours to obtain the polyamide-polyether block copolymer.

[0065] 10g of TPAE elastomer was weighed and dissolved in 100mL of hexafluoroisopropanol. 1mL of iodoethane was added, and the mixture was refluxed at 80℃ for 38 hours. Most of the HFIP was removed by rotary evaporation. The precipitate was then poured into a 1:1 mixture of isopropyl ether and petroleum ether, vacuum filtered, and dried to obtain the polyamide-polyether quaternary ammonium salt antibacterial polymer.

[0066] Example 8:

[0067] 31.7719 g of caprolactam, 12.1601 g of N-diethyl-aminocaprolactam, 5.0967 g of sebacic acid, and 6 mL of deionized water were sequentially added to a high-pressure reactor, which was then sealed. After purging with nitrogen for 10 minutes at room temperature, the reactor was heated to 250°C and maintained at this temperature for 3 hours for polymerization. The pressure was then gradually reduced to atmospheric pressure. Next, 25.2 g of polytetramethylene ether glycol (2000 g / mol) and 0.3368 g of zirconium butoxide were added to the high-pressure reactor, which was then sealed. After purging with nitrogen at room temperature, the reactor was stirred at atmospheric pressure for 10 minutes. Finally, the reactor was heated to 260°C and stirred under negative pressure for 6 hours. After polycondensation, stirring was stopped, and the polymer product was drained into cooling water, washed three times with anhydrous ethanol, and then dried in a vacuum drying oven at 60°C for 12 hours to obtain the polyamide-polyether block copolymer.

[0068] 10g of TPAE elastomer was weighed and dissolved in 100mL of hexafluoroisopropanol. 1.5mL of iodoethane was added, and the mixture was refluxed at 80℃ for 38 hours. Most of the HFIP was removed by rotary evaporation. The precipitate was poured into a 1:1 mixture of isopropyl ether and petroleum ether, vacuum filtered, and dried to obtain the polyamide-polyether quaternary ammonium salt antibacterial polymer.

[0069] Example 9:

[0070] 50.0607 g of caprolactam, 4.8722 g of N-diethyl-aminocaprolactam, 8.0285 g of sebacic acid, and 7 mL of deionized water were sequentially added to a high-pressure reactor, which was then sealed. After purging with nitrogen for 10 minutes at room temperature, the reactor was heated to 250°C and maintained at this temperature for 3 hours for polymerization. The pressure was then gradually reduced to atmospheric pressure. Next, 29.81 g of polytetramethylene ether glycol (2000 g / mol) and 0.3480 g of zirconium butoxide were added to the high-pressure reactor, which was then sealed. After purging with nitrogen at room temperature, the reactor was stirred at atmospheric pressure for 10 minutes. Finally, the reactor was heated to 260°C and stirred under negative pressure for 6 hours. After polycondensation was complete, stirring was stopped, and the polymer product was drained into cooling water, washed three times with anhydrous ethanol, and then dried in a vacuum drying oven at 60°C for 12 hours to obtain the polyamide-polyether block copolymer.

[0071] 10g of TPAE elastomer was weighed and dissolved in 100mL of hexafluoroisopropanol. 0.5mL of bromoethane was added, and the mixture was refluxed at 80℃ for 48 hours. Most of the HFIP was removed by rotary evaporation. The precipitate was poured into a 1:1 mixture of isopropyl ether and petroleum ether, vacuum filtered, and dried to obtain the polyamide-polyether quaternary ammonium salt antibacterial polymer.

[0072] Example 10:

[0073] 50.0607 g of caprolactam, 15.1722 g of N-diethyl-aminocaprolactam, 7.0175 g of sebacic acid, and 6 mL of deionized water were sequentially added to a high-pressure reactor, which was then sealed. After purging with nitrogen for 10 minutes at room temperature, the reactor was heated to 250°C and maintained at this temperature for 3 hours for polymerization. The pressure was then gradually reduced to atmospheric pressure. Next, 29.81 g of polytetramethylene ether glycol (molecular weight 2000 g / mol) and 0.3480 g of zirconium butoxide were added to the high-pressure reactor, which was then sealed. After purging with nitrogen at room temperature, the mixture was stirred at atmospheric pressure for 10 minutes. Finally, the reactor was heated to 260°C and stirred under negative pressure for 6 hours. After polycondensation was complete, stirring was stopped, and the polymer product was drained into cooling water, washed three times with anhydrous ethanol, and then dried in a vacuum drying oven at 60°C for 12 hours to obtain the polyamide-polyether block copolymer.

[0074] 10g of TPAE elastomer was weighed and dissolved in 100mL of hexafluoroisopropanol. 2mL of bromoethane was added, and the mixture was refluxed at 80℃ for 48 hours. Most of the HFIP was removed by rotary evaporation. The precipitate was poured into a 1:1 mixture of isopropyl ether and petroleum ether, vacuum filtered, and dried to obtain the polyamide-polyether quaternary ammonium salt antibacterial polymer.

[0075] Example 11

[0076] 53.9607 g of caprolactam, 0.722 g of N-diethyl-aminocaprolactam, 4.973 g of sebacic acid, and 5 mL of deionized water were sequentially added to a high-pressure reactor, which was then sealed. After purging with nitrogen for 10 minutes at room temperature, the reactor was heated to 250°C and maintained at this temperature for 3 hours for polymerization. The pressure was then gradually reduced to atmospheric pressure. Next, 29.81 g of polytetramethylene ether glycol (molecular weight 2000 g / mol) and 0.3480 g of zirconium n-butoxide were added to the high-pressure reactor, which was then sealed. After purging with nitrogen at room temperature, the reactor was stirred at atmospheric pressure for 10 minutes. Finally, the reactor was heated to 260°C and stirred under negative pressure for 6 hours. After polycondensation was complete, stirring was stopped, and the polymer product was drained into cooling water, washed three times with anhydrous ethanol, and then dried in a 60°C oven for 12 hours to obtain the polyamide-polyether block copolymer.

[0077] 10g of TPAE elastomer was weighed and dissolved in 100mL of hexafluoroisopropanol. 0.5mL of bromoethane was added, and the mixture was refluxed at 80℃ for 48 hours. Most of the HFIP was removed by rotary evaporation. The precipitate was poured into a 1:1 mixture of isopropyl ether and petroleum ether, vacuum filtered, and dried to obtain the polyamide-polyether quaternary ammonium salt antibacterial polymer.

[0078] Comparative Example 1

[0079] To compare the effects of antibacterial agents, we prepared an elastomer with added copper ion antibacterial components, as follows:

[0080] 69.9329 g of caprolactam, 5.0285 g of sebacic acid, 0.02 wt% pretreated copper acetate, and 10 mL of deionized water were sequentially added to a high-pressure reactor, which was then sealed. After purging with nitrogen for 10 minutes at room temperature, the reactor was heated to 250°C and maintained at this temperature for 3 hours for polymerization. The pressure was then gradually reduced to atmospheric pressure. Next, 29.81 g of polytetramethylene ether glycol (molecular weight 1000 g / mol) and 0.3480 g of zirconium butoxide were added to the high-pressure reactor, which was then sealed. After purging with nitrogen at room temperature, the mixture was stirred at atmospheric pressure for 10 minutes. Finally, the reactor was heated to 260°C and stirred under negative pressure for 6 hours. After polycondensation was complete, stirring was stopped, and the polymer product was drained into cooling water, washed three times with anhydrous ethanol, and then dried in a vacuum drying oven at 60°C for 12 hours to obtain the polyamide-polyether block copolymer.

[0081] The above-described embodiments are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

[0082] Table 1

[0083]

[0084] Table 2

[0085] Example number Melting point / °C Tensile strength / MPa Elongation at break / % Melt index / g / 10min Example 2 204 40.0±0.5 350±5 5.0±0.4 Example 3 196 30.5±0.3 590±4 7.8±0.3 Example 4 193 27.4±0.1 660±1 9.1±0.2 Example 5 187 25.1±0.2 740±6 15.1±0.4 Example 6 181 24.0±0.5 800±5 15.3±0.2 Example 7 179 22.3±0.1 815±3 19.7±0.3 Example 8 177 21.9±0.4 871±8 21.4±0.2 Example 9 176 15.4±0.1 900±1 23.1±0.1 Example 10 171 11.5±0.3 945±3 23.9±0.3 Example 11 169 8.0±0.1 1000±1 25.0±0.1 Comparative Example 1 203 24±0.3 250±6 7.5±0.1

Claims

1. An antibacterial bio-based polyamide elastomer, characterized in that, The polymer comprises the following structural units: The group of R1 is any one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl; R2 is selected from any one of fluoride ions, chloride ions, bromide ions, and iodide ions; x is 0-100, y is 0-100, z is 8-78, m is 0-100, and n is 0-100.

2. The method for preparing the antibacterial bio-based polyamide elastomer according to claim 1, characterized in that, Includes the following steps: Caprolactam, N-diethyl-aminocaprolactam, and sebacic acid were added in a specific molar ratio, along with deionized water, and the mixture was sealed in a high-pressure reactor. After reaching temperature T1, the pressure was maintained at P1 for reaction time A1. Then, the pressure was gradually reduced to atmospheric pressure, and the temperature was lowered to T2. Polytetramethylene ether glycol and a catalyst were added to the high-pressure reactor, and the temperature was raised to T3 with stirring for a period of time. A vacuum was then created, and the mixture was stirred for time A2. After the reaction was complete, the mixture was cooled in deionized water to obtain a polyamide block copolymer. The polyamide block copolymer was dissolved in a solvent and reacted with a haloalkane at temperature T4 for time A3 to obtain an antibacterial polyamide elastomer.

3. The preparation method according to claim 2, characterized in that, The molecular weight of the polytetramethylene glycol is 500-5000 g / mol.

4. The preparation method according to claim 2, characterized in that, The molar ratio of caprolactam, sebacic acid, and PTEMG is 100:(1-100):(1-100):(1-100).

5. The preparation method according to claim 4, characterized in that, The deionized water content is 5-15 wt%.

6. The preparation method according to claim 4, characterized in that, The catalyst is any one of zirconium n-butoxide, zirconium oxide sulfate, zirconium acetylacetonate, tetrabutyl titanate, tetraisopropyl titanate, antimony trioxide, and aluminum isopropoxide, and the amount of the catalyst is 500-10000 ppm.

7. The preparation method according to claim 4, characterized in that, The T1 temperature is 220–250℃, the A1 reaction time is 3–5 h, and the P1 pressure is 1.0–3.0 MPa. The T2 temperature is 80–140℃, the T3 temperature is 220–260℃, and the A2 reaction time is 5–12 h.

8. The preparation method according to claim 4, characterized in that, The reaction time for A3 is 24-48 h, and the temperature for T4 is 40-80 °C. The halogenated hydrocarbons are any one of the following: fluoropentane, fluorohexane, fluoroheptane, fluorooctane, fluorononane, fluorodecane, fluorododecane, chlorobutane, chloropentane, chlorohexane, chloroheptane, bromoethane, bromobutane, bromopentane, bromohexane, bromoheptane, bromooctane, bromononane, bromodecane, bromoundecane, bromododecane, iodomethane, iodoethane, iodobutane, iodobutane, iodopentane, iodohexane, iodoheptane, iodooctane, iodononane, iododecane, iodoundecane, and iodododecane.

9. The application of the polyamide elastomer of claim 1 in the field of antibacterial agents.

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