Antibacterial polyester amide and preparation method and application thereof
Antibacterial polyesteramides were prepared by using the polymerization reaction of raw materials such as caprolactone, caprolactam and ε-polylysine, which solved the problems of complicated synthesis steps and insufficient antibacterial performance, and achieved a highly efficient antibacterial effect.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- CHINA PETROLEUM & CHEMICAL CORP
- Filing Date
- 2024-12-24
- Publication Date
- 2026-06-26
AI Technical Summary
The synthesis steps of existing polyesteramide materials are cumbersome, and their antibacterial properties are insufficient, which limits their application in the field of biomedical materials.
Antibacterial polyesteramide was prepared by using caprolactone, caprolactam, and ε-polylysine as raw materials, and tetrabutyl titanate and 6-aminohexanoic acid as catalysts, in an inert atmosphere, with controlled temperature, pressure and time.
The preparation process is simple, and it has good antibacterial properties. It exhibits excellent antibacterial performance against Escherichia coli and Staphylococcus aureus, with a colony reduction rate of over 85%.
Abstract
Description
Technical Field
[0001] This invention relates to the field of polyesteramide preparation technology, specifically to an antibacterial polyesteramide, its preparation method, and its application. Background Technology
[0002] Polyesteramide materials are a new type of biodegradable polymer material that combines the characteristics of polyester and polyamide. They have rich structural and functional properties, good mechanical and chemical properties, and excellent biodegradability and non-toxicity. They can be used in both environmentally friendly and biomedical materials, and have good application prospects. They can be widely used in biomedical materials, biodegradable packaging materials, thermochromic polymer materials, resins, hot melt adhesives and adhesives, etc.
[0003] Chinese patent CN115676982A discloses a lysine-based polyesteramide polymer modified with nitroxide radicals, its preparation method, and its applications. Nitrooxide radicals, as a type of air-stable organic free radical, possess stable lone pairs of electrons. On one hand, they can achieve electrical conductivity; appropriate electrical stimulation can effectively promote the repair of skin wounds. On the other hand, they possess excellent antioxidant properties and show significant effects in antibacterial activity, promoting angiogenesis, and cell migration. However, the synthesis steps of this patented polymer are cumbersome.
[0004] Chinese patent CN113087897A discloses a method for preparing polyesteramide. This method includes adding an antioxidant and introducing nylon salt in the form of an oxygen-depleting aqueous solution after the esterification reaction. This solves the severe yellowing problem commonly encountered in polyesteramide synthesis, resulting in a polyesteramide with a low yellow index. Furthermore, fibers made using this polyesteramide exhibit higher breaking strength and good elongation at break.
[0005] In conclusion, the development of a simple-to-process polyesteramide material with antibacterial properties is of great significance for its application in the field of biomedical materials. Summary of the Invention
[0006] To achieve the above objectives, the present invention provides an antibacterial polyester amide, its preparation method, and its application.
[0007] The technical solution adopted in this invention is:
[0008] A method for preparing antibacterial polyester amide, using caprolactone, caprolactam, and ε-polylysine as raw materials; using tetrabutyl titanate and 6-aminohexanoic acid as catalysts, and polymerizing under an inert atmosphere at a certain temperature and pressure to obtain antibacterial polyester amide.
[0009] Furthermore, the molar ratio of caprolactone, caprolactam, and ε-polylysine is (1-6):(1-6):1.
[0010] Furthermore, the molar ratio of tetrabutyl titanate to 6-aminohexanoic acid is (1-2):1.
[0011] Furthermore, the amount of catalyst added is 1 to 2% of the total mass of caprolactone, caprolactam, and ε-polylysine.
[0012] Furthermore, the polymerization temperature is 120–150°C.
[0013] Furthermore, the polymerization pressure is 1–3 MPa.
[0014] Furthermore, the polymerization reaction time is 4 to 6 hours.
[0015] Furthermore, the inert atmosphere is one of nitrogen, helium, and argon.
[0016] An antibacterial polyester amide, obtained according to any of the above preparation methods.
[0017] The above-mentioned antibacterial polyester amides are used in biomedical materials.
[0018] The beneficial effects of this invention are:
[0019] The antibacterial polyester amide of the present invention has a simple preparation process and mild reaction conditions. It has good antibacterial properties against Escherichia coli and Staphylococcus aureus. After culturing for 20 hours according to the method of GB / T31402-2015, the number of colonies can be reduced by more than 85%. Detailed Implementation
[0020] To better understand the present invention, the following embodiments further illustrate its content. It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other. The present invention will now be described in detail with reference to the embodiments.
[0021] Example 1
[0022] An antibacterial polyesteramide material, the preparation method of which is as follows:
[0023] Maintaining a nitrogen atmosphere in the reactor, add 10g of caprolactam, 10g of caprolactone, and 2.15g of ε-polylysine. The molar ratio of caprolactone, caprolactam, and ε-lysine is 6:6:1. Add 1wt% of catalyst, with a catalyst ratio of tetrabutyl titanate to 6-aminohexanoic acid of 2:1. The reaction temperature is 120℃, the reaction pressure is 1MPa, and the polymerization reaction is carried out for 4 hours to obtain polyesteramide-1.
[0024] Example 2
[0025] Maintaining a nitrogen atmosphere in the reactor, add 10g of caprolactam, 10g of caprolactone, and 12.8g of ε-polylysine, with a molar ratio of caprolactone, caprolactam, and ε-polylysine of 1:1:1. Add 1wt% of catalyst, with a catalyst ratio of tetrabutyl titanate to 6-aminohexanoic acid of 2:1. The reaction temperature is 120℃, the reaction pressure is 1MPa, and the polymerization reaction is carried out for 4 hours to obtain polyesteramide-2.
[0026] Example 3
[0027] Maintaining a nitrogen atmosphere in the reactor, add 10g of caprolactam, 5g of caprolactone, and 4.3g of ε-polylysine. The molar ratio of caprolactone, caprolactam, and ε-polylysine is 3:3:1. Add 1wt% of catalyst, with a catalyst ratio of tetrabutyl titanate to 6-aminohexanoic acid of 2:1. The reaction temperature is 120℃, the reaction pressure is 1MPa, and the polymerization reaction is carried out for 5 hours to obtain polyesteramide-3.
[0028] Example 4
[0029] Maintaining a nitrogen atmosphere in the reactor, add 5g of caprolactam, 10g of caprolactone, and 6.45g of ε-polylysine. The molar ratio of caprolactone, caprolactam, and ε-polylysine is 2:2:1. Add 1wt% of catalyst, with a catalyst ratio of tetrabutyl titanate to 6-aminohexanoic acid of 2:1. The reaction temperature is 130℃, the reaction pressure is 1MPa, and the polymerization reaction is carried out for 4 hours to obtain polyesteramide-4.
[0030] Example 5
[0031] Maintaining a nitrogen atmosphere in the reactor, add 20g of caprolactam, 10g of caprolactone, and 8.4g of ε-polylysine. The molar ratio of caprolactone, caprolactam, and ε-polylysine is 3:3:2. Add 1wt% of catalyst, with a catalyst ratio of tetrabutyl titanate to 6-aminohexanoic acid of 2:1. The reaction temperature is 120℃, the reaction pressure is 1MPa, and the polymerization reaction is carried out for 4 hours to obtain polyesteramide-5.
[0032] Example 6
[0033] Maintaining a nitrogen atmosphere in the reactor, add 20g of caprolactam, 10g of caprolactone, and 12.8g of ε-polylysine. The molar ratio of caprolactone, caprolactam, and ε-polylysine is 2:1:1. Add 1wt% of catalyst, with a catalyst ratio of tetrabutyl titanate to 6-aminohexanoic acid of 2:1. The reaction temperature is 120℃, the reaction pressure is 2MPa, and the polymerization reaction is carried out for 4 hours to obtain polyesteramide-6.
[0034] Example 7
[0035] Maintaining a nitrogen atmosphere in the reactor, add 10g of caprolactam, 10g of caprolactone, and 12.8g of ε-polylysine, with a molar ratio of caprolactone, caprolactam, and ε-polylysine of 1:1:1. Add 2wt% of catalyst, with a catalyst ratio of tetrabutyl titanate to 6-aminohexanoic acid of 1:1. The reaction temperature is 120℃, the reaction pressure is 1MPa, and the polymerization reaction is carried out for 4 hours to obtain polyesteramide-7.
[0036] Comparative Example 1
[0037] Maintaining a nitrogen atmosphere in the reactor, 10g of caprolactam and 10g of caprolactone were added, along with 1wt% of catalyst. The catalyst ratio was 1:1 molar ratio of tetrabutyl titanate to 6-aminohexanoic acid. The reaction temperature was 120℃, and the reaction time was 4h, ultimately yielding polyesteramide-9.
[0038] The antibacterial properties of the products prepared in Examples 1-7 and Comparative Example 1 were tested, and the results are shown in Table 1 below.
[0039] The antibacterial properties of polyesteramide copolymers were tested according to GB / T 31402-2015, as follows:
[0040] (1) Sample preparation: The obtained polyesteramide polymer was used to prepare a 50mm×50mm sample with a thickness of no more than 10mm using a hot press.
[0041] (2) Bacterial culture: The inoculated Staphylococcus aureus was cultured at 35°C for 20 h, and then transferred to fresh slant culture medium for 20 h.
[0042] (3) Preparation of bacterial suspension: The bacterial suspension concentration was prepared to be (5.0-10.0)×10^5 cfu / ml as the experimental bacterial suspension;
[0043] (4) Sample inoculation: Place the plastic in a sterile petri dish, inoculate the bacterial solution, and then cover the inoculated bacterial solution with a film.
[0044] (5) Inoculation of inoculated samples: Place the culture dish containing the inoculation test at 35±1℃ and humidity not less than 90% for 20h;
[0045] (6) Bacterial recovery: The number of colonies was counted before and after inoculation of the polyesteramide sample.
[0046] Table 1
[0047] Example sequence number Initial colony Colonies after 20 hours Colony reduction rate % Example 1 200 148 26 Example 2 200 30 85 Example 3 200 138 39 Example 4 200 145 56 Example 5 200 75 62.5 Example 6 200 140 30 Example 7 200 100 50 Comparative Example 1 200 198 1
[0048] As can be seen from Table 1, the polyester amide of the present invention can achieve a colony reduction rate of at least 26% after 20 hours, and its antibacterial performance is more than 26 times that of the prior art.
[0049] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. For those skilled in the art, the present invention can be modified and varied in various ways, such as changing the reaction temperature and reaction time. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.
Claims
1. A method for preparing an antibacterial polyester amide, characterized in that: The antibacterial polyesteramide was obtained by polymerization reaction using caprolactone, caprolactam, and ε-polylysine as raw materials, and tetrabutyl titanate and 6-aminohexanoic acid as catalysts, under an inert atmosphere and at a certain temperature and pressure.
2. The preparation method according to claim 1, characterized in that: The molar ratio of caprolactone, caprolactam, and ε-polylysine is (1-6):(1-6):
1.
3. The preparation method according to claim 1, characterized in that: The molar ratio of tetrabutyl titanate to 6-aminohexanoic acid is (1-2):
1.
4. The preparation method according to claim 1, characterized in that: The amount of catalyst added is 1 to 2% of the total mass of caprolactone, caprolactam, and ε-polylysine.
5. The preparation method according to claim 1, characterized in that: The polymerization temperature is 120–150℃.
6. The preparation method according to claim 1, characterized in that: The polymerization pressure is 1–3 MPa.
7. The preparation method according to claim 1, characterized in that: The polymerization reaction time is 4 to 6 hours.
8. The preparation method according to claim 1, characterized in that: The inert atmosphere is one of nitrogen, helium, and argon.
9. An antibacterial polyester amide, characterized in that, Obtained by any one of the preparation methods according to claims 1-8.
10. The application of the antibacterial polyesteramide of claim 9 in biomedical materials.