CN108359089B

CN108359089B - Antibacterial polyaryletherketone material and preparation method thereof

Info

Publication number: CN108359089B
Application number: CN201810028862.3A
Authority: CN
Inventors: 汤福文; 李君�; 管月; 王延波
Original assignee: Dalian Nine Fine Chemical Co Ltd
Current assignee: Dalian Nine Fine Chemical Co Ltd
Priority date: 2018-01-11
Filing date: 2018-01-11
Publication date: 2019-12-10
Anticipated expiration: 2038-01-11
Also published as: CN108359089A

Abstract

The invention discloses a preparation method of antibacterial polyaryletherketone, belonging to the technical field of synthesis of high polymer materials. The pyridine quaternary ammonium salt antibacterial structure and the terminal amino structure are introduced into the main chain of the polyaryletherketone, so that the temperature resistance of the antibacterial structural unit is obviously improved, the dissolution rate of the material is low, and the material has longer-acting antibacterial performance. The material of the invention can be independently processed to be used as an antibacterial high polymer material, and can also be used as an antibacterial agent to be added into other high polymer materials, and the process is simple and easy to control.

Description

Antibacterial polyaryletherketone material and preparation method thereof

Technical Field

The invention belongs to the technical field of polymer synthesis, and particularly relates to antibacterial polyaryletherketone containing a naphthyridine structure and a preparation method thereof.

Background

With the improvement of living standard of people, the requirement for improving the living environment of human beings is increasingly urgent, and the effective prevention and reduction of the harm of microorganisms such as bacteria and fungi to the human society is an important link. For a long time, microorganisms such as bacteria, fungi and the like as pathogenic bacteria have great harm to human beings, animals and plants, influence the health of people and even endanger life; microorganisms also cause decomposition, deterioration, and putrefaction of various materials, causing significant economic loss, and inhibiting their growth reduces the occurrence of diseases, so that materials having bactericidal and antibacterial effects are receiving increasing attention.

The polyaryletherketone is a high polymer which is obtained by polycondensation of diphenol monomer and dihalogenated benzophenone and contains a ketone bond and two ether bonds in a main chain structure, belongs to a special high polymer material, has excellent performances of high heat resistance grade, impact resistance, high toughness, irradiation resistance, hydrolysis resistance and the like, and has wide application in the fields of aviation, aerospace, mechanical electronics, petrochemical industry and the like.

the quaternary pyridinium salt antibacterial material has the advantages of broad spectrum, high efficiency, low toxicity, safety, long-acting stability and the like, is widely applied to various fields such as industry, agriculture, construction, medical treatment, food, daily life and the like, but is often decomposed or dissolved out by heat to shorten the service life or lose the antibacterial performance. Therefore, it is urgently required to develop a polymer material having low dissolution, high stability and antibacterial properties.

Disclosure of Invention

In order to solve the technical problems, the invention aims to introduce the antibacterial structural unit containing the quaternary pyridinium salt into the polyaryletherketone high molecular material framework, so that the antibacterial effect and the use temperature of the quaternary pyridinium salt are greatly improved, and the dissolution rate is reduced. The antibacterial polyaryletherketone material can be directly injection molded into a section and can also be used as an antibacterial agent to be added into other high polymer materials.

Polyaryletherketone (PPEK-P) containing naphthyridine and pyridine structures is a main raw material of an antibacterial material, the polyaryletherketone containing naphthyridine and pyridine structures is polyaryletherketone with a repeating unit and a main chain containing naphthyridine and pyridine structures, and the number average molecular weight is about 12000-30000; the structural formula is as follows:

Wherein the number of repeating units is 20-50.

The high molecular material is prepared by introducing a pyridine quaternary ammonium salt-containing antibacterial structural unit into a main chain of polyaryletherketone, and has the following structure:

wherein: x ═ Cl, Br, I.

A method for preparing the material of the polyether-ether-ketone is characterized by comprising the following operations:

Mixing an organic solvent, PPEK-P, an inorganic base and 3-halopropylamine, and reacting at 20-80 ℃; after the reaction is finished, pouring the reaction liquid into a precipitator; filtering, separating, cleaning and drying to obtain the antibacterial polyaryletherketone with the pyridine quaternary ammonium salt structure. The reaction route is as follows:

Further, in the above technical solution, the organic solvent is selected from chloroform, dichloromethane, dichloroethane, N '-dimethylformamide or N, N' -dimethylacetamide.

Further, in the above technical solution, the mass-to-volume ratio of the PPEK-P to the solvent is 1 g: 5-20 mL; the molar ratio of PPEK-P, alkali and 3-halogenated propylamine is 1: 0.5-3: 0.1-2.

Further, in the above technical solution, the alkali is selected from sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate.

Further, in the above technical scheme, the 3-halopropylamine is selected from 3-chloropropylamine, 3-bromopropylamine or 3-iodopropylamine.

Further, in the above technical solution, the precipitating agent is selected from methanol, ethanol, isopropanol or water.

Furthermore, in the technical scheme, whether the nitrogen is protected or not has no influence on the reaction yield and the product performance.

The invention has the beneficial effects that:

1. The invention directly introduces the pyridine quaternary ammonium salt structure into the main chain of the polyaryletherketone, greatly improves the temperature resistance of the antibacterial structural unit and reduces the dissolution rate. The product is dissolved by using chloroform and no pyridine monomer structural unit is found by HPLC detection, which indicates that the dissolution rate is less than 0.1%.

2. According to the invention, the pyridine quaternary ammonium salt antibacterial structural unit is introduced, and the terminal amino structure is introduced, so that the antibacterial effect is greatly improved, and the bonding effect is favorably improved.

3. the invention can accurately adjust the proportion of the antibacterial unit by controlling the proportion of the 3-halopropylamine, and the material can be independently used as an antibacterial material and also can be used as an antibacterial agent to be added into other high polymer materials.

Drawings

FIG. 1 is a DSC spectrum of polyaryletherketone product obtained in example 1.

The specific implementation mode is as follows:

in order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

Example 1

in a three-neck flask with mechanical stirring, 15mL of dichloromethane and PPEK-P (5mmol,3.03g) are sequentially added under the protection of nitrogen, then sodium hydroxide (2.5mmol,0.10g) and 3-chloropropylamine (0.5mmol,0.047g) are added, the temperature of the reaction system is controlled to be 20-25 ℃, and the reaction is carried out for 6 h; after the reaction is finished, precipitating the reaction solution into ethanol, filtering and collecting a filter cake; and boiling the precipitate in boiling water, filtering for several times, collecting filter cake, and drying to obtain white polyaryletherketone product with quaternary ammonium salt content of 5%. The DSC of the product is shown in figure 1, the glass transition temperature of about 265 ℃ can be seen from the DSC spectrogram, the material has higher temperature resistance, and the bacteriostatic effect of the product is shown in Table 1.

TABLE 1

Example 2

Sequentially adding PPEK-P (5mmol,3.03g), potassium hydroxide (15mmol,0.84g) and 3-bromopropylamine (10mmol,1.38g) into a three-neck flask provided with a mechanical stirring and refluxing device under the protection of nitrogen, then adding 60mL of chloroform as a solvent, heating to 50-55 ℃ and reacting for 3 h; after the reaction is finished, precipitating the reaction solution into methanol, filtering and collecting a filter cake; and boiling the precipitate in boiling water, filtering for several times, collecting filter cake, and drying to obtain white polyaryletherketone product with quaternary ammonium salt content of 100%. The bacteriostatic effect of the product is shown in table 2.

TABLE 2

Example 3

Sequentially adding PPEK-P (5mmol,3.03g), sodium carbonate (5mmol, 0.53g) and 3-chloropropylamine (5mmol, 0.47g) into a three-neck flask provided with a mechanical stirrer, a thermometer and a condenser, adding 30ml of dichloroethane as a solvent, controlling the reaction system to 75-80 ℃ and reacting for 1 h; after the reaction is finished, precipitating the reaction solution into isopropanol, filtering and collecting a filter cake; and boiling the precipitate in boiling water, filtering for several times, collecting filter cake, and drying to obtain white polyaryletherketone product with quaternary ammonium salt content of 50%. The bacteriostatic effect of the product is shown in table 3.

TABLE 3

Example 4

Sequentially adding PPEK-P (5mmol,3.03g), potassium carbonate (10mmol,1.36g) and 3-bromopropylamine (2.5mmol,0.35g) into a three-neck flask with a mechanical stirrer, a thermometer and a condenser, adding 21mL of N, N' -dimethylformamide as a solvent, and controlling the reaction system to react at 70-75 ℃ for 2 hours; after the reaction is finished, precipitating the reaction solution into water, filtering and collecting a filter cake; and boiling the precipitate in boiling water, filtering for several times, collecting filter cake, and drying to obtain white polyaryletherketone product. The proportion of quaternary ammonium salt is 25 percent. The bacteriostatic effect of the product is shown in table 4.

TABLE 4

Example 5

Sequentially adding PPEK-P (5mmol,3.03g), sodium hydroxide (12.5mmol,0.50g) and 3-bromopropylamine (7.5mmol,1.04g) into a three-neck flask provided with a mechanical stirrer, a thermometer and a condenser, adding 15mL of N, N' -dimethylacetamide serving as a solvent, and controlling the reaction system to react for 4 hours at the temperature of 40-45 ℃; after the reaction is finished, precipitating the reaction solution into methanol, filtering and collecting a filter cake; and boiling the precipitate in boiling water, filtering for several times, collecting filter cake, and drying to obtain white polyaryletherketone product with quaternary ammonium salt content of 75%. The bacteriostatic effect of the product is shown in table 5.

TABLE 5

Claims

1. a polyether-ether-ketone material with antibacterial property is characterized in that: introducing a pyridine quaternary ammonium salt-containing antibacterial structural unit into a main chain of polyaryletherketone, wherein the structure is as follows:

Wherein: x ═ Cl, Br, I.

2. A method of preparing a polyetheretherketone material according to claim 1, comprising the operations of:

Mixing an organic solvent, PPEK-P, an inorganic base and 3-halopropylamine, and reacting at 20-80 ℃; after the reaction is finished, pouring the reaction liquid into a precipitator; filtering, separating, cleaning and drying to obtain the antibacterial polyaryletherketone with the pyridine quaternary ammonium salt structure; the PPEK-P is polyaryletherketone containing naphthyridine and pyridine structures, the main chain of the PPEK-P has a repeating unit and contains the polyaryletherketone containing the naphthyridine and the pyridine structures, and the number average molecular weight is 12000-30000; the structural formula is as follows:

Wherein the number of repeating structural units is 20-50.

3. The method of claim 2, wherein the polyether ether ketone material comprises: the organic solvent is selected from chloroform, dichloromethane, dichloroethane, N '-dimethylformamide or N, N' -dimethylacetamide.

4. The method of claim 2, wherein the polyether ether ketone material comprises: the alkali is selected from sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate.

5. The method of claim 2, wherein the polyether ether ketone material comprises: the mass-volume ratio of the PPEK-P to the solvent is 1 g: 5-20 mL; the molar ratio of PPEK-P, inorganic base and 3-halogenated propylamine is 1: 0.5-3: 0.1-2.

6. The method of claim 2, wherein the polyether ether ketone material comprises: the 3-halopropylamine is selected from 3-chloropropylamine, 3-bromopropylamine or 3-iodopropylamine.

7. The method of claim 2, wherein the polyether ether ketone material comprises: the precipitant is selected from methanol, ethanol, isopropanol or water.