CN108359089B - Antibacterial polyaryletherketone material and preparation method thereof - Google Patents
Antibacterial polyaryletherketone material and preparation method thereof Download PDFInfo
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- CN108359089B CN108359089B CN201810028862.3A CN201810028862A CN108359089B CN 108359089 B CN108359089 B CN 108359089B CN 201810028862 A CN201810028862 A CN 201810028862A CN 108359089 B CN108359089 B CN 108359089B
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 27
- 229920006260 polyaryletherketone Polymers 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 pyridine quaternary ammonium salt Chemical class 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 8
- 229920002530 polyetherether ketone Polymers 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- FLBAYUMRQUHISI-UHFFFAOYSA-N 1,8-naphthyridine Chemical compound N1=CC=CC2=CC=CN=C21 FLBAYUMRQUHISI-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- ZTGQZSKPSJUEBU-UHFFFAOYSA-N 3-bromopropan-1-amine Chemical compound NCCCBr ZTGQZSKPSJUEBU-UHFFFAOYSA-N 0.000 claims description 5
- BZFKSWOGZQMOMO-UHFFFAOYSA-N 3-chloropropan-1-amine Chemical group NCCCCl BZFKSWOGZQMOMO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- 150000007529 inorganic bases Chemical class 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- FZSUKGFWZOUEJF-UHFFFAOYSA-N 3-iodopropan-1-amine Chemical compound NCCCI FZSUKGFWZOUEJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical class CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 abstract description 7
- 238000004090 dissolution Methods 0.000 abstract description 5
- 239000003242 anti bacterial agent Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 14
- 238000009835 boiling Methods 0.000 description 10
- 239000012065 filter cake Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- 230000003385 bacteriostatic effect Effects 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 5
- 241000282414 Homo sapiens Species 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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
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 (7)
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.
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| CN111925518B (en) * | 2020-08-12 | 2022-06-10 | 大连九信精细化工有限公司 | Polyaryletherketone polymer containing straight-chain siloxane structure, preparation method and application |
| CN114316241A (en) * | 2021-11-30 | 2022-04-12 | 山东一诺威新材料有限公司 | Preparation method of polyether polyol for antibacterial polyurethane slow-resilience foam |
| CN114479064B (en) * | 2022-02-11 | 2024-01-02 | 吉林省登泰克牙科材料有限公司 | Antibacterial polyaryletherketone night-grinding tooth jaw pad and preparation method thereof |
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| CN101328275A (en) * | 2007-06-24 | 2008-12-24 | 山东理工大学 | Application of Pyridine Quaternary Ammonium Salt Basic or Weak Basic Polymer Membranes |
| CN102924898A (en) * | 2008-10-31 | 2013-02-13 | 重庆澳瑞玛高性能聚合物有限公司 | Polyacryletherone composition, compositions, molded product and preparation thereof |
| CN105694077A (en) * | 2016-01-20 | 2016-06-22 | 中国科学院宁波材料技术与工程研究所 | Anion exchange membrane containing pyridine skeleton as well as preparation method and application of anion exchange membrane |
| CN107501490A (en) * | 2017-08-17 | 2017-12-22 | 四川金和成科技有限公司 | A kind of preparation method of the polyether-ether-ketone of the pyridine structure containing phthalazone |
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2018
- 2018-01-11 CN CN201810028862.3A patent/CN108359089B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO1999048932A2 (en) * | 1998-03-27 | 1999-09-30 | Universität Stuttgart - Institut für Chemische Verfahrenstechnik | Modified polymer and modified polymer membrane |
| CN101328275A (en) * | 2007-06-24 | 2008-12-24 | 山东理工大学 | Application of Pyridine Quaternary Ammonium Salt Basic or Weak Basic Polymer Membranes |
| CN102924898A (en) * | 2008-10-31 | 2013-02-13 | 重庆澳瑞玛高性能聚合物有限公司 | Polyacryletherone composition, compositions, molded product and preparation thereof |
| CN105694077A (en) * | 2016-01-20 | 2016-06-22 | 中国科学院宁波材料技术与工程研究所 | Anion exchange membrane containing pyridine skeleton as well as preparation method and application of anion exchange membrane |
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