CN107814933A - The Preparation method and use of conjugation microporous polymer with bacteriostatic activity - Google Patents
The Preparation method and use of conjugation microporous polymer with bacteriostatic activity Download PDFInfo
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- CN107814933A CN107814933A CN201711173238.4A CN201711173238A CN107814933A CN 107814933 A CN107814933 A CN 107814933A CN 201711173238 A CN201711173238 A CN 201711173238A CN 107814933 A CN107814933 A CN 107814933A
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- microporous polymer
- bacteriostatic activity
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- conjugation microporous
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0616—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aliphatically bound aldehyde or keto groups, or thio analogues thereof; Derivatives thereof, e.g. acetals
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- Agronomy & Crop Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
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Abstract
The Preparation method and use of conjugation microporous polymer with bacteriostatic activity, it is the step of its method：According to 1,3 dibromos 5,5 dimethyl hydantoins and 1,3, the mol ratio 1 ~ 10 of 5 three ethynylbenzenes or Isosorbide-5-Nitrae diacetylene-benzene mixes, and is solvent Pd (0) and CuI for catalyst using toluene and triethylamine, polymerase 17 2 hours at 80 DEG C, obtain the conjugation microporous polymer with good bacteriostatic activity.Its purposes is is made on nanoporous foam, or the surface coated on porous substrate, as effective antiseptic in water.
Description
Technical field
The present invention relates to the technology of preparing of antiseptic.
Background technology
Since cooper seminars in 2007 for the first time report conjugation microporous polymer, microporous polymer CMPs has been conjugated
（Conjugated Microporous Polymers）Because of its higher physical and chemical stability（In all organic solvents all
It is insoluble, thermogravimetric analysis（TGA）Show that CMPs decomposition temperature is more than 300 DEG C）, big BET specific surface area（Up to the present
Its BET specific surface area is up to 6461 m2 g-1）.So that its it is many such as, gas storage and conversion, catalysis, electrode material,
There is good application potential in the fields such as light capture, ultracapacitor.
In traditional bactericidal agent, chlorine, chlorine dioxide and ozone gas are maximally effective bactericide, can be killed most of
Microorganism, but it is poisonous under these gas normal-temperatures, and potential hazard be present to operating personnel, which limits its application.Cause
This, the research and development of efficient water bactericidal agent are still a major challenge of field of public health.
The content of the invention
It is an object of the invention to provide a kind of Preparation method and use of the conjugation microporous polymer with bacteriostatic activity.
The present invention is the Preparation method and use of the conjugation microporous polymer with bacteriostatic activity, is the step of its method：
It is mixed according to the mol ratio 1 ~ 10 of the bromo- 5,5- dimethyl hydantoins of 1,3- bis- and the ethynylbenzenes of 1,3,5- tri- or 1,4- diacetylene-benzenes
Close, be solvent Pd (0) and CuI for catalyst using toluene and triethylamine, polymerase 17 2 hours at 80 DEG C, obtain with well antibacterial
The conjugation microporous polymer of activity.
The purposes of conjugation microporous polymer described above with bacteriostatic activity, its purposes is that nanoporous foam is made,
Or on the surface coated on porous substrate, as effective antiseptic in water.
Usefulness of the present invention is：The compound or polymer of halogen amine groups have more than single halogen amines
With application value, the more Portable safety in water body application.
Brief description of the drawings
Fig. 1 is the synthesis step that hydantoin-containing is conjugated microporous polymer, and Fig. 2 is Escherichia coli growth completely and three kinds
Inhibitor（DMH, CMPH-1 and CMPH-2）Under OD value curves, and three kinds of inhibitor（DMH, CMPH-1 and CMPH-2）To large intestine
The inhibition of bacillus, Fig. 3 are bacterium colony photo of the Escherichia coli grown completely in solid medium, and Fig. 4 is that DMH is suppression
During agent, bacterium colony photo of the Escherichia coli in solid medium, Fig. 5 is CMPH-1 when being inhibitor, and Escherichia coli are trained in solid
The bacterium colony photo in base is supported, Fig. 6 is CMPH-2 when being inhibitor, bacterium colony photo of the Escherichia coli in solid medium, and Fig. 7 is
Gold-coloured staphylococci growth and three kinds of inhibitor completely（DMH, CMPH-1 and CMPH-2）Under OD value curves, and three kinds suppression
Agent（DMH, CMPH-1 and CMPH-2）To the inhibition of gold-coloured staphylococci, Fig. 8 is that the gold-coloured staphylococci grown completely exists
Bacterium colony photo in solid medium, Fig. 9 is DMH when being inhibitor, and bacterium colony of the gold-coloured staphylococci in solid medium shines
Piece, Figure 10 is CMPH-1 when being inhibitor, and bacterium colony photo of the gold-coloured staphylococci in solid medium, Figure 11 is that CMPH-2 is
During inhibitor, bacterium colony photo of the gold-coloured staphylococci in solid medium, Figure 12 is that hydantoin-containing is conjugated into microporous polymer
The picture being applied to after thing machine-shaping in water body, Figure 13 are that hydantoin-containing conjugation microporous polymer is coated on into porous material
The picture on surface.
Embodiment
Hydantoins can be as the precursor compound of synthesis bacteriostatic agent, because the characteristic of its own has been widely used.
The present invention is the suppression that will be conjugated microporous polymer applied to strain in water body, with alkynyl benzene and bromo hydantoins
It is solvent Pd (0) and CuI for catalyst using toluene and triethylamine, the conjugation micropore with bacteriostasis of synthesis gathers for monomer
Compound, then it is applied to the suppression of gram-positive bacteria and gram-positive bacteria.
As shown in figure 1, the preparation method of the conjugation microporous polymer with bacteriostatic activity of the present invention, its step are：Press
It is mixed according to the mol ratio 1 ~ 10 of the bromo- 5,5- dimethyl hydantoins of 1,3- bis- and the ethynylbenzenes of 1,3,5- tri- or 1,4- diacetylene-benzenes
Close, be solvent Pd (0) and CuI for catalyst using toluene and triethylamine, polymerase 17 2 hours at 80 DEG C, obtain with well antibacterial
The conjugation microporous polymer of activity.
The purposes of conjugation microporous polymer described above with bacteriostatic activity, its purposes is that nanoporous foam is made,
Or on the surface coated on porous substrate, as effective antiseptic in water.
Above-described porous substrate is filter paper, cloth, sponge.
The purposes of the above-described conjugation microporous polymer with bacteriostatic activity, it is conjugated the dispersion concentration of microporous polymer
For 100 μ g mL-1When contacted with Escherichia coli in water body 120 minutes and can completely inhibit its growth.
Embodiment 1：Weigh the bromo- 5,5- dimethyl hydantoins of 1,3- bis-（1.8472 g）, 1,3,5- tri- acetylenylbenzene
（0.6007 g）, four（Triphenylphosphine）Palladium（0）（100 mg）, cuprous iodide（40 mg）It is placed in 50 mL there-necked flasks, N2Degassing
20 minutes；Measure toluene, triethylamine each 7.5 mL, N2Protection is lower to be added in there-necked flask, persistently leads to N210 minutes；After degassing
Oil bath pot temperature is slowly increased to 80 DEG C, back flow reaction 72 hours under lucifuge, as shown in Figure 1.After reaction terminates, by reactant
Be that temperature naturally cools to room temperature, crude product washed for several times until cleaning solution with chloroform, acetone, water, methanol successively
Clarification, product methanol soxhlet type 72 hours after washing；The product obtained after soxhlet type is placed in 70 in air dry oven
DEG C dry 24 hours, be named as CMPH-1.
The conjugation microporous polymer of gained is prepared in accordance with the above, is applied to antibacterial：
（1）The conjugation microporous polymer of same concentrations is scattered in the strain for suppressing different in water body, CMPH-1 is to Escherichia coli
Inhibition is optimal；
（2）By changing time of contact and polymer dispersion concentration, when the dispersion concentration of conjugation microporous polymer is 100 μ g
mL-1CMPH-1 contacted with Escherichia coli 60 minutes and can completely inhibit its growth.
Embodiment 2：Weigh the bromo- 5,5- dimethyl hydantoins of 1,3- bis-（1.8472 g）, Isosorbide-5-Nitrae-diacetylene-benzene
（0.7569 g）, four（Triphenylphosphine）Palladium（0）（100 mg）, cuprous iodide（40 mg）It is placed in 50 mL there-necked flasks, N2Degassing
20 minutes；Measure toluene, triethylamine each 7.5 mL, N2Protection is lower to be added in there-necked flask, persistently leads to N210 minutes；After degassing
Oil bath pot temperature is slowly increased to 80 DEG C, back flow reaction 72 hours under lucifuge, as shown in Figure 1.After reaction terminates, by reactant
Be that temperature naturally cools to room temperature, crude product washed for several times until cleaning solution with chloroform, acetone, water, methanol successively
Clarification, product methanol soxhlet type 72 hours after washing；The product obtained after soxhlet type is placed in 70 in air dry oven
DEG C dry 24 hours, be named as CMPH-2.
Embodiment 3：5.0 mg DMH, CMPH-1 and CMPH-2 is weighed, is scattered in 10 mL ultra-pure waters, is added dense
Spend for 106-7The CFU/L μ L of Escherichia coli 10, are contacted 60 minutes under preference temperature, pipette the μ L of mixed liquor 50 in culture medium
In, cultivated 12 hours under preference temperature, survey absorbance with ultraviolet specrophotometer, wavelength is that 600 nm absorbance is bacterium
Stand density, as shown in Fig. 2 find CMPH-1 it is antibacterial after the minimum therefore corresponding antibacterial efficiency highest of stand density.
And mixed liquor is coated in solid medium and cultivated 24 hours, bacterium colony number is counted, as shown in figure 5, CMPH-1 can press down completely
The growth of Escherichia coli processed.
Embodiment 4：5.0 mg DMH, CMPH-1 and CMPH-2 is weighed, is scattered in 10 mL ultra-pure waters, is added dense
Spend for 106-7The CFU/L μ L of gold-coloured staphylococci 10, are contacted 60 minutes under preference temperature, pipette the μ L of mixed liquor 50 in culture
In base, cultivated 12 hours under preference temperature, survey absorbance with ultraviolet specrophotometer, wavelength is that 600 nm absorbance is as thin
The stand density of bacterium, as shown in fig. 7, find CMPH-1 it is antibacterial after the minimum therefore corresponding antibacterial efficiency of stand density most
It is high.And mixed liquor is coated in solid medium and cultivated 24 hours, as shown in Figure 10, bacterium colony number is counted, by itself and gold
The clump count that staphylococcus grows completely（As shown in Figure 8）Contrast, calculates antibacterial efficiency.
Claims (4)
1. the preparation method of the conjugation microporous polymer with bacteriostatic activity, it is characterised in that its step is：According to 1,3- bis-
The mol ratio 1 ~ 10 of bromo- 5,5- dimethyl hydantoins and 1,3,5- tri- ethynylbenzenes or Isosorbide-5-Nitrae-diacetylene-benzene mixes, with toluene
It is that solvent Pd (0) and CuI is catalyst with triethylamine, polymerase 17 2 hours at 80 DEG C, obtains that there is being total to for good bacteriostatic activity
Yoke microporous polymer.
2. the purposes of the conjugation microporous polymer with bacteriostatic activity, its purposes are more for nanometer is made according to claim 1
On hole foam, or the surface coated on porous substrate, as effective antiseptic in water.
3. the purposes of the conjugation microporous polymer with bacteriostatic activity according to claim 2, it is characterised in that porous substrate
For filter paper, cloth, sponge.
4. the purposes of the conjugation microporous polymer according to claim 2 with bacteriostatic activity, it is characterised in that conjugation is micro-
The dispersion concentration of pore polymer is 100 μ g mL-1When contacted with Escherichia coli in water body 120 minutes and can completely inhibit its life
It is long.
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| CN201711173238.4A CN107814933A (en) | 2017-11-22 | 2017-11-22 | The Preparation method and use of conjugation microporous polymer with bacteriostatic activity |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108530610A (en) * | 2018-04-27 | 2018-09-14 | 兰州理工大学 | Conjugation microporous polymer and preparation method thereof with thermal insulation and anti-flammability |
| CN109535393A (en) * | 2018-11-15 | 2019-03-29 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation method and products thereof of micropore organic polymer nanosphere |
| CN110140718A (en) * | 2019-05-31 | 2019-08-20 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of nano silver/microporous polymer composite bactericidal liquid |
| CN112920382A (en) * | 2021-01-29 | 2021-06-08 | 齐齐哈尔大学 | In-situ method for preparing conjugated microporous polymer TiO2Method for compounding nano antibacterial agent |
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| DE3532325A1 (en) * | 1985-09-11 | 1987-03-19 | Gaedke Fuhrmann Elke M | Preparation of paints having a biocidal action |
| CN107151313A (en) * | 2017-06-08 | 2017-09-12 | 吉林师范大学 | A kind of organic microporous polymer of nitrogenous conjugation, preparation method and application |
-
2017
- 2017-11-22 CN CN201711173238.4A patent/CN107814933A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3532325A1 (en) * | 1985-09-11 | 1987-03-19 | Gaedke Fuhrmann Elke M | Preparation of paints having a biocidal action |
| CN107151313A (en) * | 2017-06-08 | 2017-09-12 | 吉林师范大学 | A kind of organic microporous polymer of nitrogenous conjugation, preparation method and application |
Non-Patent Citations (2)
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| FEI WANG等: ""Hierarchical porous spherical-shaped conjugated microporous polymers for the efficient removal of antibiotics from water"", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| 徐章煌等: ""1,3-二溴-5,5-二甲基乙内酰脲的合成"", 《化学试剂》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108530610A (en) * | 2018-04-27 | 2018-09-14 | 兰州理工大学 | Conjugation microporous polymer and preparation method thereof with thermal insulation and anti-flammability |
| CN109535393A (en) * | 2018-11-15 | 2019-03-29 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation method and products thereof of micropore organic polymer nanosphere |
| CN109535393B (en) * | 2018-11-15 | 2021-03-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of microporous organic polymer nano-microspheres and product thereof |
| CN110140718A (en) * | 2019-05-31 | 2019-08-20 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of nano silver/microporous polymer composite bactericidal liquid |
| CN112920382A (en) * | 2021-01-29 | 2021-06-08 | 齐齐哈尔大学 | In-situ method for preparing conjugated microporous polymer TiO2Method for compounding nano antibacterial agent |
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