CN113896877A - Main chain type ionic liquid crystal polymer based on quaternary phosphine ions, preparation method thereof and application thereof in antibiosis - Google Patents
Main chain type ionic liquid crystal polymer based on quaternary phosphine ions, preparation method thereof and application thereof in antibiosis Download PDFInfo
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- 239000004992 Ionic Liquid Crystal Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- -1 phosphine ions Chemical class 0.000 title claims abstract description 38
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 34
- 230000003115 biocidal effect Effects 0.000 title abstract description 4
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 35
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims abstract description 32
- JIFATMSCIHKDCF-UHFFFAOYSA-N 2,3-dibromobutanedioyl dichloride Chemical compound ClC(=O)C(Br)C(Br)C(Cl)=O JIFATMSCIHKDCF-UHFFFAOYSA-N 0.000 claims abstract description 22
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 21
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 12
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims abstract description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 26
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
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- 238000010438 heat treatment Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 9
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- FJWGRXKOBIVTFA-UHFFFAOYSA-N 2,3-dibromobutanedioic acid Chemical compound OC(=O)C(Br)C(Br)C(O)=O FJWGRXKOBIVTFA-UHFFFAOYSA-N 0.000 claims description 5
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
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- 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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/26—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-nitrogen bonds
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- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
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Abstract
The invention relates to a main chain type ionic liquid crystal polymer based on quaternary phosphine ions, a preparation method thereof and application thereof in antibiosis. The preparation method comprises the steps of taking D-camphoryl chloride, 2, 3-dibromosuccinyl chloride, terephthaloyl chloride and hydroquinone as raw materials, firstly synthesizing a main chain type liquid crystal polymer by adopting a condensation polymerization method, and then grafting triphenylphosphine to further obtain a main chain type ionic liquid crystal polymer containing quaternary phosphine ions. The invention combines the oriented ordered structure characteristic of the liquid crystal polymer with the antibacterial performance of triphenylphosphine to successfully prepare the novel intelligent temperature-control antibacterial material. The antibacterial performance of the ionic liquid crystal polymer is regulated and controlled by adjusting the molecular structure, and a new thought is provided for the functionalization and application of the ionic liquid crystal polymer.
Description
Technical Field
The invention relates to the field of ionic liquid crystal polymers, in particular to a main chain type ionic liquid crystal polymer containing quaternary phosphine ions, a preparation method thereof and application thereof in the antibacterial field.
Background
Microbial contamination is closely related to human health, such as: the presence of harmful microorganisms in dental equipment, food packaging and storage, water purification systems, and home hygiene areas can cause various infections and diseases in humans. Active disinfectants such as hypochlorite, hydrogen peroxide, quaternary ammonium compounds, silver salts, etc. have been tried to keep these areas free from contamination, but have the disadvantages of short action time and poor environmental safety. Therefore, macromolecular antibacterial agents (antibacterial polymers) with long-acting antibacterial effects gradually enter the sight of people, have the capability of killing or inhibiting the growth of microorganisms on the surface of materials and in the surrounding environment, are superior to small-molecular organic antibacterial agents in the aspects of reducing toxicity, reducing environmental problems, prolonging service life and the like, and become hot spots of research in recent years.
The antibacterial polymer is mainly classified into an antibacterial polymer having antibacterial activity by itself, an antibacterial polymer chemically modified to induce antibacterial activity, and the like. The polymers chemically modified to induce antibacterial activity mean that the polymers themselves have little antibacterial activity, but they induce antibacterial activity by attaching active groups or compounds. The quaternary ammonium salt active group has good antibacterial performance, the antibacterial polymer containing the quaternary phosphonium salt antibacterial active group has a similar antibacterial mechanism with the quaternary ammonium salt compound, but structurally, the phosphine atom of the quaternary phosphonium salt is larger than the ionic radius of the nitrogen atom of the quaternary ammonium salt, the polarization effect is strong, the quaternary phosphonium salt can easily adsorb thallus with negative charge, and meanwhile, because the phosphine element is positioned below the nitrogen element in the periodic table of elements, the electronegativity is relatively weak, the antibacterial activity of the quaternary phosphonium salt is stronger than that of the quaternary ammonium salt polymer.
The study of quaternary phosphonium salt antibacterial agents is still in the beginning, but their excellent properties are attracting more and more researchers. Based on the advantages of the antibacterial polymer, people strive to apply the antibacterial polymer to the contact surface of medical equipment, fibers and textiles to endow the contact surface with antibacterial property, and the modification enables the antibacterial polymer to be widely applied to various fields and provides great opportunity for scientific research, so that the realization of the antibacterial material which is nontoxic, intelligent, strong in antibacterial activity, wide in range and even reusable is very important.
Disclosure of Invention
In order to solve the problems, the invention provides a main chain type ionic liquid crystal polymer with antibacterial performance, and the antibacterial performance of quaternary phosphine ions is perfectly combined with the advantages of high strength, high modulus, easy orientation and the like of liquid crystal macromolecules. Provides theoretical and practical materials for preparing novel antibacterial materials.
The invention takes D-camphoryl chloride, 2, 3-dibromo-succinyl chloride, p-phthaloyl chloride and hydroquinone as raw materials, firstly synthesizes a main chain type liquid crystal polymer by adopting a condensation polymerization method, and then further obtains the main chain type ionic liquid crystal polymer containing quaternary phosphine ions by grafting triphenylphosphine.
The technical scheme adopted by the invention is as follows: a quaternary phosphine ion based main chain type ionic liquid crystal polymer having a structural formula shown as (I):
wherein x + y + z is 1, m is 1, n is 107-112, x/(x + y) is 0.1-0.5, and z/(x + y + z) is 0.5.
A preparation method of a main chain type ionic liquid crystal polymer based on quaternary phosphine ions comprises the following steps:
1) dissolving D-camphoryl chloride, 2, 3-dibromosuccinyl chloride, terephthaloyl chloride and hydroquinone in a proper amount of tetrahydrofuran and pyridine mixed solution, stirring at room temperature for 1h under the protection of nitrogen, heating to 66 ℃, continuing to react for 20h, after the reaction is finished, carrying out reduced pressure distillation to remove the solvent, adjusting the pH value of the obtained product to 4, and then washing the product with deionized water to obtain a main chain type liquid crystal polymer;
2) dissolving the main chain type liquid crystal polymer and triphenylphosphine in toluene, stirring at room temperature for 30min, heating to reflux, continuing to react for 10h, standing for layering after the reaction is finished, taking a lower-layer product, washing with deionized water and petroleum ether in sequence, and performing rotary evaporation to obtain the main chain type ionic liquid crystal polymer.
Further, in the above preparation method, step 1), the preparation method of D-camphoryl chloride comprises the following steps: taking D-camphoric acid, thionyl chloride and N, N-dimethylformamide, reacting for 8 hours at 60 ℃, heating to 80 ℃, and distilling under reduced pressure to obtain D-camphoryl chloride.
Furthermore, the preparation method comprises the step of mixing D-camphoric acid and thionyl chloride in a molar ratio of 1: 4-5.
Further, in the above preparation method, step 1), the preparation method of 2, 3-dibromosuccinyl chloride comprises the following steps: taking 2, 3-dibromo succinic acid, thionyl chloride and N, N-dimethylformamide to react for 8 hours at the temperature of 60 ℃, heating to 80 ℃, and carrying out reduced pressure distillation to obtain 2, 3-dibromo succinyl chloride.
Furthermore, the preparation method comprises the following step of 1: 4-5 mol ratio of 2, 3-dibromo-succinic acid and thionyl chloride.
Further, in the above preparation method, in the step 1), the molar ratio of the D-camphoryl chloride to the 2, 3-dibromosuccinyl chloride to the terephthaloyl chloride to the hydroquinone is (9-5) to (1-5) to (10-20).
Further, in the above preparation method, in step 1), the volume ratio of the tetrahydrofuran to the pyridine is 20: 1.
The invention provides an application of a main chain type ionic liquid crystal polymer based on quaternary phosphine ions in antibiosis.
Compared with the prior art, the invention has the following remarkable advantages:
according to the invention, the liquid crystal characteristics of the ionic liquid crystal polymer, namely the orientation change of the molecular arrangement of liquid crystal elements inside and outside a liquid crystal interval are utilized to explore the change of the liquid crystal molecular structure, the synergistic antibacterial action of the liquid crystal orientation structure and quaternary phosphonium salt ions is mainly researched, and the antibacterial performance is regulated and controlled by adjusting the chemical structure of the ionic liquid crystal polymer. Successfully prepares the main chain type ionic liquid crystal polymer with green, low toxicity and high efficiency and antibacterial property.
Drawings
FIG. 1 is an infrared image of a main chain type liquid crystal polymer and a main chain type ionic liquid crystal polymer prepared in example 1.
FIG. 2 is a nuclear magnetic diagram of a main chain type liquid crystalline polymer prepared in example 1.
FIG. 3 is a nuclear magnetic diagram of a main chain type ionic liquid crystal polymer prepared in example 1.
FIG. 4 is an XRD pattern of a main chain type liquid crystalline polymer prepared in example 1.
FIG. 5 is an XRD pattern of a main chain type ionic liquid crystal polymer prepared in example 1.
FIG. 6 is a DSC of main chain type liquid crystalline polymers prepared in examples 1-5.
FIG. 7 is a DSC of main chain ionic liquid crystal polymers prepared in examples 1-5.
FIG. 8 is a schematic view of the main chain type ionic liquid crystal polymer antibacterial process of the present invention.
FIG. 9 is a graph of the antibacterial properties of main chain type ionic liquid crystal polymers prepared in examples 1-5.
Detailed Description
In order that the invention may be better understood, the invention is further illustrated by the following examples, which are to be construed as being better understood and not as imposing any limitation on the scope thereof.
The synthetic route of the main chain type ionic liquid crystal polymer is as follows:
example 1 preparation of a quaternary phosphine ion based main chain ionic liquid crystalline polymer (I) comprising the following steps:
1) preparation of D-camphoryl chloride: 20.02g (0.10mol) of D-camphoric acid, 32.85mL (0.45mol) of thionyl chloride and 2mL of DMF (N, N-dimethylformamide) are sequentially added into a 250mL three-neck flask provided with a magnetic stirrer, a spherical condenser and a thermometer, the mixture is heated to 60 ℃ after reacting for 1h at room temperature, the reaction is continued for 8h, the temperature is raised to 80 ℃ for reduced pressure distillation, and excessive thionyl chloride is removed to obtain a white solid, namely D-camphoryl chloride.
2) Preparation of 2, 3-dibromosuccinyl chloride: 27.58g (0.10mol) of 2, 3-dibromo-succinic acid, 32.85mL (0.45mol) of thionyl chloride and 2mL of DMF (dimethyl formamide) are sequentially added into a 250mL three-neck flask provided with a magnetic stirrer, a spherical condenser and a thermometer, after the reaction is carried out for 1h at room temperature, the temperature is heated to 60 ℃, the reaction is continued for 8h, the temperature is increased to 80 ℃, the reduced pressure distillation is carried out, the excessive thionyl chloride is removed, and an orange-red solid, namely the 2, 3-dibromosuccinyl chloride, is obtained.
3) Preparation of main chain type liquid crystalline polymer: 0.09mol of D-camphoryl chloride, 0.01mol of 2, 3-dibromosuccinyl chloride, 0.1mol of terephthaloyl chloride and 0.2mol of hydroquinone are poured into a three-neck flask provided with a magnetic stirring bar, a spherical condenser tube and a thermometer in sequence, and dissolved by 200mL of tetrahydrofuran and pyridine mixed solution (volume ratio is 20: 1). And stirring for 1 hour at room temperature under the protection of nitrogen, heating to 66 ℃, continuing to react for 20 hours, after the reaction is finished, distilling under reduced pressure to remove the solvent, adjusting the pH of the obtained product to 4 by using dilute sulfuric acid, then washing the product for multiple times by using a large amount of deionized water to obtain a white solid, namely a main chain type liquid crystal polymer, marking as a main chain type liquid crystal polymer 1, and placing the main chain type liquid crystal polymer in a vacuum drying oven for later use.
4) Preparation of main chain type ionic liquid crystal polymer: dissolving the main chain type liquid crystal polymer 1 obtained in the step 3) and excessive triphenylphosphine in 80mL toluene in a three-neck flask provided with a magnetic stirrer, a spherical condenser tube and a thermometer, stirring at room temperature for 30min, and heating to reflux for reaction for 10 h. And after the reaction is finished, standing and layering, wherein the upper layer of the solution is a toluene solvent layer, and the lower layer of the solution is a target product layer which is light yellow. And (3) taking the lower product layer, dissolving the lower product layer by using 20mL of deionized water, washing the unreacted raw materials by using petroleum ether, and removing water by rotary evaporation to obtain a target product, namely the main chain type ionic liquid crystal polymer 1.
Example 2 preparation of quaternary phosphonium ion based main chain type ionic liquid crystalline polymer (i) the process comprises the following steps:
1) preparation of D-camphoryl chloride: same as example 1
2) Preparation of 2, 3-dibromosuccinyl chloride: same as example 1
3) Preparation of main chain type liquid crystalline polymer: 0.08mol of D-camphoryl chloride, 0.02mol of 2, 3-dibromosuccinyl chloride, 0.1mol of terephthaloyl chloride and 0.2mol of hydroquinone are poured into a three-neck flask provided with a magnetic stirring bar, a spherical condenser tube and a thermometer in sequence, and are dissolved by 200mL of tetrahydrofuran and pyridine mixed solution (the volume ratio is 20: 1). And stirring for 1 hour at room temperature under the protection of nitrogen, heating to 66 ℃, continuing to react for 20 hours, after the reaction is finished, distilling under reduced pressure to remove the solvent, adjusting the pH of the obtained product to 4 by using dilute sulfuric acid, then washing the product for multiple times by using a large amount of deionized water to obtain a white solid, namely a main chain type liquid crystal polymer, which is marked as a main chain type liquid crystal polymer 2, and placing the main chain type liquid crystal polymer in a vacuum drying oven for later use.
4) Preparation of main chain type ionic liquid crystal polymer: dissolving the main chain type liquid crystal polymer 2 obtained in the step 3) and excessive triphenylphosphine in 80mL toluene in a three-neck flask provided with a magnetic stirrer, a spherical condenser tube and a thermometer, stirring for 30min at room temperature, and heating to reflux for reaction for 10 h. And after the reaction is finished, standing and layering, wherein the upper layer of the solution is a toluene solvent layer, and the lower layer of the solution is a target product layer which is light yellow. And (3) taking the lower product layer, dissolving the lower product layer by using 20mL of deionized water, washing the unreacted raw materials by using petroleum ether, and removing water by rotary evaporation to obtain a target product, namely the main chain type ionic liquid crystal polymer, which is marked as a main chain type ionic liquid crystal polymer 2.
Example 3 preparation of a quaternary phosphine ion based main chain ionic liquid crystalline polymer (I) comprising the following steps:
1) preparation of D-camphoryl chloride: same as example 1
2) Preparation of 2, 3-dibromosuccinyl chloride: same as example 1
3) Preparation of main chain type liquid crystalline polymer: 0.07mol of D-camphoryl chloride, 0.03mol of 2, 3-dibromosuccinyl chloride, 0.1mol of terephthaloyl chloride and 0.2mol of hydroquinone are poured into a three-neck flask provided with a magnetic stirring bar, a spherical condenser tube and a thermometer in sequence, and dissolved by 200mL of tetrahydrofuran and pyridine mixed solution (volume ratio is 20: 1). And stirring for 1 hour at room temperature under the protection of nitrogen, heating to 66 ℃, continuing to react for 20 hours, after the reaction is finished, distilling under reduced pressure to remove the solvent, adjusting the pH of the obtained product to 4 by using dilute sulfuric acid, then washing the product for multiple times by using a large amount of deionized water to obtain a white solid, namely a main chain type liquid crystal polymer, which is marked as a main chain type liquid crystal polymer 3, and placing the main chain type liquid crystal polymer in a vacuum drying oven for later use.
4) Preparation of main chain type ionic liquid crystal polymer: dissolving the main chain type liquid crystal polymer 3 obtained in the step 3) and excessive triphenylphosphine in 80mL toluene in a three-neck flask provided with a magnetic stirrer, a spherical condenser tube and a thermometer, stirring for 30min at room temperature, and heating to reflux for reaction for 10 h. And after the reaction is finished, standing and layering, wherein the upper layer of the solution is a toluene solvent layer, and the lower layer of the solution is a target product layer which is light yellow. And (3) taking the lower product layer, dissolving the lower product layer by using 20mL of deionized water, washing the unreacted raw materials by using petroleum ether, and removing water by rotary evaporation to obtain a target product, namely the main chain type ionic liquid crystal polymer, which is marked as a main chain type ionic liquid crystal polymer 3.
Example 4 preparation of a quaternary phosphine ion based main chain ionic liquid crystalline polymer (I) comprising the following steps:
1) preparation of D-camphoryl chloride: same as example 1
2) Preparation of 2, 3-dibromosuccinyl chloride: same as example 1
3) Preparation of main chain type liquid crystalline polymer: 0.06mol of D-camphoryl chloride, 0.04mol of 2, 3-dibromosuccinyl chloride, 0.1mol of terephthaloyl chloride and 0.2mol of hydroquinone are poured into a three-neck flask provided with a magnetic stirring bar, a spherical condenser tube and a thermometer in sequence, and are dissolved by 200mL of tetrahydrofuran and pyridine mixed solution (volume ratio is 20: 1). And stirring for 1 hour at room temperature under the protection of nitrogen, heating to 66 ℃, continuing to react for 20 hours, after the reaction is finished, distilling under reduced pressure to remove the solvent, adjusting the pH of the obtained product to 4 by using dilute sulfuric acid, washing the product for multiple times by using a large amount of deionized water to obtain a white solid, namely a main chain type liquid crystal polymer, marking as a main chain type liquid crystal polymer 4, and placing the white solid in a vacuum drying oven for later use.
4) Preparation of main chain type ionic liquid crystal polymer: dissolving the main chain type liquid crystal polymer 4 obtained in the step 3) and excessive triphenylphosphine in 80mL toluene in a three-neck flask provided with a magnetic stirrer, a spherical condenser tube and a thermometer, stirring for 30min at room temperature, and heating to reflux for reaction for 10 h. And after the reaction is finished, standing and layering, wherein the upper layer of the solution is a toluene solvent layer, and the lower layer of the solution is a target product layer which is light yellow. And (3) taking the lower product layer, dissolving the lower product layer by using 20mL of deionized water, washing the unreacted raw materials by using petroleum ether, and removing water by rotary evaporation to obtain a target product, namely, a main chain type ionic liquid crystal polymer, wherein the mark of the target product is a main chain type ionic liquid crystal polymer 4.
Example 5 preparation of a quaternary phosphine ion based main chain ionic liquid crystalline polymer (I) comprising the following steps:
1) preparation of D-camphoryl chloride: same as example 1
2) Preparation of 2, 3-dibromosuccinyl chloride: same as example 1
3) Preparation of main chain type liquid crystalline polymer: 0.05mol of D-camphoryl chloride, 0.05mol of 2, 3-dibromosuccinyl chloride, 0.1mol of terephthaloyl chloride and 0.2mol of hydroquinone are poured into a three-neck flask provided with a magnetic stirring bar, a spherical condenser tube and a thermometer in sequence, and dissolved by 200mL of tetrahydrofuran and pyridine mixed solution (volume ratio is 20: 1). And stirring for 1 hour at room temperature under the protection of nitrogen, heating to 66 ℃, continuing to react for 20 hours, after the reaction is finished, distilling under reduced pressure to remove the solvent, adjusting the pH of the obtained product to 4 by using dilute sulfuric acid, washing the product for multiple times by using a large amount of deionized water to obtain a white solid, namely a main chain type liquid crystal polymer, marking as a main chain type liquid crystal polymer 5, and placing the white solid in a vacuum drying oven for later use.
4) Preparation of main chain type ionic liquid crystal polymer: dissolving the main chain type liquid crystal polymer 5 obtained in the step 3) and excessive triphenylphosphine in 80mL toluene in a three-neck flask provided with a magnetic stirrer, a spherical condenser tube and a thermometer, stirring for 30min at room temperature, and heating to reflux for reaction for 10 h. And after the reaction is finished, standing and layering, wherein the upper layer of the solution is a toluene solvent layer, and the lower layer of the solution is a target product layer which is light yellow. And (3) taking the lower product layer, dissolving the lower product layer by using 20mL of deionized water, washing the unreacted raw materials by using petroleum ether, and removing water by rotary evaporation to obtain a target product, namely the main chain type ionic liquid crystal polymer 5.
Example 6 Main chain Ionic liquid Crystal Polymer detection and Performance testing based on Quaternary phosphine ions
The chemical structure of the main chain type ionic liquid crystal polymer is monitored by infrared spectroscopy and nuclear magnetic resonance spectroscopy.
FIG. 1 is an infrared image of main chain type liquid crystal polymer 1 and main chain type ionic liquid crystal polymer 1 prepared in example 1. As can be seen from FIG. 1, the main chain type liquid crystal polymer shows C ═ O stretching vibration in a characteristic band of 1780cm-1The acyl chloride is changed to 1680cm-1An ester group. Main chain type ionic liquid crystal polymer 1 containing quaternary phosphine ions is characterized by appearing at 1440cm-1P of+-a C group. The characteristic bands of C-O, C-h and other groups do not vary much.
FIG. 2 is a nuclear magnetic diagram of a main chain type liquid crystalline polymer prepared in example 1. It can be seen from FIG. 2 that each peak position corresponds to a hydrogen at each position in the compound, indicating the successful synthesis of the main chain liquid crystalline polymer.
FIG. 3 is a nuclear magnetic diagram of a main chain type ionic liquid crystal polymer prepared in example 1, and it can be seen from FIG. 3 that each peak position corresponds to hydrogen at each position in the compound, illustrating the successful synthesis of a main chain type ionic liquid crystal polymer containing a quaternary phosphine ion.
FIG. 4 is an XRD pattern of a main chain type liquid crystal polymer prepared in example 1. The X-ray diffraction pattern is measured in the liquid crystal range of the polymer. As can be seen from fig. 4, the polymer has no distinct strong peaks in the small angle region (1 ° ≦ 2 θ ≦ 5 °), indicating no ordered layered structure, and a diffuse diffraction peak only at 2 θ ≦ 16.9 °. Corresponding to a molecular spacing of
Thus, in combination with the liquid crystal texture, the liquid crystal polymer is determined to be in a nematic phase.
FIG. 5 is an XRD pattern of a main chain type ionic liquid crystal polymer prepared in example 1. The X-ray diffraction pattern is measured in the liquid crystal range of the ionic liquid crystalline polymer. As can be seen in FIG. 5, the polymer has a sharp diffraction peak in the small angle region and a diffuse diffraction peak in the wide angle region. A strong small angle diffraction peak (2 θ ═ 2.68 °) indicates a film thickness of 32.9 μ, indicating that the ordered lamellar structure corresponds to a smectic layer.
FIG. 6 is a DSC curve of different main chain type liquid crystal polymers prepared in examples 1 to 5 measured at a temperature rising rate of 10 deg.C/min under a nitrogen atmosphere. As can be seen from FIG. 6, the molecular weight of the main chain type liquid crystalline polymer increases with the increase in the content of 2, 3-dibromosuccinyl chloride, resulting in an orderly increase in the glass transition temperature thereof. T of Main chain type liquid Crystal Polymer 5iImproved, but other main chain liquid crystalline polymersiThe variation is not large.
FIG. 7 is a DSC curve of different main chain type ionic liquid crystal polymers prepared in examples 1 to 5 measured at a temperature rising rate of 10 deg.C/min under a nitrogen atmosphere. As can be seen from fig. 7, the main chain type ionic liquid crystalline polymer has a wider liquid crystal range and a lower glass transition temperature than the main chain type liquid crystalline polymer because the introduction of quaternary phosphine ions leads to the formation of ionic liquid. But the introduction of quaternary phosphonium ions results in TgBecome unnormalized. As the quaternary phosphine ion content increased, the main chain ionic liquid crystal polymer prepared in example 5 had a wider liquid crystal range than the main chain ionic liquid crystal polymers prepared in examples 1-4.
Example 7 use of Quaternary phosphine ion based Main chain Ionic liquid Crystal polymers for antimicrobial applications
The Minimum Inhibitory Concentration (MIC) of the main chain type ionic liquid crystal polymer based on the quaternary phosphine ions to staphylococcus aureus is determined by a double dilution method.
The method comprises the following steps: main chain ionic liquid crystalline polymers based on quaternary phosphine ions were suspended in Mueller-Hinton (MH) broth to form homogeneous suspensions, which were then diluted to different concentrations using a two-fold dilution method (1280. mu.g/ml, 640. mu.g/ml, 320. mu.g/ml, 160. mu.g/ml.). Adding 10 into each 1ml suspension with different concentration8cfu ml-10.1ml of colonies formed a bacterial suspension. The bacterial suspension was shake-cultured at 37 ℃ for 24 h. Observing the growth of the bacteria, and observing the growth of the bacteriaThe low concentration is the Minimal Inhibitory Concentration (MIC), and the minimal inhibitory concentration is the dilution value. The MIC of the products at different molar ratios were recorded.
Fig. 8 is a graph simulating an antibacterial process of a quaternary phosphine ion-based main chain type ionic liquid crystal polymer, in which quaternary phosphine cationic groups easily adsorb negatively charged bacteria and accumulate on cell walls, thereby inhibiting the growth and death of the bacteria. At the same time, the quaternary phosphonium ions may also be compatible with the constituent teichoic acids of the bacterial cell wall, altering the permeability of the cell membrane, leading to lysis and death of the cell.
FIG. 9 is a graph of bacteriostatic activity of quaternary phosphine ion based main chain type ionic liquid crystal polymers against Staphylococcus aureus. The larger the MIC value is, the poorer the bacteriostatic property is, and the smaller the MIC value is, the better the bacteriostatic property is. As can be seen from fig. 9, the quaternary phosphine ion-based main chain type ionic liquid crystal polymer has a significant bacteriostatic effect on staphylococcus aureus, and the bacteriostatic activity of the quaternary phosphine ion-based main chain type ionic liquid crystal polymer is influenced by the content of phosphine ions. The higher the content of the phosphine ions, the stronger the bacteriostatic activity of the main chain type ionic liquid crystal polymer based on the quaternary phosphine ions, and the MIC value of the main chain type ionic liquid crystal polymer 5 with the highest content of the quaternary phosphine ions is 160 mug/ml, which is more remarkable than that of the products prepared in the other four examples (the MIC values are 640 mug/ml, 320 mug/ml and 320 mug/ml respectively).
Claims (9)
1. A quaternary phosphine ion-based main chain type ionic liquid crystal polymer, characterized by having a structural formula as shown in (I):
wherein x + y + z is 1, m is 1, n is 107 to 112, x/(x + y) is 0.1 to 0.5, and z/(x + y + z) is 0.5.
2. A preparation method of a main chain type ionic liquid crystal polymer based on quaternary phosphine ions is characterized by comprising the following steps:
1) dissolving D-camphoryl chloride, 2, 3-dibromosuccinyl chloride, terephthaloyl chloride and hydroquinone in a proper amount of tetrahydrofuran and pyridine mixed solution, stirring at room temperature for 1h under the protection of nitrogen, heating to 66 ℃, continuing to react for 20h, after the reaction is finished, carrying out reduced pressure distillation to remove the solvent, adjusting the pH value of the obtained product to 4, and then washing the product with deionized water to obtain a main chain type liquid crystal polymer;
2) dissolving the main chain type liquid crystal polymer and triphenylphosphine in toluene, stirring at room temperature for 30min, heating to reflux, continuing reflux reaction for 10h, standing for layering after the reaction is finished, taking a lower-layer product, washing with deionized water and petroleum ether in sequence, and performing rotary evaporation to obtain the main chain type ionic liquid crystal polymer.
3. The method of claim 2, wherein the method of preparing D-camphoryl chloride in step 1) comprises the steps of: taking D-camphoric acid, thionyl chloride and N, N-dimethylformamide, reacting for 8 hours at 60 ℃, heating to 80 ℃, and distilling under reduced pressure to obtain D-camphoryl chloride.
4. The preparation method according to claim 3, wherein the molar ratio of D-camphoric acid to thionyl chloride is 1: 4-5.
5. The method according to claim 2, wherein the 2, 3-dibromosuccinyl chloride is prepared in step 1) by a method comprising the steps of: taking 2, 3-dibromo succinic acid, thionyl chloride and N, N-dimethylformamide to react for 8 hours at the temperature of 60 ℃, heating to 80 ℃, and carrying out reduced pressure distillation to obtain 2, 3-dibromo succinyl chloride.
6. The method of claim 5, wherein: the molar ratio of 2, 3-dibromo-succinic acid to thionyl chloride is 1: 4-5.
7. The method according to claim 2, wherein in the step 1), the molar ratio of D-camphoryl chloride to 2, 3-dibromosuccinyl chloride to terephthaloyl chloride to hydroquinone is (9-5) to (1-5) to 10: 20.
8. The preparation method according to claim 2, wherein in the step 1), the volume ratio of tetrahydrofuran to pyridine is 20: 1.
9. Use of a quaternary phosphonium ion-based main chain type ionic liquid crystal polymer according to claim 1 for antibacterial purposes.
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| CN1215425A (en) * | 1996-04-01 | 1999-04-28 | 科莱恩有限公司 | LCP blends |
| WO2016109910A1 (en) * | 2015-01-09 | 2016-07-14 | 杨磊 | Method for preparing polyurethane coating and adhesive with antibacterial and waterproof properties |
| CN112251240A (en) * | 2020-10-20 | 2021-01-22 | 东北大学 | Quaternary ammonium salt ionic liquid crystal polymer with temperature control electronic switch performance and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1215425A (en) * | 1996-04-01 | 1999-04-28 | 科莱恩有限公司 | LCP blends |
| WO2016109910A1 (en) * | 2015-01-09 | 2016-07-14 | 杨磊 | Method for preparing polyurethane coating and adhesive with antibacterial and waterproof properties |
| CN112251240A (en) * | 2020-10-20 | 2021-01-22 | 东北大学 | Quaternary ammonium salt ionic liquid crystal polymer with temperature control electronic switch performance and preparation method and application thereof |
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