CN115785355A - Antibacterial material and method for synthesizing quaternary phosphonium salt block copolymer based on RAFT - Google Patents
Antibacterial material and method for synthesizing quaternary phosphonium salt block copolymer based on RAFT Download PDFInfo
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Abstract
The invention relates to an antibacterial material for synthesizing a quaternary phosphonium salt block copolymer based on RAFT, wherein the quaternary phosphonium salt block copolymer has a structural formula as follows:
(ii) a Wherein: r is a hydrocarbyl substituent, X is an anion, and Y is a substituent or functional group attached to the vinyl group. The invention also discloses a synthetic method of the antibacterial material. The quaternary phosphonium salt segmented copolymer is a nano microsphere with smooth surface and uniform distribution, has excellent antibacterial performance, and can be applied to preparation of antibacterial coatings and antibacterial fabrics.
Description
Technical Field
The invention relates to the technical field of synthesis of high-molecular functional materials, in particular to an antibacterial material and a method for synthesizing a quaternary phosphonium salt block copolymer based on RAFT (reversible addition-fragmentation chain transfer).
Background
In recent years, the use of a large amount of antibiotics has led to an increase in bacterial resistance in the treatment of infections, and further, the emergence of superbacteria and the like has been increasing. Such as: methicillin-resistant staphylococcus aureus (MRSA), multidrug-resistant streptococcus pneumoniae (MDRSP), vancomycin enterococci (VRE), multidrug-resistant mycobacterium tuberculosis (MDR-TB), multidrug-resistant acinetobacter baumannii (MRAB), and the like. These superbacteria are becoming one of the major risks to serious human health and even the environment. According to the World Health Organization (WHO) reports, over 70 million people are killed by superbacteria each year, including a large number of infants and young children. In addition, excessive discharge of conventional antibiotics also causes gradual enrichment of organisms and serious environmental pollution. Therefore, it is imperative to improve the antibacterial activity of antibiotics, reduce the toxicity of antibiotics, inhibit the abuse of superbacteria, and alleviate the biological contamination caused by the abuse of antibiotics.
From the molecular level, the antibacterial activity of the large-size cation is far higher than that of the traditional small-molecular antibiotic because the large-size cation has extremely high molecular polarity. Such as quaternary ammonium ions, imidazolium ions, and haloamides, among others. Thus, it is anticipated and feasible to utilize large size cations as a new generation of antimicrobial agents. At present, the synthetic polymer antibacterial agent with large-size cations is introduced, has low toxicity, optimized biodistribution, controllable pharmacokinetics, excellent biofilm penetrating capacity and high bacterial selectivity, receives more and more attention, and shows great application prospect as a new generation antibacterial agent.
The cationic polymer antibacterial material is an important functional polymer material, and can kill/inhibit the growth of microorganisms on the surface or in the surrounding environment. The antibacterial mechanism is divided into the following steps: adsorbed to the cell wall; diffuse through the cell wall; binding to cell membranes; disrupting the composition of the cell membrane; allowing intracellular material, such as: DNA, RNA, K + Eventually causing bacterial death. The cationic polymer antibacterial material has the advantages of low toxicity, excellent antibacterial effect, long acting, good stability and the like. Therefore, the antibacterial material is widely applied to water treatment, medical appliances, building materials, plastics, textile industries and the like. The main types of the antibacterial agent include natural cationic antibacterial polymer (such as chitosan), quaternary ammonium salt polymer, and N-halogenated amine polymerPolymers and guanidine salt polymers, and the like.
Compared with other quaternary ammonium salt cationic polymers, the quaternary phosphonium salt polymer has lower electronegativity and higher molecular polarity due to the larger radius of the phosphonium atom, so that the quaternary phosphonium salt polymer has more efficient antibacterial activity. In addition, the high chemical and environmental stability of the quaternary phosphonium salt polymer allows it to be used in a variety of conditions and applications. For example, the invention patent CN 110256617A discloses a poly (meth) acrylate antibacterial agent containing a quaternary phosphonium salt structure, and a preparation method and an application thereof, and the poly (meth) acrylate antibacterial agent containing the quaternary phosphonium salt structure prepared by the poly (meth) acrylate antibacterial agent can be used as an antibacterial additive of plastics and used for preparing antibacterial plastics. The invention patent CN 110352982A discloses a preparation method of a quaternary phosphonium salt modified montmorillonite loaded cobalt-doped zinc oxide quantum dot nano composite antibacterial agent, which utilizes the huge specific surface area and high absorption rate of the quaternary phosphonium salt modified montmorillonite to adsorb bacteria on the surface of the montmorillonite, and then the bacteria are killed by the synergistic effect of cobalt-doped zinc oxide quantum dots (ZnO @ QDs) loaded on the surface and between layers of the montmorillonite, and the prepared nano composite antibacterial agent has good biocompatibility and high antibacterial activity. Xie AG et al, (Long-acting antibacterial activity of quaternary phosphonium functionalized felt-layered graphite [ J ] Materials Science and Engineering B, 2011, 176: 1222-1226) prepared tetradecyl triphenylphosphonium bromide functionalized graphite, and the characteristics, morphology, thermal stability and Long-acting antibacterial performance of the tetradecyl triphenylphosphonium bromide functionalized graphite are researched by introducing phosphonium salt. In conclusion, the quaternary phosphonium salt polymer has stronger antibacterial capacity, higher environmental adaptability and wider application range.
At present, the synthesis of quaternary phosphonium salt polymers mainly adopts methods such as graft polymerization, in-situ polymerization, random copolymerization and the like. Such as: the invention patent CN 114479047A discloses a method for preparing a quaternary phosphonium salt-containing polymer from an epoxy monomer, a product and an application thereof, wherein the quaternary phosphonium salt-containing polymer is prepared by homopolymerization or copolymerization of an epoxide serving as a monomer, and is a reaction type or addition type flame-retardant polymer which is more stable and has better comprehensive performance. The invention patent CN 113461128A discloses a preparation method of a starch grafted quaternary phosphonium salt flocculant for treating bacteria-containing sewage, wherein a grafted quaternary phosphonium salt group enhances the positive charge characteristic of a polymer and has a promotion effect on the antibacterial activity of the polymer. However, the existing synthesis method of the quaternary phosphonium salt polymer is difficult to accurately design and proportionally regulate the quaternary phosphonium salt structural unit, so that the antibacterial performance/toxicity of the quaternary phosphonium salt polymer is difficult to balance.
Reversible addition-fragmentation chain transfer polymerization (RAFT) is a novel technique for preparing polymers, and has the advantages of high reactivity, high conversion rate, narrow molecular weight distribution, good repeatability and the like. Such as: the invention patent CN 109970933A discloses an amphiphilic block copolymer with temperature and light responsiveness in ionic liquid and a preparation method thereof, and the block copolymer can realize light control and temperature control self-assembly in the ionic liquid. The invention patent CN 107828032A discloses a hyperbranched star-shaped polyion liquid and a preparation method and application thereof, the hyperbranched star-shaped polyion liquid takes hyperbranched polyglycidyl as a core and takes polyion liquid as an arm, hyperbranched star-shaped copolymer is obtained through RAFT polymerization, and finally the hyperbranched star-shaped copolymer and a nitrogen-containing heterocyclic compound are reacted to synthesize the hyperbranched star-shaped polyion liquid. The ionic liquid is a novel cation, is a meltable salt containing an organic structure, and can be applied to synthesis of quaternary phosphonium salt polymers. The invention patent CN 106939014A discloses a quaternary phosphonium salt ionic liquid and a preparation method and application thereof, and the quaternary phosphonium salt ionic liquid provided by the invention has the advantages of high catalytic activity, high reaction selectivity, less byproducts and high recycling performance in the esterification reaction between catalytic carboxylic acid and hydroxyl-containing organic matters. However, RAFT as a new synthesis technology, ionic liquids as a new reaction medium and molecular building blocks, and many unknown principles of reaction and technical bottlenecks remain.
In summary, the design and synthesis of many functional cationic polymer materials is facilitated by the high degree of designability and selectivity of the chemical structure of the cations and anions in the ionic liquids. Phosphonium ions are introduced into an ionic liquid system, so that the selectivity of the cation type is widened, and the high-selectivity high-molecular antibacterial material can be further designed. Therefore, the invention takes the quaternary phosphonium salt ionic liquid as an antibacterial functional monomer, adopts reversible addition-fragmentation chain transfer polymerization (RAFT) to accurately control the structural unit, and designs an antibacterial quaternary phosphonium salt polymer with controllable synthesis and excellent antibacterial capability, thereby developing a novel antibacterial high polymer material.
Disclosure of Invention
The invention aims to solve the technical problem of providing an antibacterial material of a quaternary phosphonium salt block copolymer synthesized based on RAFT, which has excellent antibacterial performance.
The invention also aims to provide a method for synthesizing the quaternary phosphonium salt block copolymer antibacterial material based on RAFT.
In order to solve the problems, the antibacterial material for synthesizing the quaternary phosphonium salt block copolymer based on RAFT is characterized in that: the quaternary phosphonium salt block copolymer has the structural formula:
wherein: r is a hydrocarbyl substituent, X is an anion, and Y is a substituent or functional group attached to the vinyl group.
R is phenyl or butyl; x is Cl - 、Br - 、I - 、SCN - 、BF 4 - 、PF 6 - 、SbF 6 - 、OH - 、CO 3 2- Or AlCl 4 - One kind of (1).
The method for synthesizing the quaternary phosphonium salt block copolymer antibacterial material based on RAFT comprises the following steps:
the method comprises the steps of synthesizing a quaternary phosphonium salt macromolecular chain transfer agent:
sequentially adding 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid, quaternary phosphonium salt ionic liquid monomer and reaction solvent into a container A, stirring to completely dissolve the monomers, adding an initiator, and performing vacuum-pumping and nitrogen-introducing circulation operation for 30-60 min; then sealing the container A, and immersing the container A in a heating bath at the temperature of 70-80 ℃ for polymerization reaction for 10-24 h to obtain a reaction product; the seal was broken to expose the reaction product to air, and vessel a was dropped into liquid nitrogen to terminate the reaction. After thawing, dialyzing the solution containing the reaction product for 24-36 h by deionized water to obtain a light yellow precipitate A, and freeze-drying the precipitate A to obtain a solid powdery quaternary phosphonium salt macromolecular chain transfer agent; the molar ratio of the 2- (dodecyl trithiocarbonate) -2-methylpropionic acid to the quaternary phosphonium salt ionic liquid monomer is 1 to 10-1; the dosage of the initiator is 0.5-5.0% of the mass of the quaternary phosphonium salt ionic liquid monomer.
Synthesizing a quaternary phosphonium salt-containing block copolymer:
sequentially adding the quaternary phosphonium salt macromolecular chain transfer agent, a reaction solvent and an initiator into a container B, stirring to completely dissolve the quaternary phosphonium salt macromolecular chain transfer agent, adding a Y comonomer, and performing cyclic operation of freezing, vacuumizing and filling nitrogen for 3~8 times; then unfreezing to room temperature, and immersing in a heating bath at 70-80 ℃ for polymerization reaction for 12-36 h; the reaction was then terminated by immersing container B in liquid nitrogen. After unfreezing, adding a precipitator to obtain a precipitate B, and washing, purifying, freezing and drying the precipitate B to obtain a solid powdery quaternary phosphonium salt block copolymer; the molar ratio of the quaternary phosphonium salt macromolecular chain transfer agent to the Y comonomer is 1 to 30-1; the using amount of the initiator is 0.5-5.0% of the mass of the Y comonomer.
The quaternary phosphonium salt ionic liquid monomer in the steps refers to triphenyl-benzyl quaternary phosphonium salt ionic liquid or tributyl-benzyl triphenyl quaternary phosphonium salt ionic liquid.
The Y comonomer in the step II is one or a mixture of two of styrene, butadiene, 4-vinylbenzyl chloride, N-vinyl pyrrolidone, methyl methacrylate, ethylene glycol dimethacrylate and other monomers.
The reaction solvent in the steps is one or two mixtures of anhydrous methanol, ethanol, acetonitrile, 1,4-dioxane, N-dimethylformamide, tetrahydrofuran and acetone.
The initiator in the first step and the second step is azobisisobutyronitrile or azobisisoheptonitrile.
The heating bath in the step I and the step II is an oil bath or a sand bath.
The interception relative molecular weight of the dialysis bag in the step is 8000-14000.
In the step II, the precipitator is diethyl ether or tetrahydrofuran.
Compared with the prior art, the invention has the following advantages:
1. the invention takes quaternary phosphonium salt ionic liquid as an antibacterial unit, and prepares a quaternary phosphonium salt block copolymer antibacterial material based on reversible addition-fragmentation chain transfer (RAFT) polymerization, wherein the quaternary phosphonium salt block copolymer is a nano microsphere with smooth surface and uniform distribution. The microspheres have larger specific surface area due to smaller size, so that the probability of contacting with bacteria can be increased, and better antibacterial performance is shown.
The target product (quaternary phosphonium salt block copolymer) and the intermediate (quaternary phosphonium salt macromolecular chain transfer agent) synthesized by the method are characterized, analyzed and tested:
[ Hydrogen nuclear magnetic resonance ]
FIG. 1 and FIG. 2 are nuclear magnetic hydrogen spectra of synthesized phenyl quaternary phosphonium salt macromolecular chain transfer agent and butyl quaternary phosphonium salt macromolecular chain transfer agent, respectively. As can be seen from FIG. 1, the hydrogen atom assignments of the phenyl quaternary phosphonium salt macromolecular chain transfer agent are 7.57 (P-Ar-H), 7.30 (P-Ar-H), 6.49 (H-Ar-CH) 2 -P），5.90（H-Ar-CH 2 -P），1.2（P-(CH 2 ) 3 -CH 3 And main chains CH and CH 2 ），0.6（P-(CH 2 ) 3 -CH 3 And CH 3 ). It can be seen from FIG. 2 that the assignment of hydrogen atom in butyl quaternary phosphonium salt macromolecular chain transfer agent is 7.09 (Ar-H, CH) 2 -P），6.39（Ar-CH 2 -P），3.63（P-CH 2 -(CH 2 ) 2 CH 3 ），2.00（P-CH 2 -CH 2 -CH 2 -CH 3 And main chain CH), 1.24 (P- (CH) 2 ) 2 -CH 2 -CH 3 And a main chain CH 2 ），0.71（P-(CH 2 ) 3 -CH 3 And main chain CH 3 ）。
FIG. 3 and FIG. 4 are nuclear magnetic resonance hydrogen spectra of a phenyl quaternary phosphonium salt-styrene block copolymer and a butyl quaternary phosphonium salt-styrene block copolymer, respectively. The assignment of hydrogen atoms in the phenyl quaternary phosphonium salt-styrene block copolymer and the butyl quaternary phosphonium salt-styrene block copolymer can be clearly seen from fig. 3 and 4, and the results show that 2 kinds of target products have been successfully prepared.
[ Infrared Spectrum ]
FIG. 5 is an infrared spectrum of a phenyl quaternary phosphonium salt macromolecular chain transfer agent (1) and a phenyl quaternary phosphonium salt-styrene block copolymer (2). As can be seen, 3442, 1730, 1180 and 1028 cm -1 Characteristic peaks of (D) appear in the quaternary phosphonium salt macromolecular chain transfer agent and the phenyl quaternary phosphonium salt-styrene block copolymer, which are assigned to O-H, C = O and thiocarbonyl (C = S) in 2- (dodecylthiocarbonylthio) -2-methylpropionic acid, respectively. And 1109 and 755 cm -1 ，3000、3021 cm -1 And 1630 cm -1 Respectively, a characteristic peak of P-C, an aromatic C-H stretching peak and an aromatic C = C stretching peak, further indicating that the quaternary phosphonium salt macromolecular chain transfer agent and the phenyl quaternary phosphonium salt-styrene block copolymer have been successfully prepared.
[ microcosmic morphology ]
FIG. 6 is a scanning electron microscope image of microspheres of phenyl quaternary phosphonium salt-styrene block copolymer having a size of 200 nm. As can be seen from the figure, after various monomers participate in the polymerization reaction together, the obtained phenyl quaternary phosphonium salt-styrene segmented copolymer microspheres are smooth nanoparticles, the size is about 250 nm, the microspheres have large specific surface area, and the microspheres are easy to contact with bacteria so as to achieve the aim of antibiosis.
[ antibacterial Properties ]
Escherichia coli (E.coli) and staphylococcus aureus (S.aureus) which are easy to generate drug resistance are selected as bacterial colonies, nutrient agar paste is used as a solid culture medium, and the antibacterial performance of the quaternary phosphonium salt block copolymer is tested by a plate counting method and a densitometry method. FIG. 7 is a digital photograph and an optical density measurement (OD) of the bacteriostatic effect of the phenyl quaternary phosphonium salt-styrene block copolymer prepared according to the present invention on Escherichia coli and Staphylococcus aureus at different concentrations. It can be seen that when the concentration of the phenyl quaternary phosphonium salt-styrene block copolymer is 10. Mu.g.mL -1 When it is concentrated, it shows a remarkable bacteriostatic effectThe degree of reaction was 30. Mu.g/mL -1 The bacteriostasis rate can reach 99.9 percent.
2. The preparation method of the antibacterial quaternary phosphonium salt block copolymer has the characteristics of high reaction selectivity, high conversion rate, easy regulation and control of chemical structure and the like, and can be widely adapted to the application requirements of antibacterial agents in various fields, such as solubility, long-acting property, low toxicity and the like.
3. The antibacterial quaternary phosphonium salt block copolymer prepared by the invention can be applied to the preparation of antibacterial coatings and antibacterial fabrics.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 shows the nuclear magnetic resonance hydrogen spectrum of the macromolecular chain transfer agent of phenyl quaternary phosphonium salt prepared by the invention.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the butyl quaternary phosphonium salt macromolecular chain transfer agent prepared by the invention.
FIG. 3 shows the NMR spectrum of a phenyl quaternary phosphonium salt-styrene block copolymer prepared according to the present invention.
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of a butyl quaternary phosphonium salt-styrene block copolymer prepared by the present invention.
FIG. 5 is an infrared spectrum of a phenyl quaternary phosphonium salt macromolecular chain transfer agent (1) and a phenyl quaternary phosphonium salt-styrene block copolymer (2) prepared by the method.
FIG. 6 is a scanning electron microscope image of a phenyl quaternary phosphonium salt-styrene block copolymer prepared by the present invention.
FIG. 7 shows the inhibition effect of the phenyl quaternary phosphonium salt-styrene block copolymer prepared by the present invention on Escherichia coli and Staphylococcus aureus, digital photographs of the inhibitory effect at different concentrations, and the measured values of Optical Density (OD).
Detailed Description
A quaternary phosphonium salt block copolymer antibacterial material is synthesized based on RAFT, and the quaternary phosphonium salt block copolymer has the structural formula:
wherein: r is a hydrocarbyl substituent, X is an anion, and Y is a substituent or functional group attached to the vinyl group.
Wherein: r is phenyl or butyl; x is Cl - 、Br - 、I - 、SCN - 、BF 4 - 、PF 6 - 、SbF 6 - 、OH - 、CO 3 2- Or AlCl 4 - One kind of (1).
The method for synthesizing the quaternary phosphonium salt block copolymer antibacterial material based on RAFT comprises the following steps:
the method comprises the steps of synthesizing a quaternary phosphonium salt macromolecular chain transfer agent:
sequentially adding 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid, a quaternary phosphonium salt ionic liquid monomer and a reaction solvent into a container A, wherein the molar ratio of the 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid to the quaternary phosphonium salt ionic liquid monomer is 1 to 10-1. Stirring to completely dissolve the quaternary phosphonium salt ionic liquid monomer, and adding an initiator, wherein the dosage of the initiator is 0.5-5.0% of the mass of the quaternary phosphonium salt ionic liquid monomer. And performing vacuum-pumping and nitrogen-introducing circulation operation for 30 to 60 min to remove oxygen; then sealing the container A, and immersing the container A in a heating bath at the temperature of 70-80 ℃ for polymerization reaction for 10-24 h to obtain a reaction product; the reaction product was exposed to air by releasing the seal, and the vessel a was put into liquid nitrogen to terminate the reaction. And after thawing, dialyzing the solution containing the reaction product for 24-36 h by using deionized water to obtain a light yellow precipitate A, and freeze-drying the precipitate A to obtain the solid powdery quaternary phosphonium salt macromolecular chain transfer agent.
Synthesizing a quaternary phosphonium salt-containing block copolymer:
and (2) sequentially adding a quaternary phosphonium salt macromolecular chain transfer agent, a reaction solvent and an initiator into the container B, stirring to completely dissolve the quaternary phosphonium salt macromolecular chain transfer agent, the reaction solvent and the initiator, and adding a Y comonomer, wherein the molar ratio of the quaternary phosphonium salt macromolecular chain transfer agent to the Y comonomer is 1 to 1000, and the dosage of the initiator is 0.5-5.0% of the mass of the Y comonomer. Adopting refrigeration-vacuum-nitrogen-filling circulation operation 3~8 times to remove oxygen in the reaction liquid in the container B; then unfreezing to room temperature, and immersing in a heating bath at 70-80 ℃ for polymerization reaction for 12-36 h; the reaction was then terminated by immersing container B in liquid nitrogen. And after thawing, adding a precipitant to obtain a precipitate B, and washing, purifying, freezing and drying the precipitate B to obtain the solid powdery quaternary phosphonium salt block copolymer.
Wherein: the quaternary phosphonium salt ionic liquid monomer refers to triphenyl-benzyl quaternary phosphonium salt ionic liquid (R = phenyl) or tributyl-benzyl triphenyl quaternary phosphonium salt ionic liquid (R = butyl).
The Y comonomer (i.e. the vinyl monomer with the Y functional group) refers to one or a mixture of two of styrene, butadiene, 4-vinylbenzyl chloride, N-vinyl pyrrolidone, methyl methacrylate, ethylene glycol dimethacrylate and the like.
The reaction solvent is one or two of anhydrous methanol, ethanol, acetonitrile, 1,4-dioxane, N-dimethylformamide, tetrahydrofuran and acetone.
The initiator is azobisisobutyronitrile or azobisisoheptonitrile.
The heating bath is oil bath or sand bath.
The cut-off relative molecular weight of the dialysis bag is 8000 to 14000.
The precipitant is diethyl ether or tetrahydrofuran.
Example 1
The method comprises the steps of synthesizing a quaternary phosphonium salt macromolecular chain transfer agent:
600 mg of 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid, 6 g phenyl quaternary phosphonium salt ionic liquid monomer and 20 g anhydrous methanol are respectively added into a container A, stirred to be completely dissolved, 9 mg azodiisobutyronitrile is added, and the circulation operation is carried out for 30 min by vacuumizing and introducing nitrogen to remove oxygen. After the polymerization of 10 h in a 70 ℃ oil bath with container a sealed and immersed, the resulting reaction product was exposed to air and the reaction was terminated by placing container a in liquid nitrogen. After thawing, the solution containing the reaction product was transferred to a dialysis bag and dialyzed against deionized water 24 h. And (3) carrying out freeze drying on the light yellow precipitate A generated in the dialysis process to obtain the solid powdery phenyl quaternary phosphonium salt macromolecular chain transfer agent.
Synthesizing a quaternary phosphonium salt-containing block copolymer:
1 mg azodiisobutyronitrile, 220 mg phenyl quaternary phosphonium salt macromolecular chain transfer agent and 2 mL methanol are sequentially added into a container B, stirred and dissolved, and then 150 mg styrene is added. Freezing, vacuumizing, filling nitrogen for 3 times, then unfreezing to room temperature, and immersing in a heating bath at 70 ℃ for polymerization reaction of 12 h; the reaction was then terminated by immersing container B in liquid nitrogen. After thawing, the solution containing the reaction product was added with ether as a precipitant to obtain precipitate B. Washing the precipitate B with diethyl ether for 3 times, and freeze drying to obtain solid powdered phenyl quaternary phosphonium salt block-styrene copolymer.
Example 2
The method comprises the steps of synthesizing a quaternary phosphonium salt macromolecular chain transfer agent:
27 mg of 2- (dodecyltrithiocarbonate) -2-methylpropanoic acid, 5 g butyl quaternary phosphonium salt ionic liquid monomer and 30 g anhydrous methanol were added to vessel A, stirred to dissolve completely, 10 mg azobisisobutyronitrile was added, and the operation was cycled for 45 min by vacuum-introducing nitrogen to remove oxygen. After the polymerization reaction of 15 h in an oil bath at 80 ℃ with container a sealed, the resulting reaction product was exposed to air, and the reaction was terminated by placing container a in liquid nitrogen. After thawing, the solution containing the reaction product was transferred to a dialysis bag and dialyzed against deionized water 24 h. And (3) carrying out freeze drying on the light yellow precipitate A generated in the dialysis process to obtain the solid powdery butyl quaternary phosphonium salt macromolecular chain transfer agent.
Synthesizing a quaternary phosphonium salt-containing block copolymer:
0.6 mg azodiisobutyronitrile, 200 mg butyl quaternary phosphonium salt macromolecular chain transfer agent and 3 mL methanol are sequentially added into a container B, stirred and dissolved, and then 160 mg styrene is added. Freezing, vacuumizing, filling nitrogen for 8 times, then unfreezing to room temperature, and immersing in a heating bath at 80 ℃ for polymerization reaction of 20 h; the reaction was then terminated by immersing container B in liquid nitrogen. After thawing, the precipitant tetrahydrofuran was added to the solution containing the reaction product to obtain a precipitate B. Washing the precipitate B with tetrahydrofuran for 3 times, and freeze drying to obtain solid powdered butyl quaternary phosphonium salt-styrene block copolymer.
Example 3
The method comprises the steps of synthesizing a quaternary phosphonium salt macromolecular chain transfer agent:
95 mg of 2- (dodecyltrithiocarbonate) -2-methylpropanoic acid, 7 g phenyl quaternary phosphonium salt macromolecular chain transfer agent monomer and 30 g anhydrous methanol are respectively added into a container A, stirred to be completely dissolved, 9 mg azodiisoheptanonitrile is added, and the operation is carried out for 60 min by vacuumizing and introducing nitrogen for circulation so as to remove oxygen. After the vessel A was then sealed and immersed in a 75 ℃ oil bath for polymerization 24 h, the resulting reaction product was exposed to air and the vessel A was placed in liquid nitrogen to terminate the reaction. After thawing, the solution containing the reaction product was transferred to a dialysis bag and dialyzed against deionized water 24 h. And (3) carrying out freeze drying on the faint yellow precipitate A generated in the dialysis process to obtain the solid powdery phenyl quaternary phosphonium salt macromolecular chain transfer agent.
Synthesizing a quaternary phosphonium salt-containing block copolymer:
4 mg azodiisoheptanonitrile, 217 mg phenyl quaternary phosphonium salt macromolecular chain transfer agent and 50 mL methanol are sequentially added into a container B, stirred and dissolved, and then 60 mg ethylene glycol dimethacrylate is added. Freezing, vacuumizing, filling nitrogen for 6 times, then unfreezing to room temperature, and immersing in a heating bath at 75 ℃ for polymerization reaction 36 h; the reaction was then terminated by immersing container B in liquid nitrogen. After thawing, the solution containing the reaction product was added with ether as a precipitant to obtain precipitate B. Washing the precipitate B with diethyl ether for 3 times, and freeze drying to obtain solid powdered quaternary phosphonium salt cross-linked block copolymer.
Claims (10)
1. A quaternary phosphonium salt block copolymer antibacterial material based on RAFT synthesis is characterized in that: the quaternary phosphonium salt block copolymer has the structural formula:
wherein: r is a hydrocarbyl substituent, X is an anion, and Y is a substituent or functional group attached to the vinyl group.
2. The method of claim 1The antibacterial material for synthesizing the quaternary phosphonium salt block copolymer based on RAFT is characterized in that: r is phenyl or butyl; x is Cl - 、Br - 、I - 、SCN - 、BF 4 - 、PF 6 - 、SbF 6 - 、OH - 、CO 3 2- Or AlCl 4 - To (3) is provided.
3. The RAFT-based synthesis method of the quaternary phosphonium salt block copolymer antibacterial material according to claim 1, comprising the following steps:
the method comprises the steps of synthesizing a quaternary phosphonium salt macromolecular chain transfer agent:
sequentially adding 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid, quaternary phosphonium salt ionic liquid monomer and reaction solvent into a container A, stirring to completely dissolve the monomers, adding an initiator, and performing vacuum-pumping and nitrogen-introducing circulation operation for 30-60 min; then sealing the container A, and immersing the container A in a heating bath at the temperature of 70-80 ℃ for polymerization reaction for 10-24 h to obtain a reaction product; the reaction product was exposed to air by releasing the seal, and the vessel a was put into liquid nitrogen to terminate the reaction. And after thawing, dialyzing the solution containing the reaction product for 24-36 h by using deionized water to obtain a light yellow precipitate A, and freeze-drying the precipitate A to obtain the solid powdery quaternary phosphonium salt macromolecular chain transfer agent. The molar ratio of the 2- (dodecyl trithiocarbonate) -2-methylpropionic acid to the quaternary phosphonium salt ionic liquid monomer is 1 to 10-1; the dosage of the initiator is 0.5-5.0% of the mass of the quaternary phosphonium salt ionic liquid monomer.
Synthesizing a quaternary phosphonium salt-containing block copolymer:
sequentially adding the quaternary phosphonium salt macromolecular chain transfer agent, a reaction solvent and an initiator into a container B, stirring to completely dissolve the quaternary phosphonium salt macromolecular chain transfer agent, adding a Y comonomer, and performing refrigeration-vacuumizing-nitrogen filling circulation operation for 3~8 times; then unfreezing to room temperature, and immersing in a heating bath at 70-80 ℃ for polymerization reaction for 12-36 h; the reaction was then terminated by immersing container B in liquid nitrogen. And after thawing, adding a precipitant to obtain a precipitate B, and washing, purifying, freezing and drying the precipitate B to obtain the solid powdery quaternary phosphonium salt block copolymer. The molar ratio of the quaternary phosphonium salt macromolecular chain transfer agent to the Y comonomer is 1 to 30-1; the using amount of the initiator is 0.5-5.0% of the mass of the Y comonomer.
4. The method for synthesizing the quaternary phosphonium salt block copolymer antibacterial material based on RAFT according to claim 1, wherein: the quaternary phosphonium salt ionic liquid monomer in the steps refers to triphenyl-benzyl quaternary phosphonium salt ionic liquid or tributyl-benzyl triphenyl quaternary phosphonium salt ionic liquid.
5. The method for synthesizing the quaternary phosphonium salt block copolymer antibacterial material based on RAFT according to claim 1, wherein: the Y comonomer in the step II is one or a mixture of two of styrene, butadiene, 4-vinylbenzyl chloride, N-vinyl pyrrolidone, methyl methacrylate, ethylene glycol dimethacrylate and other monomers.
6. The method for synthesizing the quaternary phosphonium salt block copolymer antibacterial material based on RAFT according to claim 1, wherein: the reaction solvent in the steps is one or two mixtures of anhydrous methanol, ethanol, acetonitrile, 1,4-dioxane, N-dimethylformamide, tetrahydrofuran and acetone.
7. The method for synthesizing the quaternary phosphonium salt block copolymer antibacterial material based on RAFT according to claim 1, wherein: the initiator in the steps comprises azodiisobutyronitrile or azodiisoheptanonitrile.
8. The method for synthesizing the quaternary phosphonium salt block copolymer antibacterial material based on RAFT according to claim 1, wherein: the heating bath in the step I and the step II is an oil bath or a sand bath.
9. The method for synthesizing the quaternary phosphonium salt block copolymer antibacterial material based on RAFT according to claim 1, wherein: the dialysis bag in the step is subjected to interception with a relative molecular weight of 8000-14000.
10. The method for synthesizing the quaternary phosphonium salt block copolymer antibacterial material based on RAFT according to claim 1, wherein: in the step II, the precipitator is diethyl ether or tetrahydrofuran.
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