Preparation method and application of antibacterial graphene modified polystyrene plastic

Abstract

The invention relates to the technical field of polystyrene, and discloses an antibacterial graphene modified polystyrene plastic, a bromine atom of bromobutane triphenylphosphonium bromide and a hydroxyl group of polyol are subjected to a nucleophilic substitution reaction to obtain a hydroxyl-terminated triphenylphosphonium bromide, and the hydroxyl-terminated triphenylphosphonium bromide is used as a quaternary phosphonium salt antibacterial monomer to prepare the antibacterial graphene modified polystyrene plastic. A plurality of hydroxyl groups contained at the chain end can increase reaction sites and accelerate esterification reaction with acyl chloride groups of graphene, so that quaternary phosphonium salt antibacterial monomers are chemically bonded to the surface of graphene to obtain functionalized graphene with high antibacterial activity, and triphenylphosphonium bromide modified on the surface of graphene contains a large number of benzene ring structures, so that the antibacterial activity of the graphene is improved. Compared with the prior art, the graphene has the advantages that the polarity of the graphene is similar to that of styrene, the interface affinity and compatibility of graphene and polystyrene can be improved, dispersion of graphene is promoted, agglomeration is reduced, and polystyrene is endowed with excellent antibacterial performance and tensile strength.

Description

Technical Field

[0001] The invention relates to the technical field of polystyrene, in particular to a preparation method and application of antibacterial graphene-modified polystyrene plastic. Background Art

[0002] Polystyrene is hard, transparent, rigid, has good electrical insulation and is easy to process. It is one of the four general-purpose plastics and has important applications in the fields of containers, packaging materials, furniture and home appliances, building materials and medical materials. However, traditional polystyrene has poor impact resistance and low tensile strength, and polystyrene does not have antibacterial activity, which hinders the development of practical applications of polystyrene materials. Therefore, it is of great practical significance to research and develop polystyrene with high tensile and antibacterial properties to improve people's living environment, reduce the spread of pathogens and infections, and thus protect human health.

[0003] Graphene is a two-dimensional carbon nanomaterial with unique mechanical, optical, electrical and other properties. It is an ideal functional filler for polymer materials. Studies have found that graphene can destroy and decompose cell membranes through mechanical cutting and extraction of phospholipid molecules on cell membranes, causing the outflow of substances in cells, inhibiting and killing bacteria and microorganisms. Graphene has no drug resistance and is an antibacterial material with great development prospects. Graphene can be oxidized to contain abundant oxygen-containing groups such as hydroxyl and carboxyl, and can be modified with abundant chemical functional groups, thereby introducing antibacterial groups such as quaternary phosphonium salts, quaternary ammonium salts, and thiazoles, giving it more excellent chemical antibacterial activity. Among them, quaternary phosphonium salts have the advantages of high efficiency, rapidity, broad spectrum and low toxicity, and are a widely used antibacterial agent.

[0004] 1. Technical issues to be resolved In view of the deficiencies in the prior art, the present invention provides a method for preparing and applying antibacterial graphene-modified polystyrene plastic, which solves the problem of poor antibacterial and tensile properties of polystyrene materials.

[0005] (II) Technical solution To achieve the above object, the present invention provides the following technical solution: an antibacterial graphene-modified polystyrene plastic, wherein the preparation method of the antibacterial graphene-modified polystyrene plastic is as follows: (1) Add triphenylphosphine and 1,4-dibromobutane in a mass ratio of 80-92:100 to toluene solvent, react for 12-24 h in a nitrogen atmosphere, distill under reduced pressure, and wash with ether to obtain bromobutyl triphenylphosphonium bromide with the molecular formula C 22 H 23 Br2P.

[0006] (2) Adding butyl bromide and polyol to N,N-dimethylformamide solvent to carry out nucleophilic substitution reaction, adding distilled water and ethyl acetate to extract after the reaction, taking the ethyl acetate organic phase, distilling it under reduced pressure, and washing it with ether to obtain terminal hydroxy triphenyl phosphonium bromide.

[0007] (3) Graphene oxide is treated with thionyl chloride to obtain chlorinated graphene.

[0008] (4) Adding acyl chloride graphene and terminal hydroxy triphenylphosphonium bromide into N,N-dimethylformamide solvent, uniformly dispersing by ultrasonication to carry out esterification reaction, removing the solvent by centrifugation, washing with distilled water and ethanol, and obtaining triphenylphosphonium bromide modified graphene.

[0009] (5) Polystyrene resin, triphenylphosphonium bromide modified graphene, lubricant zinc stearate and antioxidant 1010 are placed in a screw extruder for melt blending, and then the masterbatch is extruded and blown into a film to obtain antibacterial graphene modified polystyrene plastic.

[0010] Preferably, the polyol in step (2) is propylene glycol or pentaerythritol.

[0011] Preferably, the molecular formula of the terminal hydroxy triphenylphosphonium bromide in step (2) is C 25 H 30 BrO3P or C 27 H 34 BrO4P.

[0012] Preferably, the mass ratio of bromobutyltriphenylphosphonium bromide to polyol in step (2) is 100:25-45.

[0013] Preferably, the temperature of the nucleophilic substitution reaction in step (2) is 60-100° C., and the reaction time is 12-24 h.

[0014] Preferably, the mass ratio of the chlorinated graphene to the terminal hydroxy triphenylphosphonium bromide in step (4) is 10:15-40.

[0015] Preferably, the temperature of the esterification reaction in step (4) is 50-80°C, and the reaction time is 24-72 h.

[0016] Preferably, the mass ratio of the polystyrene resin, triphenylphosphonium bromide-modified graphene, zinc stearate and 1010 in the step (5) is 100:0.2-0.8:0.5-1.5:0.5-2.

[0017] 3. Beneficial technical effects Compared with the prior art, the present invention has the following beneficial technical effects: The invention discloses an antibacterial graphene-modified polystyrene plastic. The bromine atom of bromobutyl triphenylphosphonium bromide undergoes nucleophilic substitution reaction with a hydroxyl group of a polyol to obtain terminal hydroxyl triphenylphosphonium bromide. The terminal hydroxyl triphenylphosphonium bromide is used as a quaternary phosphonium salt antibacterial monomer. The multiple hydroxyl groups contained in the chain end of the bromobutyl triphenylphosphonium bromide can increase the reaction sites, thereby accelerating the esterification reaction with the acyl chloride group of the graphene to obtain the brominated triphenylphosphonium modified graphene. The quaternary phosphonium salt antibacterial monomer is chemically bonded to the surface of the graphene to obtain the functionalized graphene with high antibacterial activity.

[0018] The antibacterial graphene-modified polystyrene plastic has triphenylphosphonium bromide modified on the surface of graphene, which contains a large number of benzene ring structures and has a polarity similar to that of styrene. It can improve the interface affinity and compatibility between graphene and polystyrene, promote the dispersion of graphene, and reduce agglomeration, thereby giving polystyrene excellent antibacterial properties. In addition, graphene has unique mechanical properties and is evenly dispersed in a polystyrene matrix, which greatly improves the tensile properties of the polystyrene material, such as tensile strength. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 It is the reaction formula of bromobutyltriphenylphosphonium bromide and glycerol; Figure 2 It is the reaction formula of bromobutyltriphenylphosphonium bromide and pentaerythritol. DETAILED DESCRIPTION

[0020] To achieve the above object, the present invention provides the following specific implementation methods and examples: A method for preparing an antibacterial graphene-modified polystyrene plastic is as follows: (1) Add triphenylphosphine and 1,4-dibromobutane in a mass ratio of 80-92:100 to toluene solvent, react for 12-24 h in a nitrogen atmosphere, distill under reduced pressure, and wash with ether to obtain bromobutyl triphenylphosphonium bromide with the molecular formula C 22 H 23 Br2P.

[0021] (2) Adding butyl bromide and polyol in a mass ratio of 100:25-45 to N,N-dimethylformamide solvent, wherein the polyol is propylene glycol or pentaerythritol, to carry out nucleophilic substitution reaction, the reaction temperature is 60-100°C, the reaction time is 12-24 h, after the reaction is completed, distilled water and ethyl acetate are added for extraction, the ethyl acetate organic phase is taken, after reduced pressure distillation, it is washed with ether to obtain terminal hydroxy triphenyl phosphonium bromide, the molecular formula is C 25 H 30 BrO3P or C 27 H 34 BrO4P.

[0022] (3) Graphene oxide is treated with thionyl chloride to obtain chlorinated graphene.

[0023] (4) Adding acylated graphene and terminal hydroxy triphenylphosphonium bromide in a mass ratio of 10:15-40 to N,N-dimethylformamide solvent, uniformly dispersing by ultrasonication to carry out esterification reaction, the reaction temperature is 50-80 °C, the reaction time is 24-72 h, centrifuging to remove the solvent, washing with distilled water and ethanol, and obtaining triphenylphosphonium bromide modified graphene.

[0024] (5) Polystyrene resin, triphenylphosphonium bromide modified graphene, lubricant zinc stearate and antioxidant 1010 in a mass ratio of 100:0.2-0.8:0.5-1.5:0.5-2 are placed in a screw extruder for melt blending, and then the masterbatch is extruded and blown into a film to obtain an antibacterial graphene-modified polystyrene plastic.

[0025] Example 1

[0026] (1) Triphenylphosphine and 1,4-dibromobutane in a mass ratio of 80:100 were added to a toluene solvent, and the mixture was reacted for 12 h in a nitrogen atmosphere. The mixture was then distilled under reduced pressure and washed with ether to obtain bromobutyl triphenylphosphonium bromide with the molecular formula C 22 H 23 Br2P.

[0027] (2) Add butyl bromide triphenylphosphonium bromide and polyol glycerol in a mass ratio of 100:25 to N,N-dimethylformamide solvent to carry out nucleophilic substitution reaction at a reaction temperature of 60 °C for 12 h. After the reaction, distilled water and ethyl acetate are added for extraction. The ethyl acetate organic phase is taken, distilled under reduced pressure, and washed with ether to obtain terminal hydroxy triphenylphosphonium bromide with a molecular formula of C 25 H 30 BrO3P, the structural formula is .

[0028] (3) Graphene oxide is treated with thionyl chloride to obtain chlorinated graphene.

[0029] (4) Add acylated graphene and terminal hydroxy triphenylphosphonium bromide in a mass ratio of 10:15 into N,N-dimethylformamide solvent, and perform esterification reaction uniformly by ultrasonic dispersion. The reaction temperature is 50 °C and the reaction time is 24 h. The solvent is removed by centrifugation, and the product is washed with distilled water and ethanol to obtain triphenylphosphonium bromide-modified graphene.

[0030] (5) Polystyrene resin, triphenylphosphonium bromide modified graphene, lubricant zinc stearate and antioxidant 1010 in a mass ratio of 100:0.2:0.5:0.5 are placed in a screw extruder for melt blending, and then the masterbatch is extruded and blown into a film to obtain an antibacterial graphene-modified polystyrene plastic.

[0031] Example 2

[0032] (1) Triphenylphosphine and 1,4-dibromobutane in a mass ratio of 82:100 were added to a toluene solvent, and the mixture was reacted for 12 h in a nitrogen atmosphere. The mixture was then distilled under reduced pressure and washed with ether to obtain bromobutyl triphenylphosphonium bromide with the molecular formula C 22 H 23 Br2P.

[0033] (2) Add butyl bromotriphenylphosphonium bromide and polyol pentaerythritol in a mass ratio of 100:30 to N,N-dimethylformamide solvent to carry out nucleophilic substitution reaction at a reaction temperature of 80 °C for 24 h. After the reaction, distilled water and ethyl acetate are added for extraction. The ethyl acetate organic phase is taken, distilled under reduced pressure, and washed with ether to obtain terminal hydroxy triphenylphosphonium bromide with a molecular formula of C 27 H 34 BrO4P, the structural formula is .

[0034] (3) Graphene oxide is treated with thionyl chloride to obtain chlorinated graphene.

[0035] (4) Graphene chloride and terminal hydroxy triphenylphosphonium bromide in a mass ratio of 10:25 were added to N,N-dimethylformamide solvent, and the esterification reaction was carried out uniformly by ultrasonic dispersion. The reaction temperature was 60 °C and the reaction time was 36 h. The solvent was removed by centrifugation, and the graphene was washed with distilled water and ethanol to obtain triphenylphosphonium bromide modified graphene.

[0036] (5) Polystyrene resin, triphenylphosphonium bromide modified graphene, lubricant zinc stearate and antioxidant 1010 in a mass ratio of 100:0.4:0.8:1 were placed in a screw extruder for melt blending, and then the masterbatch was extruded and blown into a film to obtain an antibacterial graphene-modified polystyrene plastic.

[0037] Example 3

[0038] (1) Add triphenylphosphine and 1,4-dibromobutane in a mass ratio of 88:100 to toluene solvent, react for 18 hours in a nitrogen atmosphere, distill under reduced pressure, and wash with ether to obtain bromobutyl triphenylphosphonium bromide with the molecular formula C 22 H 23 Br2P.

[0039] (2) Add butyl bromide triphenylphosphonium bromide and polyol glycerol in a mass ratio of 100:38 to N,N-dimethylformamide solvent to carry out nucleophilic substitution reaction at a reaction temperature of 80 °C and a reaction time of 18 h. After the reaction is completed, distilled water and ethyl acetate are added for extraction. The ethyl acetate organic phase is taken, distilled under reduced pressure, and washed with ether to obtain terminal hydroxy triphenylphosphonium bromide with a molecular formula of C 25 H 30 BrO3P, the structural formula is .

[0040] (3) Graphene oxide is treated with thionyl chloride to obtain chlorinated graphene.

[0041] (4) Graphene chloride and terminal hydroxy triphenylphosphonium bromide in a mass ratio of 10:32 were added to N,N-dimethylformamide solvent, and the esterification reaction was carried out uniformly by ultrasonic dispersion. The reaction temperature was 60 °C and the reaction time was 48 h. The solvent was removed by centrifugation, and the graphene was washed with distilled water and ethanol to obtain triphenylphosphonium bromide modified graphene.

[0042] (5) Polystyrene resin, triphenylphosphonium bromide modified graphene, lubricant zinc stearate and antioxidant 1010 in a mass ratio of 100:0.6:1.2:1.5 were placed in a screw extruder for melt blending, and then the masterbatch was extruded and blown into a film to obtain an antibacterial graphene-modified polystyrene plastic.

[0043] Example 4

[0044] (1) Triphenylphosphine and 1,4-dibromobutane in a mass ratio of 92:100 were added to a toluene solvent, and the mixture was reacted for 24 h in a nitrogen atmosphere. The mixture was then distilled under reduced pressure and washed with ether to obtain bromobutyl triphenylphosphonium bromide with the molecular formula C 22 H 23 Br2P.

[0045] (2) Add butyl bromotriphenylphosphonium bromide and polyol pentaerythritol in a mass ratio of 100:45 to N,N-dimethylformamide solvent to carry out nucleophilic substitution reaction at a reaction temperature of 100 °C for a reaction time of 24 h. After the reaction is completed, distilled water and ethyl acetate are added for extraction. The ethyl acetate organic phase is taken, distilled under reduced pressure, and washed with ether to obtain terminal hydroxy triphenylphosphonium bromide with a molecular formula of C 27 H 34 BrO4P, the structural formula is .

[0046] (3) Graphene oxide is treated with thionyl chloride to obtain chlorinated graphene.

[0047] (4) Graphene chloride and terminal hydroxy triphenylphosphonium bromide in a mass ratio of 10:40 were added to N,N-dimethylformamide solvent, and the esterification reaction was carried out uniformly by ultrasonic dispersion. The reaction temperature was 80 °C and the reaction time was 72 h. The solvent was removed by centrifugation, and the graphene was washed with distilled water and ethanol to obtain triphenylphosphonium bromide modified graphene.

[0048] (5) Polystyrene resin, triphenylphosphonium bromide modified graphene, lubricant zinc stearate and antioxidant 1010 in a mass ratio of 100:0.8:1.5:2 were placed in a screw extruder for melt blending, and then the masterbatch was extruded and blown into a film to obtain an antibacterial graphene-modified polystyrene plastic.

[0049] Comparative Example 1 (1) Triphenylphosphine and 1,4-dibromobutane in a mass ratio of 88:100 were added to a toluene solvent, and the mixture was reacted for 24 h in a nitrogen atmosphere. The mixture was then distilled under reduced pressure and washed with ether to obtain bromobutyl triphenylphosphonium bromide with the molecular formula C 22 H 23 Br2P.

[0050] (2) Add butyl bromotriphenylphosphonium bromide and polyol pentaerythritol in a mass ratio of 100:40 to N,N-dimethylformamide solvent to carry out nucleophilic substitution reaction at 80 °C for 24 h. After the reaction, distilled water and ethyl acetate are added for extraction. The ethyl acetate organic phase is taken, distilled under reduced pressure, and washed with ether to obtain terminal hydroxy triphenylphosphonium bromide with the molecular formula C 27 H 34 BrO4P, the structural formula is .

[0051] (3) Graphene oxide is treated with thionyl chloride to obtain chlorinated graphene.

[0052] (4) Graphene chloride and terminal hydroxy triphenylphosphonium bromide in a mass ratio of 10:8 were added to N,N-dimethylformamide solvent, and the esterification reaction was carried out uniformly by ultrasonic dispersion. The reaction temperature was 60 °C and the reaction time was 36 h. The solvent was removed by centrifugation, and the graphene was washed with distilled water and ethanol to obtain triphenylphosphonium bromide modified graphene.

[0053] (5) Polystyrene resin, triphenylphosphonium bromide modified graphene, lubricant zinc stearate and antioxidant 1010 in a mass ratio of 100:0.08:0.5:0.5 are placed in a screw extruder for melt blending, and then the masterbatch is extruded and blown into a film to obtain an antibacterial graphene-modified polystyrene plastic.

[0054] Comparative Example 2 (1) Triphenylphosphine and 1,4-dibromobutane in a mass ratio of 92:100 were added to a toluene solvent, and the mixture was reacted for 24 h in a nitrogen atmosphere. The mixture was then distilled under reduced pressure and washed with ether to obtain bromobutyl triphenylphosphonium bromide with the molecular formula C 22 H 23 Br2P.

[0055] (2) Add butyl bromide triphenylphosphonium bromide and polyol glycerol in a mass ratio of 100:25 to N,N-dimethylformamide solvent to carry out nucleophilic substitution reaction at 80 °C for 24 h. After the reaction, distilled water and ethyl acetate are added for extraction. The ethyl acetate organic phase is taken, distilled under reduced pressure, and washed with ether to obtain terminal hydroxy triphenylphosphonium bromide with the molecular formula C 25 H 30 BrO3P, the structural formula is .

[0056] (3) Graphene oxide is treated with thionyl chloride to obtain chlorinated graphene.

[0057] (4) Graphene chloride and terminal hydroxy triphenylphosphonium bromide in a mass ratio of 10:50 were added to N,N-dimethylformamide solvent, and the esterification reaction was carried out uniformly by ultrasonic dispersion. The reaction temperature was 80 °C and the reaction time was 36 h. The solvent was removed by centrifugation, and the graphene was washed with distilled water and ethanol to obtain triphenylphosphonium bromide modified graphene.

[0058] (5) Polystyrene resin, triphenylphosphonium bromide modified graphene, lubricant zinc stearate and antioxidant 1010 in a mass ratio of 100:1:1.5:2 were placed in a screw extruder for melt blending, and then the masterbatch was extruded and blown into a film to obtain an antibacterial graphene-modified polystyrene plastic.

[0059] The antibacterial graphene-modified polystyrene plastics in the embodiment and the comparative example were respectively placed in culture dishes, peptone culture medium and activated Staphylococcus aureus suspension were added, and the dishes were placed in an incubator for culture. The antibacterial properties of the modified polystyrene plastics were tested by an inhibition zone experiment.

[0060] Inhibition zone experiment of antibacterial graphene-modified polystyrene plastic

[0061] The tensile strength of antibacterial graphene-modified polystyrene plastic was tested using a C610M electronic tensile testing machine.

[0062] Tensile strength test of graphene-modified polystyrene plastic

Claims

1. An antibacterial graphene-modified polystyrene plastic, characterized in that: The preparation method of the antibacterial graphene-modified polystyrene plastic is as follows: (1) Add triphenylphosphine and 1,4-dibromobutane in a mass ratio of 80-92:100 to toluene solvent, and react in a nitrogen atmosphere for 12-24 h to obtain bromobutyl triphenylphosphonium bromide with the molecular formula C 22 H 23 Br2P; (2) adding butyl bromide and polyol to N,N-dimethylformamide solvent to carry out nucleophilic substitution reaction to obtain terminal hydroxy triphenyl phosphonium bromide; (3) using thionyl chloride to chlorinate graphene oxide to obtain chlorinated graphene; (4) adding chlorinated graphene and terminal hydroxy triphenylphosphonium bromide to N,N-dimethylformamide solvent, and uniformly dispersing by ultrasonication to carry out esterification reaction to obtain triphenylphosphonium bromide modified graphene; (5) Polystyrene resin, triphenylphosphonium bromide modified graphene, lubricant zinc stearate and antioxidant 1010 are placed in a screw extruder for melt blending, and then the masterbatch is extruded and blown into a film to obtain antibacterial graphene modified polystyrene plastic.

2. The antibacterial graphene-modified polystyrene plastic according to claim 1, characterized in that: The polyol in step (2) is propylene glycol or pentaerythritol.

3. The antibacterial graphene-modified polystyrene plastic according to claim 1, characterized in that: The molecular formula of the terminal hydroxy triphenylphosphonium bromide in step (2) is C 25 H 30 BrO3P or C 27 H 34 BrO4P.

4. The antibacterial graphene-modified polystyrene plastic according to claim 1, characterized in that: The mass ratio of bromobutyltriphenylphosphonium bromide to polyol in the step (2) is 100:25-45.

5. The antibacterial graphene-modified polystyrene plastic according to claim 1, characterized in that: The temperature of the nucleophilic substitution reaction in step (2) is 60-100°C, and the reaction time is 12-24 h.

6. The antibacterial graphene-modified polystyrene plastic according to claim 1, characterized in that: The mass ratio of the chlorinated graphene to the terminal hydroxy triphenylphosphonium bromide in the step (4) is 10:15-40.

7. The antibacterial graphene-modified polystyrene plastic according to claim 1, characterized in that: The temperature of the esterification reaction in step (4) is 50-80°C, and the reaction time is 24-72 h.

8. The antibacterial graphene-modified polystyrene plastic according to claim 1, characterized in that: The mass ratio of the polystyrene resin, triphenylphosphonium bromide modified graphene, zinc stearate and 1010 in the step (5) is 100:0.2-0.8:0.5-1.5:0.5-2.

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