Preparation method of antibacterial polystyrene foam material

Abstract

The invention discloses a preparation method of an antibacterial polystyrene foam material. Comprising the following steps: step 1, mixing modified polystyrene, glass fibers and a flame retardant to obtain a premix; and 2, melting the premix, injecting a foaming agent into the melt of the premix, foaming and extruding through a heat exchanger, and shaping and cooling to obtain the polystyrene foam material. The preparation method has the beneficial effects that a modified monomer with antibacterial and flame-retardant properties is synthesized and successfully introduced into a polystyrene system, so that the antibacterial and flame-retardant properties of the polystyrene foam material are remarkably improved, and the mechanical property, the thermal stability and the like are remarkably improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of foamed materials, and specifically, relates to a preparation method of an antibacterial polystyrene foamed material. Background Art

[0002] Polystyrene foamed material (EPS) is a lightweight, porous polymer material widely used in fields such as packaging, building insulation, and food containers. Its unique porous structure endows the material with excellent heat insulation, sound insulation, and impact resistance, making it perform outstandingly in heat insulation and buffering packaging. In addition, polystyrene foamed material also has advantages such as convenient processing and low cost, further promoting its wide application in multiple industries. Moreover, with the continuous expansion of application fields, especially in fields with high requirements for hygiene and safety such as food packaging, medical devices, and building materials.

[0003] However, traditional polystyrene foamed materials have obvious defects during use, especially in terms of antibacterial and flame retardant properties. In the prior art, antibacterial agents and flame retardants are usually added to polystyrene in a physical mixing manner, and this addition method has many problems: on the one hand, antibacterial agents and flame retardants are prone to loss from the material surface, resulting in the attenuation of their antibacterial and flame retardant properties over time; on the other hand, the dispersibility of physically mixed antibacterial agents and flame retardants in the polystyrene matrix is poor and it is difficult to be evenly distributed, thus affecting the overall performance of the material. In addition, the separate addition of antibacterial agents and flame retardants in the traditional method may also cause interference between the two, further reducing the comprehensive performance of the material.

[0004] Therefore, to solve the above problems, the present invention prepares an antibacterial polystyrene foamed material. Summary of the Invention

[0005] The purpose of the present invention is to overcome the defects of the prior art and provide a preparation method of an antibacterial polystyrene foamed material.

[0006] The purpose of the present invention can be achieved by the following technical solutions:

[0007] A preparation method of an antibacterial polystyrene foamed material, comprising the following steps:

[0008] Step 1: Mix modified polystyrene, glass fiber, and a flame retardant to obtain a premix;

[0009] Step 2: Melt the premix, then inject a foaming agent into the melt of the premix, perform foaming and extrusion through a heat exchanger, and then perform shaping and cooling to obtain a polystyrene foamed material.

[0010] Preferably, the raw materials of the polystyrene foam material include the following components: by weight, 100-110 parts of modified polystyrene, 5-8 parts of glass fiber, 1-2 parts of flame retardant, and 2-3 parts of foaming agent; wherein the foaming agent includes one or more of ammonium carbonate, triterpenoid saponin, and diazoaminobenzene.

[0011] Preferably, the preparation process of the modified polystyrene is as follows:

[0012] (1) Under a nitrogen atmosphere, pentamethyldiethylenetriamine, ethyl 2-bromoisobutyrate, styrene, cuprous bromide, and N,N-dimethylformamide are mixed, stirred evenly, and then placed in an oil bath at 100-120°C for a polymerization reaction for 2-3 hours. After the reaction, ethanol precipitation, washing, and drying are used to obtain brominated polystyrene;

[0013] (2) Brominated polystyrene, modified monomer, cuprous bromide, pentamethyldiethylenetriamine, and N,N-dimethylformamide are mixed, and the oxygen in the system is removed by nitrogen bubbling. The temperature is raised to 100-110°C, and the reaction is carried out for 4-5 hours. After cooling to room temperature, filtration, washing, and drying are carried out to obtain modified polystyrene.

[0014] Preferably, the brominated polystyrene includes the following components: by weight, 6-8 parts of pentamethyldiethylenetriamine, 3-4 parts of ethyl 2-bromoisobutyrate, 100-120 parts of styrene, 1-2 parts of cuprous bromide, and 200-220 parts of N,N-dimethylformamide;

[0015] The modified polystyrene includes the following components: by weight, 13-15 parts of brominated polystyrene, 80-100 parts of modified monomer, 1-2 parts of cuprous bromide, 3-4 parts of pentamethyldiethylenetriamine, and 200-250 parts of N,N-dimethylformamide.

[0016] Preferably, the preparation process of the modified monomer is as follows:

[0017] S1: Allylbiphenol, sodium hydroxide, and toluene are mixed, stirred for 10-15 minutes, and a 1,4-dibromobutane solution is slowly added dropwise. After the addition is complete, the reaction is carried out at 60-70°C for 6-8 hours. After cooling, the impurities are removed by rotary evaporation to obtain brominated biphenol;

[0018] S2: Under a protective atmosphere, diphenylphosphinic chloride and dichloromethane are mixed, stirred evenly, methyl diethanolamine and triethylamine are added, and the reaction is carried out at room temperature for 1-2 hours to obtain tertiary amine phenylphosphonate;

[0019] S3: Brominated biphenol, tertiary amine phenylphosphonate, and ethanol are mixed, potassium carbonate is added, the temperature is raised to 70-80°C, and the reaction is carried out for 3-4 hours. After cooling to room temperature, filtration, washing, and drying are carried out to obtain the modified monomer.

[0020] Preferably, the brominated biphenol includes the following components: by weight, 2-3 parts of allyl biphenol, 0.9-1 part of sodium hydroxide, 20-22 parts of toluene, 5-6 parts of 1,4-dibromobutane solution; wherein the mass fraction of the 1,4-dibromobutane solution is 10-15 wt%.

[0021] Preferably, the tertiary amine phenylphosphonate includes the following components: by weight, 10-12 parts of diphenylphosphinous chloride, 70-80 parts of dichloromethane, 16-18 parts of methyldiethanolamine, 0.1-0.2 part of triethylamine.

[0022] Preferably, the modified monomer includes the following components: by weight, 12-15 parts of brominated biphenol, 18-20 parts of tertiary amine phenylphosphonate, 100-150 parts of ethanol, 0.2-0.3 part of potassium carbonate.

[0023] Preferably, the temperature for melting and extrusion is 200-210 °C; the temperature for foaming is 110-130 °C.

[0024] Advantages of the present invention:

[0025] By synthesizing a modified monomer with both antibacterial and flame retardant properties and successfully introducing it into the polystyrene system, the present invention not only significantly improves the antibacterial and flame retardant properties of the polystyrene foam material, but also shows significant improvements in mechanical properties and thermal stability, etc. Specifically as follows:

[0026] First: In the solution, through a chemical synthesis method, antibacterial and flame retardant functional groups are integrated into a single monomer; this monomer not only has antibacterial properties (such as biphenyl and quaternary ammonium salt structures), but also contains flame retardant groups (such as tertiary amine phenylphosphonate structures). The core of this design concept is to integrate antibacterial and flame retardant functions into a single molecular structure, thus avoiding problems such as poor compatibility and unstable performance that may occur when antibacterial agents and flame retardants are added separately in traditional methods;

[0027] Second: In the solution, by reacting the synthesized modified monomer with brominated polystyrene, antibacterial and flame retardant groups are successfully introduced into the main chain of polystyrene through a radical coupling reaction; this chemical modification method not only significantly improves the antibacterial and flame retardant properties of polystyrene, but also ensures the stability and durability of the modification effect through a covalent bond binding method; at the same time, the modified monomer polymerizes onto the polystyrene macromolecular chain, forming a main chain structure that is consistent with the main chain structure of polystyrene and an increased molecular weight, making it easier for the polymer chain to change its conformation, thereby improving the physical properties. Specific embodiments

[0028] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0029] Embodiment 1: A preparation method of an antibacterial polystyrene foam material, comprising the following steps:

[0030] Step 1: Mix 100 parts of modified polystyrene, 5 parts of glass fiber, and 1 part of flame retardant to obtain a premix;

[0031] Step 2: Melt the premix at 200 °C, then inject 2 parts of ammonium carbonate into the melt of the premix, perform foaming at 110 °C through a heat exchanger, extrude at 200 °C, and then perform shaping and cooling to obtain a polystyrene foam material;

[0032] Among them, the preparation process of the modified polystyrene is as follows:

[0033] (1) Under a nitrogen atmosphere, mix 6 parts of pentamethyldiethylenetriamine, 3 parts of ethyl 2-bromoisobutyrate, 100 parts of styrene, 1 part of cuprous bromide, and 200 parts of N,N-dimethylformamide, stir evenly, and place it in an oil bath at 100 °C for a 2-hour polymerization reaction. After the reaction is completed, precipitate with ethanol, wash, and dry to obtain brominated polystyrene;

[0034] (2) Mix 13 parts of brominated polystyrene, 80 parts of modified monomer, 1 part of cuprous bromide, 3 parts of pentamethyldiethylenetriamine, and 200 parts of N,N-dimethylformamide, remove the oxygen in the system by nitrogen bubbling, raise the temperature to 100 °C, react for 4 hours, cool to room temperature, filter, wash, and dry to obtain modified polystyrene;

[0035] Among them, the preparation process of the modified monomer is as follows:

[0036] S1: Mix 2 parts of allylbiphenol, 0.9 part of sodium hydroxide, and 20 parts of toluene, stir for 10 minutes, slowly dropwise add 5 parts of a 10 wt% 1,4-dibromobutane toluene solution. After the addition is complete, react at 60-70 °C for 6-8 hours. After cooling, remove impurities by rotary evaporation to obtain brominated biphenol;

[0037] S2: Under nitrogen, mix 10 parts of diphenylphosphinic chloride and 70 parts of dichloromethane, stir evenly, add 16 parts of methyldiethanolamine and 0.1 part of triethylamine, and react at room temperature for 1 hour to obtain tertiary amine phenylphosphonate;

[0038] S3: Mix 12 parts of brominated biphenyl diphenol, 18 parts of tertiary amine phenylphosphonate, and 100 parts of ethanol, add 0.2 part of potassium carbonate, heat up to 70 °C, react for 3 h, cool to room temperature, filter, wash and dry to obtain the modified monomer.

[0039] Example 2: A preparation method of an antibacterial polystyrene foam material, comprising the following steps:

[0040] Step 1: Mix 110 parts of modified polystyrene, 8 parts of glass fiber, and 2 parts of flame retardant to obtain a premix;

[0041] Step 2: Melt the premix at 210 °C, then inject 3 parts of ammonium carbonate into the melt of the premix, carry out foaming at 130 °C through a heat exchanger, extrude at 210 °C, and then carry out shaping and cooling to obtain the polystyrene foam material;

[0042] Among them, the preparation process of the modified polystyrene is as follows:

[0043] (1) Under a nitrogen atmosphere, mix 8 parts of pentamethyldiethylenetriamine, 4 parts of ethyl 2-bromoisobutyrate, 120 parts of styrene, 2 parts of cuprous bromide, and 220 parts of N,N-dimethylformamide, stir evenly, and place in an oil bath at 120 °C for a 3-h polymerization reaction. After the reaction is completed, precipitate with ethanol, wash, and dry to obtain brominated polystyrene;

[0044] (2) Mix 15 parts of brominated polystyrene, 100 parts of modified monomer, 2 parts of cuprous bromide, 4 parts of pentamethyldiethylenetriamine, and 250 parts of N,N-dimethylformamide, remove the oxygen in the system by nitrogen bubbling, heat up to 110 °C, react for 5 h, cool to room temperature, filter, wash, and dry to obtain the modified polystyrene;

[0045] Among them, the preparation process of the modified monomer is as follows:

[0046] S1: Mix 3 parts of allyl biphenyl diphenol, 1 part of sodium hydroxide, and 22 parts of toluene, stir for 15 min, slowly dropwise add 6 parts of a 15 wt% 1,4-dibromobutane toluene solution. After the addition is complete, react at 70 °C for 8 h, cool, and rotary evaporate to remove impurities to obtain brominated biphenyl diphenol;

[0047] S2: Under nitrogen, mix 12 parts of diphenylphosphinous chloride and 80 parts of dichloromethane, stir evenly, add 18 parts of methyldiethanolamine and 0.2 part of triethylamine, and react at room temperature for 2 h to obtain tertiary amine phenylphosphonate;

[0048] S3: Mix 15 parts of brominated biphenyl diphenol, 20 parts of tertiary amine phenylphosphonate, and 150 parts of ethanol, add 0.3 part of potassium carbonate, heat up to 80 °C, react for 4 h, cool to room temperature, filter, wash, and dry to obtain the modified monomer.

[0049] Example 3: A preparation method of an antibacterial polystyrene foam material, comprising the following steps:

[0050] Step 1: Mix 105 parts of modified polystyrene, 6 parts of glass fiber, and 1.5 parts of flame retardant to obtain a premix;

[0051] Step 2: Melt the premix at 205°C, then inject 2.5 parts of ammonium carbonate into the melt of the premix, carry out foaming at 120°C through a heat exchanger, extrude at 205°C, and then carry out shaping and cooling to obtain a polystyrene foam material;

[0052] Among them, the preparation process of the modified polystyrene is as follows:

[0053] (1) Under a nitrogen atmosphere, mix 7 parts of pentamethyldiethylenetriamine, 3.5 parts of ethyl 2-bromoisobutyrate, 110 parts of styrene, 1.5 parts of cuprous bromide, and 210 parts of N,N-dimethylformamide, stir evenly, and place in an oil bath at 110°C for a polymerization reaction for 2.5 h. After the reaction is completed, precipitate with ethanol, wash, and dry to obtain brominated polystyrene;

[0054] (2) Mix 14 parts of brominated polystyrene, 90 parts of modified monomer, 1.5 parts of cuprous bromide, 3.5 parts of pentamethyldiethylenetriamine, and 220 parts of N,N-dimethylformamide, remove the oxygen in the system by nitrogen bubbling, raise the temperature to 105°C, react for 4.5 h, cool to room temperature, filter, wash, and dry to obtain modified polystyrene;

[0055] Among them, the preparation process of the modified monomer is as follows:

[0056] S1: Mix 2.5 parts of allyl biphenol, 1 part of sodium hydroxide, and 21 parts of toluene, stir for 12 min, slowly dropwise add 5.5 parts of a 12 wt% 1,4-dibromobutane toluene solution. After the addition is completed, react at 65°C for 7 h. After cooling, remove impurities by rotary evaporation to obtain brominated biphenol;

[0057] S2: Under nitrogen, mix 11 parts of diphenylphosphinic chloride and 75 parts of dichloromethane, stir evenly, add 17 parts of methyldiethanolamine and 0.1 part of triethylamine, and react at room temperature for 1.5 h to obtain tertiary amine phenylphosphonate;

[0058] S3: Mix 14 parts of brominated biphenol, 19 parts of tertiary amine phenylphosphonate, and 120 parts of ethanol, add 0.25 part of potassium carbonate, raise the temperature to 75°C, react for 3.5 h, cool to room temperature, filter, wash, and dry to obtain the modified monomer.

[0059] Comparative Example 1: The polystyrene was not modified, and the flame retardant and the antibacterial agent were separately added to the reaction system, specifically as follows:

[0060] Step 1: Mix 105 parts of modified polystyrene, 6 parts of glass fiber, 1.5 parts of flame retardant, and 2 parts of antibacterial agent to obtain a premix;

[0061] Step 2: Melt the premix at 205°C, then inject 2.5 parts of ammonium carbonate into the melt of the premix, carry out foaming at 120°C through a heat exchanger, extrude at 205°C, and then carry out shaping and cooling to obtain a polystyrene foam material.

[0062] Comparative Example 2: Using allyl biphenol as the modification monomer, and the rest is the same as in Example 3, specifically as follows:

[0063] Step 1: Mix 105 parts of modified polystyrene, 6 parts of glass fiber, and 1.5 parts of flame retardant to obtain a premix;

[0064] Step 2: Melt the premix at 205°C, then inject 2.5 parts of ammonium carbonate into the melt of the premix, carry out foaming at 120°C through a heat exchanger, extrude at 205°C, and then carry out shaping and cooling to obtain a polystyrene foam material;

[0065] Among them, the preparation process of the modified polystyrene is as follows:

[0066] (1) Under a nitrogen atmosphere, mix 7 parts of pentamethyldiethylenetriamine, 3.5 parts of ethyl 2-bromoisobutyrate, 110 parts of styrene, 1.5 parts of cuprous bromide, and 210 parts of N,N-dimethylformamide, stir evenly, and place it in an oil bath at 110°C for a polymerization reaction for 2.5 h. After the reaction, precipitate with ethanol, wash, and dry to obtain brominated polystyrene;

[0067] (2) Mix 14 parts of brominated polystyrene, 90 parts of allyl biphenol, 1.5 parts of cuprous bromide, 3.5 parts of pentamethyldiethylenetriamine, and 220 parts of N,N-dimethylformamide, remove the oxygen in the system by nitrogen bubbling, raise the temperature to 105°C, react for 4.5 h, cool to room temperature, filter, wash and dry to obtain modified polystyrene.

[0068] Detection test: (1) The polystyrene foam materials obtained in the examples and comparative examples were crushed, and then shaken and cultured with the test bacterial solution of Staphylococcus aureus for 24 hours, and then the number of bacteria was calculated to obtain the antibacterial rate; (2) The polystyrene foam materials obtained in the examples and comparative examples were measured for the limiting oxygen index according to GB / T 2408-2009, and the size of the specimen was 130 mm × 10 mm × 10 mm; (3) The polystyrene foam materials obtained in the examples and comparative examples were measured for the impact strength according to GJB 1585A-2004, and the size of the specimen was 120 mm × 15 mm × 10 mm. The data obtained are shown in the following table:

[0069]

[0070] Table 1

[0071] Conclusion: The present invention successfully prepared a polystyrene foam material with both antibacterial and flame retardant properties by chemically synthesizing a modified monomer and introducing it into the polystyrene system. Among them, the antibacterial rate of Example 3 was significantly increased to 99.8%, far higher than that of the unmodified material (84.8%) and the material using only allyl biphenol (90.1%); the limiting oxygen index was significantly increased to 34.8%, far higher than that of the unmodified material (15.7%) and the material using only allyl biphenol (15.9%); the impact strength was increased to 0.51 kJ / m 2 , significantly higher than that of the unmodified material (0.35 kJ / m 2 ) and the material using only allyl biphenol (0.37 kJ / m 2 ); In summary, the modified polystyrene foam material shows significant improvement in antibacterial, flame retardant and mechanical properties, and has good application prospects.

[0072] In the description of the specification, the description of reference terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0073] The above content is only an example and illustration of the present invention. Those skilled in the art of the present technology make various modifications or supplements to the described specific embodiments or use similar ways to replace them. As long as they do not deviate from the invention or exceed the scope defined by the claims of the present invention, they should all fall within the protection scope of the present invention.

Claims

1. A preparation method of an antibacterial polystyrene foaming material, characterized in that: It includes the following steps: Step 1: Mix modified polystyrene, glass fiber, and flame retardant to obtain a premix; Step 2: Melt the premix, then inject a foaming agent into the melt of the premix, carry out foaming and extrusion through a heat exchanger, and then carry out shaping and cooling to obtain a polystyrene foamed material.

2. The preparation method of an antibacterial polystyrene foaming material according to claim 1, characterized in that: The raw materials of the polystyrene foamed material include the following components: by weight, 100 - 110 parts of modified polystyrene, 5 - 8 parts of glass fiber, 1 - 2 parts of flame retardant, 2 - 3 parts of foaming agent; among them, the foaming agent includes one or more of ammonium carbonate, triterpenoid saponin, and diazoaminobenzene.

3. The preparation method of an antibacterial polystyrene foam material according to claim 1, characterized in that: The preparation process of the modified polystyrene is as follows: (1) Under a nitrogen atmosphere, mix pentamethyldiethylenetriamine, ethyl 2 - bromoisobutyrate, styrene, cuprous bromide, and N,N - dimethylformamide, stir evenly, and place it in an oil bath at 100 - 120 °C for a polymerization reaction for 2 - 3 h. After the reaction, precipitate with ethanol, wash, and dry to obtain brominated polystyrene; (2) Mix brominated polystyrene, modified monomer, cuprous bromide, pentamethyldiethylenetriamine, and N,N - dimethylformamide, remove the oxygen in the system by nitrogen bubbling, raise the temperature to 100 - 110 °C, react for 4 - 5 h, cool to room temperature, filter, wash, and dry to obtain modified polystyrene.

4. The preparation method of an antibacterial polystyrene foam material according to claim 3, characterized in that: The brominated polystyrene includes the following components: by weight, 6 - 8 parts of pentamethyldiethylenetriamine, 3 - 4 parts of ethyl 2 - bromoisobutyrate, 100 - 120 parts of styrene, 1 - 2 parts of cuprous bromide, 200 - 220 parts of N,N - dimethylformamide; The modified polystyrene includes the following components: by weight, 13 - 15 parts of brominated polystyrene, 80 - 100 parts of modified monomer, 1 - 2 parts of cuprous bromide, 3 - 4 parts of pentamethyldiethylenetriamine, 200 - 250 parts of N,N - dimethylformamide.

5. The preparation method of an antibacterial polystyrene foam material according to claim 3, characterized in that: The preparation process of the modified monomer is as follows: S1: Mix allyl biphenol, sodium hydroxide, and toluene, stir for 10 - 15 min, slowly dropwise add a 1,4 - dibromobutane solution. After the addition is complete, react at 60 - 70 °C for 6 - 8 h. After cooling, rotary evaporate to remove impurities to obtain brominated biphenol; S2: Under a protective atmosphere, mix diphenylphosphinic chloride and dichloromethane, stir evenly, add methyldiethanolamine and triethylamine, and react at room temperature for 1 - 2 h to obtain tertiary amine phenylphosphonate; S3: Mix brominated biphenol, tertiary amine phenylphosphonate, and ethanol, add potassium carbonate, raise the temperature to 70 - 80 °C, react for 3 - 4 h, cool to room temperature, filter, wash, and dry to obtain the modified monomer.

6. The preparation method of an antibacterial polystyrene foam material according to claim 5, characterized in that: The brominated biphenol includes the following components: by weight, 2 - 3 parts of allyl biphenol, 0.9 - 1 part of sodium hydroxide, 20 - 22 parts of toluene, 5 - 6 parts of 1,4 - dibromobutane solution; among them, the mass fraction of the 1,4 - dibromobutane solution is 10 - 15 wt%.

7. The preparation method of an antibacterial polystyrene foam material according to claim 5, characterized in that: The tertiary amine phenylphosphonate includes the following components: by weight, 10 - 12 parts of diphenylphosphinic chloride, 70 - 80 parts of dichloromethane, 16 - 18 parts of methyldiethanolamine, 0.1 - 0.2 parts of triethylamine.

8. The preparation method of an antibacterial polystyrene foamed material according to claim 5, characterized in that: The modified monomer comprises the following components: 12-15 parts by weight of brominated biphenol, 18-20 parts by weight of tertiary amine phenylphosphonate, 100-150 parts by weight of ethanol, and 0.2-0.3 parts by weight of potassium carbonate.

9. The preparation method of an antibacterial polystyrene foam material according to claim 1, characterized in that: The temperature for melting and extrusion is 200-210 °C; the temperature for foaming is 110-130 °C.

10. A polystyrene foam material obtained by the preparation method of an antibacterial polystyrene foam material according to any one of claims 1-9.

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